JPS6328474B2 - - Google Patents
Info
- Publication number
- JPS6328474B2 JPS6328474B2 JP58140875A JP14087583A JPS6328474B2 JP S6328474 B2 JPS6328474 B2 JP S6328474B2 JP 58140875 A JP58140875 A JP 58140875A JP 14087583 A JP14087583 A JP 14087583A JP S6328474 B2 JPS6328474 B2 JP S6328474B2
- Authority
- JP
- Japan
- Prior art keywords
- weight
- present
- polyol
- polyisocyanate
- urethane resin
- 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.)
- Expired
Links
- 239000005056 polyisocyanate Substances 0.000 claims description 14
- 229920001228 polyisocyanate Polymers 0.000 claims description 14
- 229920005862 polyol Polymers 0.000 claims description 14
- 229920002803 thermoplastic polyurethane Polymers 0.000 claims description 12
- 239000004359 castor oil Substances 0.000 claims description 10
- 235000019438 castor oil Nutrition 0.000 claims description 10
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 claims description 10
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 10
- 238000009499 grossing Methods 0.000 claims description 9
- 150000003077 polyols Chemical class 0.000 claims description 9
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 7
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- 239000007795 chemical reaction product Substances 0.000 claims description 6
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 5
- 239000008199 coating composition Substances 0.000 claims description 5
- 150000004985 diamines Chemical class 0.000 claims description 5
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims description 4
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 3
- 239000003973 paint Substances 0.000 description 23
- 239000011248 coating agent Substances 0.000 description 21
- 238000000576 coating method Methods 0.000 description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- -1 amine polyol Chemical class 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 238000001035 drying Methods 0.000 description 6
- 239000003822 epoxy resin Substances 0.000 description 6
- 229920000647 polyepoxide Polymers 0.000 description 6
- 239000000203 mixture Substances 0.000 description 5
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 4
- 229910000831 Steel Inorganic materials 0.000 description 4
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 4
- 239000000049 pigment Substances 0.000 description 4
- 239000010959 steel Substances 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 229910001018 Cast iron Inorganic materials 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 2
- 229910021536 Zeolite Inorganic materials 0.000 description 2
- 239000010426 asphalt Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- JXCHMDATRWUOAP-UHFFFAOYSA-N diisocyanatomethylbenzene Chemical compound O=C=NC(N=C=O)C1=CC=CC=C1 JXCHMDATRWUOAP-UHFFFAOYSA-N 0.000 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 2
- 239000002075 main ingredient Substances 0.000 description 2
- 238000010422 painting Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000000454 talc Substances 0.000 description 2
- 229910052623 talc Inorganic materials 0.000 description 2
