JP2018100404A - 吹き付け塗装用のポリオール組成物、発泡性ポリウレタンプレミックス組成物、および発泡性ポリウレタン組成物 - Google Patents
吹き付け塗装用のポリオール組成物、発泡性ポリウレタンプレミックス組成物、および発泡性ポリウレタン組成物 Download PDFInfo
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- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 description 1
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical class CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 1
- 150000004072 triols Chemical class 0.000 description 1
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 description 1
- ODHXBMXNKOYIBV-UHFFFAOYSA-N triphenylamine Chemical class C1=CC=CC=C1N(C=1C=CC=CC=1)C1=CC=CC=C1 ODHXBMXNKOYIBV-UHFFFAOYSA-N 0.000 description 1
- FIQMHBFVRAXMOP-UHFFFAOYSA-N triphenylphosphane oxide Chemical compound C=1C=CC=CC=1P(C=1C=CC=CC=1)(=O)C1=CC=CC=C1 FIQMHBFVRAXMOP-UHFFFAOYSA-N 0.000 description 1
- WUUHFRRPHJEEKV-UHFFFAOYSA-N tripotassium borate Chemical compound [K+].[K+].[K+].[O-]B([O-])[O-] WUUHFRRPHJEEKV-UHFFFAOYSA-N 0.000 description 1
- WTLBZVNBAKMVDP-UHFFFAOYSA-N tris(2-butoxyethyl) phosphate Chemical compound CCCCOCCOP(=O)(OCCOCCCC)OCCOCCCC WTLBZVNBAKMVDP-UHFFFAOYSA-N 0.000 description 1
- QEEHNBQLHFJCOV-UHFFFAOYSA-N tris(2-phenylphenyl) phosphate Chemical compound C=1C=CC=C(C=2C=CC=CC=2)C=1OP(OC=1C(=CC=CC=1)C=1C=CC=CC=1)(=O)OC1=CC=CC=C1C1=CC=CC=C1 QEEHNBQLHFJCOV-UHFFFAOYSA-N 0.000 description 1
- LIPMRGQQBZJCTM-UHFFFAOYSA-N tris(2-propan-2-ylphenyl) phosphate Chemical compound CC(C)C1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C(C)C)OC1=CC=CC=C1C(C)C LIPMRGQQBZJCTM-UHFFFAOYSA-N 0.000 description 1
- BSVBQGMMJUBVOD-UHFFFAOYSA-N trisodium borate Chemical compound [Na+].[Na+].[Na+].[O-]B([O-])[O-] BSVBQGMMJUBVOD-UHFFFAOYSA-N 0.000 description 1
- 239000004246 zinc acetate Substances 0.000 description 1
- 239000011667 zinc carbonate Substances 0.000 description 1
- 235000004416 zinc carbonate Nutrition 0.000 description 1
- 229910000010 zinc carbonate Inorganic materials 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 1
- CHJMFFKHPHCQIJ-UHFFFAOYSA-L zinc;octanoate Chemical compound [Zn+2].CCCCCCCC([O-])=O.CCCCCCCC([O-])=O CHJMFFKHPHCQIJ-UHFFFAOYSA-L 0.000 description 1
- 150000003754 zirconium Chemical class 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
Description
1.ポリイソシアネート
