CN105849166A - 酚醛树脂发泡体 - Google Patents

酚醛树脂发泡体 Download PDF

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CN105849166A
CN105849166A CN201480071348.8A CN201480071348A CN105849166A CN 105849166 A CN105849166 A CN 105849166A CN 201480071348 A CN201480071348 A CN 201480071348A CN 105849166 A CN105849166 A CN 105849166A
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hydrocarbon
phenol resin
less
resin foam
carbon
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CN105849166B (zh
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浜岛雅人
向山滋美
井原健
熊田淳
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Asahi Kasei Construction Materials Corp
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Priority to JP2013271896 priority
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Priority to JP2014-050214 priority
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Priority to PCT/JP2014/084404 priority patent/WO2015099086A1/ja
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Abstract

本发明公开了一种酚醛树脂发泡体,其含有酚醛树脂、碳数为6以下的烃和选自由氢氟烯烃以及氢氯氟烯烃组成的组中的至少1种含氢卤代烯烃,前述酚醛树脂发泡体的密度为10kg/m3以上且150kg/m3以下,酚醛树脂发泡体内的平均每22.4×10‑3m3的空间体积中,碳数为6以下的烃的含量与含氢卤代烯烃的含量的总和为0.23~0.90mol,并且,碳数为6以下的烃的含量为0.03~0.85mol,且含氢卤代烯烃的含量为0.05~0.85mol。

Description

酚醛树脂发泡体
技术领域
[0001 ]本发明涉及酚醛树脂发泡体。
背景技术
[0002] 近年来由于涉及节能性的意识以及新一代节能性标准的任务化等而谋求住宅的 高气密、高绝热。如此,伴随住宅的绝热性能提高,预想到所需要的绝热材料的厚度增加,但 在室内的居住空间的压迫以及墙体内的空间上存在限制,因此产生随着绝热材料的追加而 必须变更设计的问题。绝热材料由于向墙体内施工而使得居住同时的更换非常困难,因此 需要经过长时间而维持绝热性能。
[0003] 作为住宅用途的绝热材料,使用以玻璃棉、岩棉为代表的纤维系的绝热材料或使 苯乙烯、氨基甲酸酯、酚醛树脂发泡而成的发泡塑料系的绝热材料。其中,可知发泡塑料系 的绝热材料根据气泡内所内含的发泡剂的种类以及状态而使绝热性能受到较大影响。