- 239000010457 zeolite Substances 0.000 description 2
- HXKKHQJGJAFBHI-UHFFFAOYSA-N 1-aminopropan-2-ol Chemical compound CC(O)CN HXKKHQJGJAFBHI-UHFFFAOYSA-N 0.000 description 1
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 239000004606 Fillers/Extenders Substances 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 235000004443 Ricinus communis Nutrition 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- SLINHMUFWFWBMU-UHFFFAOYSA-N Triisopropanolamine Chemical compound CC(O)CN(CC(C)O)CC(C)O SLINHMUFWFWBMU-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000010425 asbestos Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 1
- 239000010428 baryte Substances 0.000 description 1
- 229910052601 baryte Inorganic materials 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 235000011116 calcium hydroxide Nutrition 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- 235000012255 calcium oxide Nutrition 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000004567 concrete Substances 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- LVTYICIALWPMFW-UHFFFAOYSA-N diisopropanolamine Chemical compound CC(O)CNCC(C)O LVTYICIALWPMFW-UHFFFAOYSA-N 0.000 description 1
- 229940043276 diisopropanolamine Drugs 0.000 description 1
- CZZYITDELCSZES-UHFFFAOYSA-N diphenylmethane Chemical class C=1C=CC=CC=1CC1=CC=CC=C1 CZZYITDELCSZES-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 125000005456 glyceride group Chemical group 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical compound OCCN(C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-N 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 239000011295 pitch Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 229920005906 polyester polyol Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 239000004848 polyfunctional curative Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- WBHHMMIMDMUBKC-XLNAKTSKSA-N ricinelaidic acid Chemical compound CCCCCC[C@@H](O)C\C=C\CCCCCCCC(O)=O WBHHMMIMDMUBKC-XLNAKTSKSA-N 0.000 description 1
- 229960003656 ricinoleic acid Drugs 0.000 description 1
- FEUQNCSVHBHROZ-UHFFFAOYSA-N ricinoleic acid Natural products CCCCCCC(O[Si](C)(C)C)CC=CCCCCCCCC(=O)OC FEUQNCSVHBHROZ-UHFFFAOYSA-N 0.000 description 1
- 229910052895 riebeckite Inorganic materials 0.000 description 1
- 238000007761 roller coating Methods 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000010454 slate Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000011269 tar Substances 0.000 description 1
- 239000011271 tar pitch Substances 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 239000013638 trimer Chemical class 0.000 description 1
- 239000003981 vehicle Substances 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Landscapes
- Polyurethanes Or Polyureas (AREA)
- Paints Or Removers (AREA)
Description
本発明は、厚塗り塗装可能な無溶剤型ウレタン
樹脂塗料組成物に関するものである。
従来、高耐久性、高耐食性等が要求される鋼構
造物、例えば、鋳鉄管、タンク、橋梁、海洋構造
物等の被塗物には厚膜型エポキシ樹脂塗料、ター
ルエポキシ樹脂塗料あるいはタールウレタン樹脂
塗料等が主として使用されていた。
しかしながらこれら、これらの塗料は乾燥が遅
く、常温では、ハンドリング可能となるまでに通
常１乃至数日かかり、特に冬場の低温時には、さ
らに長い日数を要するという問題点があつた。前
記に於て被塗物を加熱乾燥すれば乾燥時間を大巾
に短縮することが出来るが、それが大型の場合に
は、附髄設備の観点から通常困難であり、また省
資源、省力化の観点からみても好ましくないこと
であつた。そこで乾燥性のよい、ポリエーテルポ