ポリイソシアネート化合物としては、例えば、芳香族ポリイソシアネート、脂環族ポリイソシアネート、脂肪族ポリイソシアネート等が挙げられる。
ウレタン樹脂の硬化剤であるポリオールとしては、例えばポリラクトンポリオール、ポリカーボネートポリオール、芳香族ポリオール、脂環族ポリオール、脂肪族ポリオール、ポリエステルポリオール、ポリマーポリオール、ポリエーテルポリオール等が挙げられる。
ポリラクトンポリオールとしては、例えば、ポリプロピオラクトングリコール、ポリカプロラクトングリコール、ポリバレロラクトングリコールなどが挙げられる。
触媒としては、例えば、トリエチルアミン、N−メチルモルホリンビス(2−ジメチルアミノエチル)エーテル、N,N,N’,N”, N”−ペンタメチルジエチレントリアミン、N, N, N’−トリメチルアミノエチル−エタノールアミン、ビス(2−ジメチルアミノエチル)エーテル、N−メチル, N’−ジメチルアミノエチルピペラジン、イミダゾール環中の第2級アミン官能基をシアノエチル基で置換したイミダゾール化合物等の窒素原子含有触媒等が挙げられる。
また発泡性ポリウレタン組成物に使用する発泡剤は、ウレタン樹脂の発泡を促進する。
発泡剤は一種もしくは二種以上を使用することができる。
発泡性ポリウレタン組成物に使用する整泡剤としては、例えば、ポリオキシアルキレンアルキルエーテル等のポリオキシアルキレン整泡剤、オルガノポリシロキサン等のシリコーン整泡剤等の界面活性剤等が挙げられる。
整泡剤はそれぞれ一種もしくは二種以上を使用することができる。
次に、本発明の発泡性ポリウレタン組成物に使用される難燃剤について説明する。
臭素化ビスフェノールAを原料として製造されたポリカーボネートオリゴマー、前記ポリカーボネートオリゴマーとビスフェノールAとの共重合物等の臭素化ポリカーボネート、
臭素化ビスフェノールAとエピクロルヒドリンとの反応によって製造されるジエポキシ化合物、臭素化フェノール類とエピクロルヒドリンとの反応によって得られるモノエポキシ化合物等の臭素化エポキシ化合物、
ポリ(臭素化ベンジルアクリレート)、
臭素化ポリフェニレンエーテル、
臭素化ビスフェノールA、塩化シアヌールおよび臭素化フェノールの縮合物、
臭素化(ポリスチレン)、ポリ(臭素化スチレン)、架橋臭素化ポリスチレン等の臭素化ポリスチレン、
架橋または非架橋臭素化ポリ(−メチルスチレン)等のハロゲン化された臭素化合物ポリマーが挙げられる。
さらに発泡性ポリウレタン組成物は、それぞれ本発明の目的を損なわない範囲で、必要に応じて、フェノール系、アミン系、イオウ系等の酸化防止剤、熱安定剤、金属害防止剤、帯電防止剤、安定剤、架橋剤、滑剤、軟化剤、顔料、粘着付与樹脂等の補助成分、ポリブテン、石油樹脂等の粘着付与剤を含むことができる。
また、本発明は以下の構成を採用することもできる。
[1]ポリイソシアネート化合物と反応させてポリウレタン発泡体を得るためのポリオール組成物であって、ポリオール、触媒、発泡剤、整泡剤、および難燃剤を含有し、ポリオール100重量部に対する前記触媒の量が10重量部〜56重量部である、吹き付け塗装用のポリオール組成物。
[2]前記触媒が、ポリオール100重量部に対して3〜28重量部の三量化触媒と、0.3〜28重量部のウレタン化触媒とを含む[1]に記載の吹き付け塗装用のポリオール組成物。
[4]25℃における粘度が50〜2000mPa・sの範囲である[1]〜[3]のいずれかに記載の吹き付け塗装用のポリオール組成物。
[5][1]〜[4]のいずれかに記載の吹き付け塗装用のポリオール組成物およびポリイソシアネート化合物を分離して含む、吹き付け塗装用の発泡性ポリウレタンプレミックス組成物。
[7]被塗構造体の温度が5℃の場合のクリームタイムが1秒以内である[6]に記載の吹き付け塗装用の発泡性ポリウレタン組成物。
[8][6]または[7]に記載の吹き付け塗装用の発泡性ポリウレタン組成物が硬化したポリウレタン発泡体。
[9]成形体であることを特徴とする[8]に記載のポリウレタン発泡体。
表1に示した配合により、実施例1〜15および比較例1〜5に係るポリオール組成物および発泡性ウレタン樹脂組成物を準備した。表中の各成分の詳細は次の通りである。
(1)イソシアネート化合物 (以下、「ポリイソシアネート」という)
(A)4,4’−ジフェニルメタンジイソシアネート(4,4’−MDI)(万華化学ジャパン株式会社製、製品名:PM200)。
・ポリオール(B)
p−フタル酸ポリエステルポリオール(川崎化成工業社製、製品名:マキシモールRFK−087、水酸基価=200mgKOH/g)
・三量化触媒(C)
(C−1)3量化触媒(サンアプロ株式会社製、製品名:U−CAT 18X)。 (C−2)3量化触媒(東ソー社製、製品名:TOYOCAT−TR20)
(C−3)3量化触媒(モメンティブ・パフォーマンス・マテリアル・ジャパン社製、製品名:K-zero G)
・ウレタン化触媒(D)
(D−1)ウレタン化触媒(サンアプロ株式会社製、製品名:U−CAT 202)
(D−2)N,N,N'−トリメチルアミノエチルエタノ−ルアミン(東ソー社製、商品名:TOYOCAT−RX5)
(D−3)ウレタン化触媒(東ソー社製、製品名:TOYOCAT−TT)