[0004] 以往,发泡塑料系绝热材料中将气体的热导率低的氯氟烃(CFC)用作发泡剂,但严 重导致臭氧层的破坏以及气候变动,因此根据1987年所签订的蒙特利尔议定书而规定废止 使用。其结果,作为发泡剂,进行了发泡剂向臭氧破坏系数、全球变暖系数较低的氢氟烃 (HFC)的转变。然而,HFC依然具有高的全球变暖系数,因此谋求向烃系的发泡剂的转变。
[0005] 对于烃系的发泡剂,如上所述的臭氧破坏系数、全球变暖系数极其低,从环境破坏 的观点来看为非常优异的发泡剂,另一方面,与以往的氯氟烃系发泡剂相比,存在热导率高 以及可燃性的问题,谋求解决该问题。
[0006] 专利文献1、专利文献2中公开了多种气体种类作为臭氧破坏系数为零、全球变暖 系数低的含氢卤代烯烃。
[0007] 现有技术文献
[0008] 专利文献
[0009] 专利文献1:日本特开2013-64139号公报
[0010] 专利文献2:日本特表2010-522819号公报
发明内容
[0011] 发明要解决的问题
[0012] 然而,专利文献1、专利文献2中,作为发泡剂,仅叙述了聚氨酯树脂发泡体或聚异 氰脲酸酯树脂发泡体中所应用的具体例子,并未记载应用于酚醛树脂发泡体的例子。前述 技术并未针对酚醛树脂发泡体用途进行优化,在酚醛树脂中使用的情况下,所得到的泡沫 的初始的K系数不充分。
[0013] 上述专利文献1、专利文献2中公开了大量的含氢卤代烯烃。
[0014]例如,1-氯_3,3,3-三氟丙烯具有臭氧破坏系数以及全球变暖系数极其低的特征。 然而,该物质的沸点为19°C是比较高的,因此在10°C等低温区域,存在发泡剂液化,热导率 恶化的问题。对于酚醛树脂发泡体的热导率的经时变化没有公开,但是,上述1-氯_3,3,3_ 三氟丙烯与酚醛树脂的亲和性高,因此推断在单独使用的情况下,独立气泡率的降低以及 发泡剂向发泡体外的扩散速度变快,因此热导率的经时变化变大。上述含氢卤代烯烃是非 常昂贵的,单独使用在经济上的优点少。
[0015] 1,3,3,3_四氟丙烯具有臭氧破坏系数以及全球变暖系数极低的特征。然而,该物 质的沸点为_19°C是较低的,因此成形时剧烈发生发泡,从而独立气泡率降低,存在以下的 问题:热导率恶化;以及,在成形中发泡剂变得容易挥发,因此需要大量的发泡剂。对于酚醛 树脂发泡体的热导率的经时变化没有公开,但是,上述1,3,3,3_四氟丙烯与酚醛树脂的亲 和性高,因此预想到在单独使用时独立气泡率的降低以及发泡剂向发泡体外的扩散速度变 快,因此推断热导率的经时变化变大。
[0016] 1,1,1,4,4,4_六氟-2-丁烯具有臭氧破坏系数以及全球变暖系数极低的特征。然 而,该物质的沸点为33°C是比较高的,因此在10°C等低温区域,存在发泡剂液化、热导率恶 化的问题。对于酚醛树脂发泡体的热导率的经时变化没有公开,但是,上述1,1,1,4,4,4-六 氟-2-丁烯与酚醛树脂的亲和性高,因此预想到在单独使用时独立气泡率的降低以及发泡 剂向发泡体外的扩散速度变快,因此推断热导率的经时变化变大。
[0017] 本发明的目的在于,提供通过使用臭氧破坏系数实质上为零、全球变暖系数极低 的发泡剂,将环境负载设为最小限度,并且可以经过长时间维持优异的绝热性能的酚醛树 脂发泡体。
[0018] 用于解决问题的方案
[0019] 本发明人等为了达成上述目的而反复进行深入研究,结果发现,将含氢卤代烯烃 与烃以特定的比率共混,并且,将发泡体内存在的发泡剂量设为特定的范围,从而可以使初 始绝热性能优异并且经过长时间维持低热导率,从而完成本发明。
[0020] 本发明提供以下的[1]~[23]。
[0021] [1]-种酚醛树脂发泡体,其含有酚醛树脂、碳数为6以下的烃和选自由氢氟烯烃 以及氢氯氟烯烃组成的组中的至少1种含氢卤代烯烃,所述酚醛树脂发泡体的密度为l〇kg/ m 3以上且150kg/m3以下,酸醛树脂发泡体内的平均每22.4Xl(T3m 3的空间体积中,碳数为6以 下的烃的含量与含氢卤代烯烃的含量的总和为0.23~0.90mol,并且,碳数为6以下的烃的 含量为〇. 03~0.85mol,且含氢卤代烯烃的含量为0.05~0.85mol。