リオールあるいはポリエステルポリオールとポリ
イソシアネートからなるウレタン樹脂が近年注目
されているが、前記のような従来公知の塗料と同
等程度の耐久性、耐食性を有し、しかもスプレー
塗装が可能な無溶剤型ウレタン樹脂塗料は、未だ
知られていない。
本発明者等は、前記の如き現状に鑑み、耐久
性、耐食性等が優れ、かつ乾燥時間の短かい、ス
プレー塗装が可能な無溶剤型ウレタン樹脂塗料に
つき鋭意検討の結果、本発明に到達した。
すなわち、本発明は
(A)(i) ひまし油………… 40〜90重量％
(ii) (イ)モノアミン又はジアミンと(ロ)エチレンオ
キサイド又はプロピレンオキサイドとの反応
生成物である、水酸基価300〜1000、数平均
分子量600以下のポリオール…………
５〜50重量％及び
(iii) 平滑性助剤………… ２〜50重量％
とからなる主剤成分と
(B) ポリイソシアネートからなる硬化剤成分とを
硬化剤成分のイソシアネート基対主剤成分の水
酸基の当量比（NCO／OH）が（0.9〜1.6／1.0）
になるように配合してなるウレタン樹脂塗料組成
物に関するものである。
本発明は、このようにひまし油、モノアミン又
はジアミンとエチレンオキサイド又はプロピレン
オキサイドとの反応生成物であるポリオール及び
平滑性助剤を主成分としてなるものである。
本発明に於て、「ひまし油」はトウゴマの種子
から圧搾法によつて、得られる不乾性油であつ
て、リシノール酸のグリセライドを主成分とする
ものである。普通、１分子中に、平均約2.5個の
水酸基を有し、粘度約６〜９ストークスポイズ
（20℃において）である。
なお、トリメチロールプロパン、グリセリン、
ペンタエリスリトール等の多価アルコールで変性
した変性ひまし油も本発明において使用出来る。
本発明に於てポリオール成分がひまし油単独で
あると、ポリイソシアネートとの反応が著しく遅
く、また得られた塗膜は粘着性である。そこで、
本発明では、さらにモノアミン又はジアミンとエ
チレンオキサイド又はプロピレンオキサイドとの
反応生成物であるポリオール（以下これを便宜
上、アミン系ポリオールいう）を使用する。
本発明に於て使用するアミン系ポリオールは、
モノエタノールアミン、ジエタノールアミン、ト
リエタノールアミン、Ｎ−メチルジエタノールア
ミン、モノイソプロパノールアミン、ジイソプロ
パノールアミン、トリイソプロパノールアミン、
アンモニア等の「モノアミン」、あるいはエチレ
ンジアミン、トルイレンジアミン等の「ジアミ
ン」と、エチレンオキサイド又はプロピレンオキ
サイドとを、モル比１／２〜１／12の割合で付加
反応させたものであり、その水酸基価は300〜
1000、数平均分子量は600以下のものである。
なお、水酸基価が300未満であつたり、あるい
は数平均分子量が600を越えたりすると、得られ
る塗膜は柔かすぎ、粘着性が残りやすくなる。逆
に、水酸基価が1000を越えると得られる塗膜は、
もろくなる。それ故何れにしろ前記特定のもの以
外のものは、いずれも好ましくない。
特に本発明においてはエチレンジアミンのプロ
ピレンオキサイド付加物が塗装作業性が良く、塗
膜の機械的強度が優れているので最も好ましいも
のである。
本発明においては主剤成分としてさらに、平滑
性助剤を配合する。該平滑性助剤は、水分を吸着
したり、水と反応する機能を有するもので、具体
的にはゼオライト、焼セツコウ、消石灰、生石灰
等を挙げることができる。それ等の粒径は約
500μ以下特に100μ以下の粉末が好ましい。
ウレタン樹脂は周知の通りイソシアネート基と
水酸基との反応により樹脂化する。その際、どん
な状態であるにしろ、水分（例えば塗料原料中、
被塗物表面、大気中の水分）が存在していると、
その水分とポリイソシアネートとが反応し、炭酸
ガスを発生する。その結果、塗膜にピンホール等
が生じ、平滑で均一な塗膜が得られにくい。
本発明においては、それ故水分を吸着したり、
又は水と反応したりするような作用を有する平滑
性助剤を組成物中に配合し、ポリイソシアネート
と反応する水分を除去することにより、前記問題
点を解消している。
特にゼオライトは、水分の吸着速度が早いため
本発明において好適である。
なお、平滑性助剤は、多量に使用した場合、充
填剤としての機能を併せ有する。
本発明は以上の構成成分よりなり、その配合割
合はひまし油40〜90重量％、特に好ましくは65〜
85重量％、アミン系ポリオール５〜50重量％、特
に好ましくは14〜40重量％、平滑性助剤２〜50重
量％の組成が適当である。
前記に於てひまし油が前記組成範囲より少ない
と、塗料の流動性が少なくなり、塗装作業性、顔
料との混和性が悪くなる。また得られる塗膜は、
可撓性が悪い。一方前記組成範囲より多過ぎる
と、硬化速度が遅くなり、また得られる塗膜は粘
着性が残るため、いずれの場合も好ましくない。
またアミン系ポリオールについては、前記範囲
より少ないと硬化速度が遅くなり、また逆に多過
ぎると、ポツトライフが短かくなり塗装作業に困
難をきたし、さらに得られた塗膜は脆くなる。そ
れ故いずれの場合も好ましくない。
さらに平滑性助剤については、前記範囲より少
ないと添加効果が認められず、逆に多過ぎると塗
膜の耐水性、耐化学薬品性等が低下するのでいず
れにしろ好ましくない。
本発明において硬化剤成分(B)としてポリイソシ
アネートを使用する。
該ポリイソシアネートとしては、トルイレンジ
ソシアネート（TDI）、ジフエニルメタンジイソ
シアネート（MDI）、ポリフエニルメタンポリイ
ソシアネート（クルードMDI）、変性ジフエニル
メタンポリイソシアネート（変性MDI）、キシリ
レンジイソシアネート（XDI）、ヘキサメチレン
ジイソシアネート（HMDI）あるいはこれらポ
リイソシアネートの三量体化合物、これらポリイ
ソシアネートとポリオールの反応生成物等が代表
的なものとして挙げられる。
該ポリイソシアネートは、前記主剤成分(A)と、
使用（塗装）直前に混合して塗料化する。その配
合割合は硬化剤成分のイソシアネート基対主剤成
分の水酸基の当量比（NCO／OH）が（0.9〜
1.6／1.0）となる範囲が好ましい。この範囲をは
ずれると、本来のウレタン樹脂の性能が発揮まれ
ないので好ましくない。
本発明においては、必要に応じ主剤成分に各種
着色顔料；防食顔料；シリカ、バライト、炭酸カ
ルシウム、クレー、タルク、マイカ等の体質顔
料；第３級アミン、有機金属化合物等の添加剤；
ガラス繊維、アスベスト、ナイロン、炭素繊維等
の繊維性物質；その他タール、タールピツチ、ア
スフアルト、アスフアルトピツチ、各種可塑剤、
各種合成樹脂等の改質剤を配合することも可能で
ある。
さらに本発明のウレタン樹脂塗料組成物は、ス
プレー塗装、ローラー塗装、ハケ塗装等の手段に
より塗装可能であり、１回塗りで0.1〜５mm程度
の厚塗りが出来る。ハンドリング可能となる乾燥
時間も数分〜数時間で、従来公知のこの種塗料に
比較して、大巾に短縮可能である。
また得られる塗膜は耐久性、耐食性に優れ、か
つ平滑で緻密な塗膜が得られるという特長をもつ
ている。
加うるに被塗物も、既に述べた鋳鉄管、タン
ク、橋梁、プラント、鉄道車両、海洋構造物等の
鋼構造物だけでなく、コンクリート、モルタル、