(D−4)ウレタン化触媒(日東化成株式会社製、製品名:U−830)
・発泡剤(E)
(E−1)水
(E−2)HFC HFC−365mfc(1,1,1,3,3−ペンタフルオロブタン、日本ソルベイ社製)
(E−3)HFC−245fa(1,1,1,3,3−ペンタフルオロプロパン、セントラル硝子社製)
(E−4)LBA (ハネウェルジャパン株式会社、製品名:ソルスティスLBA)
・整泡剤(F)
ポリアルキレングリコール系整泡剤(東レダウコーニング社製、製品名:SH−193)
・難燃剤
液体難燃剤(G)
トリス(β−クロロプロピル)ホスフェート(大八化学社製、製品名:TMCPP、以下「TMCPP」という。)
粉体難燃剤
(H)赤リン (燐化学工業社製、製品名:ノーバエクセル140)
(I)ウォラストナイト(SiO2・CaO)(キンセイマテック社製、無機フィラー、製品名:SH−1250)。
(J)ホウ酸亜鉛(早川商事株式会社製、遷移金属化合物、製品名:Firebrake ZB)
(K)ヘキサブロモベンゼン(マナック社製、製品名:HBB−b、以下「HBB」)
上記発泡体を下記の基準により評価し、結果を表1に示した(各成分の割合をウレタン樹脂100重量部に対する重量部で示す)。
[粘度の測定]
ポリイソシアネート以外の成分を1000mLポリプロピレン製ビーカーに取り、撹拌してポリオール組成物を調製した。撹拌後、1時間ほど時間を置いて溶液を安定させ、ポリオール組成物を500mLポリプロピレン製ビーカーに300mL量りとった。ポリオール組成物を水浴にて25℃に調製した後、VISCOTECH社製B型粘度計を用いて粘度を測定した。測定にはR3の回転子を使用し、回転数は60rpmとした。
前記難燃性ウレタン樹脂組成物を被塗構造物に吹き付けた後、ポリオール組成物とポリイソシアネートの混合溶液が反応を開始し、溶液の色が変色を始めた時間を目視で観察し、クリームタイムとした。
[総発熱量の測定]
硬化物から発泡性ウレタン樹脂組成物(被塗構造物の厚み除く)のサイズが100mm×100mm×20mmになるようにコーンカロリーメーター試験用サンプルを切り出し、ISO−5660に準拠し、輻射熱強度50kW/m2にて20分間加熱したときの総発熱量を測定した結果を表1に記載した。
Claims (9)
- ポリイソシアネート化合物と反応させてポリウレタン発泡体を得るためのポリオール組成物であって、ポリオール、触媒、発泡剤、整泡剤、および難燃剤を含有し、ポリオール100重量部に対する前記触媒の量が10重量部〜56重量部である、吹き付け塗装用のポリオール組成物。
- 前記触媒が、ポリオール100重量部に対して3〜28重量部の三量化触媒と、0.3〜28重量部のウレタン化触媒とを含む請求項1記載の吹き付け塗装用のポリオール組成物。
- 前記難燃剤は粉体難燃剤を含み、粉体難燃剤の量がポリオール100重量部に対して13〜99重量部であり、ポリオール100重量部に対して13〜59重量部の赤リンを含む請求項1または2に記載の吹き付け塗装用のポリオール組成物。
- 25℃における粘度が50〜2000mPa・sの範囲である請求項1〜3のいずれかに記載の吹き付け塗装用のポリオール組成物。
- 請求項1〜4のいずれかに記載の吹き付け塗装用のポリオール組成物およびポリイソシアネート化合物を分離して含む、吹き付け塗装用の発泡性ポリウレタンプレミックス組成物。
- 請求項1〜4のいずれかに記載の吹き付け塗装用のポリオール組成物とポリイソシアネート化合物との混合物である、吹き付け塗装用の発泡性ポリウレタン組成物。
- 被塗構造体の温度が5℃の場合のクリームタイムが1秒以内である請求項6に記載の吹き付け塗装用の発泡性ポリウレタン組成物。
- 請求項6または7記載の吹き付け塗装用の発泡性ポリウレタン組成物が硬化したポリウレタン発泡体。
- 成形体であることを特徴とする請求項8記載のポリウレタン発泡体。
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JP7288371B2 (ja) | 2018-08-31 | 2023-06-07 | 株式会社エフコンサルタント | 硬化性組成物 |
WO2020116526A1 (ja) * | 2018-12-04 | 2020-06-11 | 積水化学工業株式会社 | ポリウレタン組成物原料液剤、ポリウレタン組成物、及び混合システム |
JPWO2020116526A1 (ja) * | 2018-12-04 | 2021-05-20 | 積水化学工業株式会社 | ポリウレタン組成物原料液剤、ポリウレタン組成物、及び混合システム |
JP7478048B2 (ja) | 2019-07-08 | 2024-05-02 | 積水化学工業株式会社 | ポリオール含有組成物、発泡性ポリウレタン組成物及びポリウレタンフォーム |
WO2021039289A1 (ja) * | 2019-08-28 | 2021-03-04 | 積水化学工業株式会社 | ポリオール含有組成物、発泡性ポリウレタン組成物及びポリウレタンフォーム |
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