[0022] [2]根据[1]的酚醛树脂发泡体,其中,含氢卤代烯烃包含选自由1-氯_3,3,3_三氟 丙烯、1,3,3,3_四氟丙烯、以及1,1,1,4,4,4_六氟-2-丁烯组成的组中的至少1种。
[0023] [3]根据[1]或[2]的酚醛树脂发泡体,其中,碳数为6以下的烃与含氢卤代烯烃的 沸点平均值为_15°C~48°C。
[0024] [4]根据[1]~[3]中任一项的酚醛树脂发泡体,其中,碳数为6以下的烃包含戊烷 和/或戊烯。
[0025] [5]根据[2]的酚醛树脂发泡体,其中,含氢卤代烯烃为1-氯_3,3,3_三氟丙烯。
[0026] [6]根据[5]的酚醛树脂发泡体,其中,碳数为6以下的烃与1-氯_3,3,3_三氟丙烯 的沸点平均值为15°C~45°C。
[0027] [7]根据[5]或[6]的酚醛树脂发泡体,其中,碳数为6以下的烃包含戊烷和/或戊 稀。
[0028] [8]根据[7]的酚醛树脂发泡体,其中,碳数为6以下的烃相对于该烃总量包含总计 60~lOOmol %的戊烷和/或戊烯、以及0~40mol %的选自沸点为-50°C~5°C的烃的1种或2 种以上,碳数为6以下的烃的沸点平均值为0°C以上且50°C以下。
[0029] [9]根据[8]的酚醛树脂发泡体,其中,沸点为-50°C~5°C的烃包含异丁烷。
[0030] [10]根据[2]的酚醛树脂发泡体,其中,含氢卤代烯烃为1,3,3,3_四氟丙烯。
[0031] [11]根据[10]的酚醛树脂发泡体,其中,碳数为6以下的烃与1,3,3,3_四氟丙烯的 沸点平均值为-15 °C~45 °C。
[0032] [12]根据[10]或[11]的酚醛树脂发泡体,其中,碳数为6以下的烃包含戊烷和/或 戊稀。
[0033] [13]根据[12]的酚醛树脂发泡体,其中,碳数为6以下的烃相对于该烃总量包含总 计40~100mo 1 %的戊烷和/或戊烯、以及0~60mo 1 %的选自沸点为-50 °C~5 °C的烃的1种或 2种以上,碳数为6以下的烃的沸点平均值为10°C以上且50°C以下。
[0034] [14]根据[13]的酚醛树脂发泡体,其中,沸点为-50°C~5°C的烃包含异丁烷。
[0035] [15]根据[2]的酚醛树脂发泡体,其中,含氢卤代烯烃为1,1,1,4,4,4-六氟-2_丁 稀。
[0036] [16]根据[15]的酚醛树脂发泡体,其中,碳数为6以下的烃与1,1,1,4,4,4_六氟-2_丁烯的沸点平均值为0°C~48°C。
[0037] [17]根据[15]或[16]的酚醛树脂发泡体,其中,碳数为6以下的烃包含戊烷和/或 戊稀。
[0038] [18]根据[17]的酚醛树脂发泡体,其中,碳数为6以下的烃相对于该烃总量包含总 计5~100mo 1 %的戊烷和/或戊烯、以及0~95mo 1 %的选自沸点为-50 °C~5 °C的烃的1种或2 种以上,碳数为6以下的烃的沸点平均值为-10°C以上且50°C以下。
[0039] [19]根据[18]的酚醛树脂发泡体,其中,沸点为-50°C~5°C的烃包含异丁烷。
[0040] [ 20 ]根据[1 ]~[19 ]中任一项的酚醛树脂发泡体,其中,10 °C以及23 °C环境下的热 导率均不足0.0205W/m • k。
[0041] [21]根据[1]~[20]中任一项的酚醛树脂发泡体,其中,独立气泡率为90%以上, 且平均气泡直径为40mi以上且300mi以下,并且孔隙面积率为0.2 %以下。
[0042] [22]根据[1]~[21]中任一项的酚醛树脂发泡体,其中,酚醛树脂具有脲键。
[0043] [23]根据[1]~[22]中任一项的酚醛树脂发泡体,其中,在110°C气氛中14天的条 件下放置后的l〇°C环境下的热导率不足0.020W/m • k。
[0044] 发明的效果