スレート、木材等の被塗物にも適用可能となる。
以下本発明を実施例によりさらに詳細に説明す
る。
なお、実施例中「部」、「％」は、重量基準であ
る。
実施例 １
第１表に示す主剤成分を撹拌機又はサンドミル
で十分撹拌混合し、１日間密閉下に放置した後、
第１表に示すポリイソシアネートと混合し、得ら
れたウレタン樹脂塗料をサンドブラスト鋼板に乾
燥膜厚約２mmとなるようスプレー塗装し、常温
（20℃）乾燥させた。
得られた塗膜につき、塗膜外観、密着性、可撓
性、耐水性、耐アルカリ性、耐酸性、耐塩水性の
各種試験を行ない、その結果を第１表下段に記載
した。
実施例２〜14及び比較例１〜４
実施例１と同様にして第１表に示す塗料を塗装
し、前記各種試験を行ないその結果を第１表下段
に記載した。
比較例 ５
ビスフエノールＡ型エポキシ樹脂（エポキシ当
量480）９％、ビスフエノールＡ型エポキシ樹脂
（エポキシ当量250）９％、精製タール35％、カー
ボンブラツク１％、タルク25％、溶剤21％からな
る主剤成分85部とポリアミド樹脂（アミン価250）
40％、溶剤60％からなる硬化剤成分15部とを混合
した、市販のタールエポキシ樹脂塗料をサンドブ
ラスト鋼板にスプレー塗装し、１日間常温乾燥さ
せ、同様にしてさらに２回塗り重ね、全乾燥膜厚
約２mmとした。得られた塗膜につき、前記各種試
験を行ないその結果を第１表下段に記載した。
The present invention relates to a solvent-free urethane resin coating composition that can be coated in thick coats. Conventionally, thick-film epoxy resin paints, tar epoxy resin paints, or tar urethane paints have been used for steel structures that require high durability and high corrosion resistance, such as cast iron pipes, tanks, bridges, and marine structures. Resin paints etc. were mainly used. However, these paints have a problem in that they dry slowly and usually take one to several days before they can be handled at room temperature, and even longer at low temperatures, especially in winter. In the above case, if the object to be coated is heated and dried, the drying time can be greatly shortened, but in the case of large-sized objects, it is usually difficult to do so from the viewpoint of supporting equipment, and it is also difficult to save resources and labor. From this point of view, this was not desirable. Therefore, urethane resins made of polyether polyol or polyester polyol and polyisocyanate, which have good drying properties, have been attracting attention in recent years. A solvent-free urethane resin paint that can do this is not yet known. In view of the above-mentioned current situation, the inventors of the present invention have arrived at the present invention as a result of intensive research into a solvent-free urethane resin paint that has excellent durability, corrosion resistance, etc., has a short drying time, and can be spray painted. . That is, the present invention provides (A) (i) Castor oil...40 to 90% by weight (ii) A reaction product of (a) monoamine or diamine and (b) ethylene oxide or propylene oxide, which has a hydroxyl value of 300. ~1000, polyol with a number average molecular weight of 600 or less…………
5 to 50% by weight and (iii) smoothing aid...... 2 to 50% by weight, and (B) a curing agent component consisting of polyisocyanate, with the isocyanate group of the curing agent component versus the main component. The equivalent ratio of hydroxyl groups (NCO/OH) is (0.9 to 1.6/1.0)
The present invention relates to a urethane resin coating composition that is blended so as to have the following properties. The main components of the present invention are a polyol, which is a reaction product of castor oil, a monoamine or diamine, and ethylene oxide or propylene oxide, and a smoothing aid. In the present invention, "castor oil" is a non-drying oil obtained from castor seeds by a pressing method, and is mainly composed of glyceride of ricinoleic acid. Usually, it has an average of about 2.5 hydroxyl groups in one molecule, and a viscosity of about 6 to 9 Stokes Poise (at 20°C). In addition, trimethylolpropane, glycerin,
Modified castor oil modified with polyhydric alcohols such as pentaerythritol can also be used in the present invention. In the present invention, when the polyol component is castor oil alone, the reaction with the polyisocyanate is extremely slow and the resulting coating film is sticky. Therefore,
The present invention further uses a polyol (hereinafter referred to as amine polyol for convenience) which is a reaction product of a monoamine or diamine and ethylene oxide or propylene oxide. The amine polyol used in the present invention is
Monoethanolamine, diethanolamine, triethanolamine, N-methyldiethanolamine, monoisopropanolamine, diisopropanolamine, triisopropanolamine,
It is an addition reaction of "monoamine" such as ammonia, or "diamine" such as ethylenediamine, toluylene diamine, etc., and ethylene oxide or propylene oxide at a molar ratio of 1/2 to 1/12, and the hydroxyl group Price is 300~
1000, and the number average molecular weight is 600 or less. If the hydroxyl value is less than 300 or the number average molecular weight exceeds 600, the resulting coating film will be too soft and will tend to remain sticky. On the other hand, the coating film obtained when the hydroxyl value exceeds 1000 is
Becomes brittle. Therefore, anything other than those specified above is not preferred. In particular, in the present invention, a propylene oxide adduct of ethylenediamine is most preferred because it has good coating workability and the mechanical strength of the coating film. In the present invention, a smoothing aid is further blended as a main component. The smoothing aid has the function of adsorbing water or reacting with water, and specific examples include zeolite, calcined lime, slaked lime, and quicklime. Their particle size is approx.
Powders with a particle size of 500 μm or less, especially 100 μm or less are preferred. As is well known, urethane resins are converted into resins by the reaction between isocyanate groups and hydroxyl groups. At that time, no matter what the state is, moisture (for example, in paint raw materials,
If moisture (on the surface of the object to be coated or in the atmosphere) is present,
The moisture and polyisocyanate react to generate carbon dioxide gas. As a result, pinholes etc. occur in the coating film, making it difficult to obtain a smooth and uniform coating film. Therefore, in the present invention, moisture is adsorbed,
Alternatively, the above-mentioned problems are solved by incorporating into the composition a smoothing aid that has an action of reacting with water and removing water that reacts with the polyisocyanate. In particular, zeolite is suitable for the present invention because it has a fast water adsorption rate. Note that the smoothing aid also has the function of a filler when used in a large amount. The present invention consists of the above-mentioned components, and the blending ratio is 40 to 90% by weight of castor oil, particularly preferably 65 to 90% by weight.