[0045] 根据本发明,能够提供初始绝热性能优异并且可以经过长时间维持低热导率的酚 醛树脂发泡体。此外,本发明与单独使用非常昂贵的含氢卤代烯烃的情况相比,在经济上是 有利的。
具体实施方式
[0046] 以下,对于用于实施本发明的方式(以下,称为"本实施方式")进行详细地说明。需 要说明的是,本发明并不限于以下的实施方式。
[0047] 本实施方式的酚醛树脂发泡体含有酚醛树脂、碳数为6以下的烃和选自由氢氟烯 烃以及氢氯氟烯烃组成的组中的至少1种含氢卤代烯烃。其是酚醛树脂发泡体的密度为 l〇kg/m3以上且150kg/m3以下的酚醛树脂发泡体。酚醛树脂发泡体内的平均每22.4Xl(T 3m3 的空间体积中,碳数为6以下的烃的含量与含氢卤代烯烃的含量的总和为0.23~0.90mo 1, 并且,碳数为6以下的经的含量为0.03~0.85mol,且含氢卤代稀经的含量为0.05~ 0.85mol〇
[0048] 本实施方式的酚醛树脂发泡体含有选自由氢氟烯烃以及氢氯氟烯烃组成的组中 的至少1种含氢卤代烯烃。含氢卤代烯烃与酚醛树脂具有高亲和性,因此在作为发泡剂而单 独使用时,存在使发泡时的树脂的粘度降低,不能形成足够的独立气泡结构的情况。因此, 存在发泡剂向发泡体外的扩散速度高,施工后经过长时间后的热导率与刚施工之后相比显 著恶化的问题。因此,本发明人等发现以特定的比例共混含氢卤代烯烃与碳数6以下的烃, 并且使发泡体内存在的发泡剂量处于特定的范围,从而可以解决上述问题。
[0049] 氢氟烯烃是指具有键合于碳原子的氢原子以及氟原子、且具有碳-碳不饱和键的 化合物。氢氯氟烯烃是指具有键合于碳原子的氢原子、氟原子以及氯原子、且具有碳-碳不 饱和键的化合物。作为本实施方式的选自由氢氟烯烃以及氢氯氟烯烃组成的组中的至少1 种含氢卤代烯烃,例如,可以列举出1-氯-3,3,3-三氟丙烯、1,3,3,3-四氟丙烯、1,1,1,4,4, 4_六氟-2-丁烯、2,3,3,3-四氟-1-丙烯。作为含氢卤代烯烃,其中,优选1-氯-3,3,3-三氟丙 烯、1,3,3,3_四氟丙烯或1,1,1,4,4,4_六氟-2-丁烯。对于这些含氢卤代烯烃,可以单独使 用、也可以组合使用2种以上,进而,还可以添加其它的饱和含氢卤代烯烃来使用。
[0050] 本实施方式的碳数为6以下的烃为仅由氢原子和碳原子构成的化合物,例如,可以 列举出甲烷、乙烷、乙烯、丙烷、丙烯、正丁烷、异丁烷、丁烯、丁二烯、正戊烷、异戊烷、新戊 烷、戊烯、正己烷、异己烷、己烯等链烷、链烯、二烯烃等脂肪族烃、以及环丁烷、环戊烷、环己 烯等环烷、环烯等环状脂肪族烃。
[0051] 本实施方式的酚醛树脂发泡体中的、碳数为6以下的烃的含量与含氢卤代烯烃的 含量的总和(总量)在酚醛树脂发泡体内的平均每22.4 X 1 (T3m3(22.4L)的空间体积中为 0 • 23~0 • 90mol,优选为0 • 25~0 • 90mol、更优选为0 • 3~0 • 80mol、进一步优选为0 • 35~ 0.75mol、特别优选为0.40~0.70mol。碳数为6以下的烃以及含氢卤代烯烃的总量少于上述 0.23mol时,存在在绝热材料施工后气泡中内含的这些发泡气体随着时间经过而被置换成 空气的过程中绝热性能的降低变大的担心,进而,存在气泡中的内压过度降低而导致压缩 强度降低的倾向。碳数为6以下的烃以及含氢卤代烯烃的总量多于上述0.90mol时,气泡内 的内压变高,因此存在气泡中内含的气体容易液化,特别是1 〇 °C的初始绝热性能降低的担 心。
[0052] 本实施方式的酚醛树脂发泡体中的、含氢卤代烯烃的含量在酚醛树脂发泡体内的 平均每22 • 4 X 10-3m3 (22 • 4L)的空间体积中为0.05~0.85mol、优选为0 • 1~0 • 7mo 1、更优选 为0.2~0.6mol。含氢卤代烯烃的含量少于上述0.05mol时,存在不能充分地利用气体的热 导率低的特性,HTC以及23°C的初始绝热性能降低的倾向。含氢卤代烯烃的含量多于上述 0.85mol时,由于含氢卤代烯烃与酚醛树脂的高亲和性所造成的树脂的增塑而使发泡时的 酚醛树脂粘度变低。其结果,存在酚醛树脂发泡体的泡孔膜破裂,不能形成充分的独立气泡 结构,长期的绝热性能降低的担心。