A suitable composition is 85% by weight of the amine polyol, 5 to 50% by weight of the amine polyol, particularly preferably 14 to 40% by weight, and 2 to 50% by weight of the smoothing agent. In the above, if the amount of castor oil is less than the above composition range, the fluidity of the coating material will decrease, and the coating workability and miscibility with pigments will deteriorate. In addition, the resulting coating film is
Poor flexibility. On the other hand, if the amount exceeds the above range, the curing speed will be slow and the resulting coating will remain sticky, which is not preferable in either case. Regarding amine polyols, if the amount is less than the above range, the curing speed will be slow, and if it is too much, the pot life will be shortened, making painting work difficult, and the resulting coating film will become brittle. Therefore, neither case is preferable. Furthermore, with regard to the smoothness aid, if the amount is less than the above range, no effect will be observed, and if it is too much, the water resistance, chemical resistance, etc. of the coating film will be reduced, which is not preferable in any case. In the present invention, polyisocyanate is used as the curing agent component (B). Examples of the polyisocyanate include toluylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), polyphenylmethane polyisocyanate (crude MDI), modified diphenylmethane polyisocyanate (modified MDI), xylylene diisocyanate (XDI), Representative examples include hexamethylene diisocyanate (HMDI), trimer compounds of these polyisocyanates, and reaction products of these polyisocyanates and polyols. The polyisocyanate comprises the base component (A) and
Mix it into a paint just before use (painting). The compounding ratio is such that the equivalent ratio (NCO/OH) of the isocyanate group of the curing agent component to the hydroxyl group of the main component is (0.9~
1.6/1.0) is preferable. If it deviates from this range, it is not preferable because the original performance of the urethane resin will not be exhibited. In the present invention, various coloring pigments; anticorrosion pigments; extender pigments such as silica, barite, calcium carbonate, clay, talc, mica; additives such as tertiary amines and organometallic compounds;
Fibrous substances such as glass fiber, asbestos, nylon, and carbon fiber; other tar, tar pitch, asphalt, asphalt pitch, various plasticizers,
It is also possible to blend modifiers such as various synthetic resins. Further, the urethane resin coating composition of the present invention can be coated by means such as spray coating, roller coating, brush coating, etc., and a thick coating of about 0.1 to 5 mm can be achieved in one coat. The drying time required for handling is from several minutes to several hours, which can be significantly shortened compared to conventionally known paints of this type. Furthermore, the resulting coating film has excellent durability and corrosion resistance, and is characterized by being smooth and dense. In addition, the objects to be coated include not only steel structures such as cast iron pipes, tanks, bridges, plants, railway vehicles, and marine structures, but also concrete, mortar,
It can also be applied to coated objects such as slate and wood. The present invention will be explained in more detail below using examples. In addition, "part" and "%" in the examples are based on weight. Example 1 The main ingredients shown in Table 1 were thoroughly stirred and mixed using a stirrer or sand mill, and left in a sealed state for one day.
The resulting urethane resin paint was mixed with the polyisocyanate shown in Table 1 and spray-painted onto a sandblasted steel plate to a dry film thickness of about 2 mm, and dried at room temperature (20°C). The resulting coating film was subjected to various tests on coating appearance, adhesion, flexibility, water resistance, alkali resistance, acid resistance, and salt water resistance, and the results are listed in the lower row of Table 1. Examples 2 to 14 and Comparative Examples 1 to 4 The paints shown in Table 1 were applied in the same manner as in Example 1, and the various tests described above were conducted, and the results are listed in the lower row of Table 1. Comparative Example 5 Consists of 9% bisphenol A type epoxy resin (epoxy equivalent: 480), 9% bisphenol A type epoxy resin (epoxy equivalent: 250), 35% purified tar, 1% carbon black, 25% talc, 21% solvent. 85 parts of main ingredient and polyamide resin (amine value 250)
A commercially available tar epoxy resin paint mixed with 15 parts of hardener component consisting of 40% solvent and 60% solvent was spray-painted on a sandblasted steel plate, dried at room temperature for 1 day, and coated two more times in the same manner to form a completely dry film. The thickness was approximately 2 mm. The resulting coating film was subjected to the various tests described above, and the results are listed in the lower row of Table 1.
【表】【table】
【表】【table】
【表】
第１表より明らかの如く本発明のウレタン樹脂
塗料は硬化時間が短かく、かつ得られた塗膜は、
優れた塗膜性能を有していた。
一方ひまし油量の少ない塗料を使用した比較例
１及びひまし油を含有しない塗料を使用した比較
例４は、可使時間が極めて短かく、得られた塗膜
は、非常に脆いものであり、耐久性、耐アルカリ
性、耐酸性、耐塩水性とも不良であつた。
またアミン系ポリオールを含有しない塗料を使
用した比較例２は、塗膜がいつまでも粘着性をも
つており、耐久性、耐アルカリ性、耐酸性とも不
良であつた。
さらに平滑性助剤を含有しない塗料を使用した
比較例３は、塗膜に発泡が残つていた。
また従来のタールエポキシ樹脂塗料を使用した
比較例５は、塗膜性能は優れていたが、乾燥時間
が、非常に遅かつた。
かくて、本発明の組成物は極めて優れたもので
あることが理解されよう。[Table] As is clear from Table 1, the urethane resin paint of the present invention has a short curing time, and the resulting paint film has
It had excellent coating performance. On the other hand, Comparative Example 1, which used a paint with a small amount of castor oil, and Comparative Example 4, which used a paint that did not contain castor oil, had an extremely short pot life, and the resulting paint films were extremely brittle and had poor durability. , alkali resistance, acid resistance, and salt water resistance were all poor. In addition, in Comparative Example 2 in which a paint containing no amine polyol was used, the paint film remained sticky for a long time and was poor in durability, alkali resistance, and acid resistance. Furthermore, in Comparative Example 3 in which a paint containing no smoothing aid was used, foaming remained in the paint film. Furthermore, in Comparative Example 5, which used a conventional tar epoxy resin paint, the coating film performance was excellent, but the drying time was extremely slow. It will thus be understood that the composition of the present invention is extremely superior.