[0053] 本实施方式的酚醛树脂发泡体中的、碳数为6以下的烃的含量在酚醛树脂发泡体 内的平均每22.4\10-3111 3(22.礼)的空间体积中为0.03~0.85111〇1、优选为0.05~0.85111〇1、 更优选为0.05~0.8mol、进一步优选为0.05~0.7mol、特别优选为0.05~0.6mol、最优选为 0.05~0.5mol。碳数为6以下的经的含量少于上述0.03mol时,不能抑制由含氢卤代稀经造 成的酚醛树脂的增塑,发泡时的酚醛树脂粘度变低。其结果,存在酚醛树脂发泡体的泡孔膜 破裂,不能形成充分的独立气泡结构,长期的绝热性能降低的担心。碳数为6以下的烃的含 量多于上述〇.85mol时,存在所得到的酚醛树脂发泡体的阻燃性恶化的倾向。
[0054] 本实施方式的酚醛树脂发泡体优选包含戊烷和/或戊烯(以下有时记载为戊烷类) 作为碳数6以下的烃。在本实施方式中,戊烷可以列举出正戊烷、异戊烷、新戊烷、环戊烷等。 所使用的戊烷类没有特别限制,从气体状态的热导率、发泡性、沸点等出发,适宜地使用环 戊烷以及异戊烷,特别适宜地使用环戊烷。这些戊烷类可以单独使用、也可以组合使用2种 以上的气体,进而,还可以混合其它的烃。
[0055] 本实施方式的酚醛树脂发泡体中的、碳数为6以下的烃与含氢卤代烯烃的沸点平 均值XI为-15 °C~48 °C即可。
[0056]作为含氢卤代烯烃,使用1-氯_3,3,3_三氟丙烯的情况下,本实施方式的酚醛树脂 发泡体中的、碳数为6以下的烃与1-氯-3,3,3-三氟丙烯的沸点平均值XI为15°C~45 °C即 可,优选为15 °C~40 °C、更优选为19 • 5 °C~37 °C。
[0057]作为含氢卤代烯烃,使用1,3,3,3_四氟丙烯的情况下,本实施方式的酚醛树脂发 泡体中的、碳数为6以下的烃与1,3,3,3-四氟丙烯的沸点平均值乂1为-15°(:~45°(:即可,优 选为-5 °C~40 °C、更优选为0 °C~30 °C。
[0058] 作为含氢卤代烯烃,使用1,1,1,4,4,4_六氟-2-丁烯的情况下,本实施方式的酚醛 树脂发泡体中的、碳数为6以下的烃与1,1,1,4,4,4_六氟-2-丁烯的沸点平均值XI为0°C~ 48 °C即可,优选为5 °C~40 °C、更优选为10 °C~35 °C。
[0059] 沸点平均值过低时,存在发泡速度变得过快,在发泡时泡孔膜破裂的倾向,因此担 心长期的绝热性能容易降低。另一方面,沸点平均值过高时,存在发泡剂容易液化,l〇°C下 的热导率上升的倾向。
[0060] 本实施方式的多种物质的沸点平均值X可以通过以下的式(1)而求出。
[0061 ]沸点平均值X = a X Ta+b X Tb+c X Tc+". (1)
[0062](上述式(1)中,作为对象的物质(A、B、C、"_)各自的含有率为a、b、c、'"(摩尔分 数)、沸点为 Ta、Tb、Tc、'"(°C)。)
[0063]本实施方式中的酚醛树脂发泡体优选在后述10°C以及23°C环境下所测定的热导 率均不足0.0205W/m • k、更优选不足0.0190W/m • k、进一步优选不足0.0185W/m • k、特别优 选不足0.0180W/m • k、最优选不足0.0175W/m • k。通常存在温度越低,绝热材料的热导率越 低的倾向。在后述l〇°C的环境下所测定的热导率优选不足0.0190W/m • k、更优选不足 0.0180W/m • k、进一步优选不足0.0175W/m • k、特别优选不足0.0170W/m • k、最优选不足 0.0165ff/m • k〇
[0064]在本实施方式中,对应于长时间使用的加速试验后的热导率