Claims (1)
イド又はプロピレンオキサイドとの反応生成
物である、水酸基価300〜1000、数平均分子
量600以下のポリオール…………
５〜50重量％及び (iii) 平滑性助剤………… ２〜50重量％ とからなる主剤成分と (B) ポリイソシアネートからなる硬化剤成分と
を、 硬化剤成分のイソシアネート基対主剤成分の水
酸基の当量比（NCO／OH）が（0.9〜1.6／1.0）
になるように配合してなるウレタン樹脂塗料組成
物。 ２ 前記ポリオール(ii)がエチレンジアミンとプロ
ピレンオキサイドとの反応生成物であることを特
徴とする特許請求の範囲第１項記載のウレタン樹
脂塗料組成物。[Scope of Claims] 1 (A)(i) Castor oil...40 to 90% by weight (ii) A reaction product of a monoamine or diamine and ethylene oxide or propylene oxide, with a hydroxyl value of 300 to 1000 and a number Polyol with an average molecular weight of 600 or less…………
5 to 50% by weight and (iii) smoothing aid...... 2 to 50% by weight, and (B) a curing agent component consisting of polyisocyanate, with the isocyanate group of the curing agent component versus the main component. The equivalent ratio of hydroxyl groups (NCO/OH) is (0.9 to 1.6/1.0)
A urethane resin coating composition that is formulated to have the following properties. 2. The urethane resin coating composition according to claim 1, wherein the polyol (ii) is a reaction product of ethylenediamine and propylene oxide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58140875A JPS6032857A (en) | 1983-08-01 | 1983-08-01 | Urethane resin coating compound composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58140875A JPS6032857A (en) | 1983-08-01 | 1983-08-01 | Urethane resin coating compound composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6032857A JPS6032857A (en) | 1985-02-20 |
| JPS6328474B2 true JPS6328474B2 (en) | 1988-06-08 |
Family
ID=15278786
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP58140875A Granted JPS6032857A (en) | 1983-08-01 | 1983-08-01 | Urethane resin coating compound composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6032857A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0641664U (en) * | 1992-11-12 | 1994-06-03 | 株式会社新屋製作所 | Boots cleaning equipment |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60166353A (en) * | 1984-02-09 | 1985-08-29 | Dai Ichi Kogyo Seiyaku Co Ltd | Polyurethane metal corrosion-proof coating composition |
| ATE466896T1 (en) * | 2006-10-04 | 2010-05-15 | Basf Se | POLYURETHANE-BASED CASTING COMPOUNDS |
| JP5279184B2 (en) * | 2006-12-19 | 2013-09-04 | アイカ工業株式会社 | Coating material composition |
| JP2012117352A (en) * | 2010-12-03 | 2012-06-21 | Konishi Co Ltd | Coating agent and external wall separation prevention method using the coating agent |
| CN108138022A (en) * | 2016-09-29 | 2018-06-08 | Dic株式会社 | Bonding agent, stacked film and bonding agent glycol composition using it |
| JP7315425B2 (en) * | 2019-09-25 | 2023-07-26 | アイカ工業株式会社 | Urethane resin composition containing no catalyst |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6015470A (en) * | 1983-07-06 | 1985-01-26 | Dai Ichi Kogyo Seiyaku Co Ltd | Corrosion-resistant paint composition |
-
1983
- 1983-08-01 JP JP58140875A patent/JPS6032857A/en active Granted
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6015470A (en) * | 1983-07-06 | 1985-01-26 | Dai Ichi Kogyo Seiyaku Co Ltd | Corrosion-resistant paint composition |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0641664U (en) * | 1992-11-12 | 1994-06-03 | 株式会社新屋製作所 | Boots cleaning equipment |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6032857A (en) | 1985-02-20 |
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