CN116529080A - 甲醛清除配制剂 - Google Patents
甲醛清除配制剂 Download PDFInfo
- Publication number
- CN116529080A CN116529080A CN202180077437.3A CN202180077437A CN116529080A CN 116529080 A CN116529080 A CN 116529080A CN 202180077437 A CN202180077437 A CN 202180077437A CN 116529080 A CN116529080 A CN 116529080A
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- CN
- China
- Prior art keywords
- dry mass
- formaldehyde
- flame retardant
- scavenger
- formulation
- 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.)
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- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 claims description 50
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Abstract
本发明涉及改善的甲醛清除配制剂及其在以下项中的用途:罩网和建筑产品,包括天花板砖,包括保温板、特别是酚醛保温板的板,以及包括木基面板和木材板的板和面板,同时涉及用于减少建筑产品的甲醛排放的方法。
Description
技术领域
本发明涉及改善的甲醛清除配制剂及其用途。特别的用途包括在以下项中:罩网(veils)(特别是非织造罩网)和建筑产品,包括天花板砖,包括保温板、特别是酚醛保温板的板,以及包括木基面板的板和面板,织物,纺织品,并且在其他基材上或被施加到其他基材。还公开了用于减少建筑产品的甲醛排放的方法。
背景技术
甲醛具有高潜在毒性,并且是一种刺激物,该刺激物可能会引起过敏反应和其他健康问题,包括对人类皮肤、呼吸道或眼睛的刺激。出版物《WHO Guidelines for IndoorAir Quality:Selected Pollutants》(World Health Organization,2010年,ISBN 978 92890 0213 4,第103-156页)进一步详细介绍了甲醛对健康的影响。Golden,R.(Crit RevToxicol.2011年9月;41(8):672–721;doi:10.3109/10408444.2011.573467;PMID:21635194)提供了对甲醛室内空气暴露极限的建议。
排放标准通过各种国家法律设定,包括法国法律Décret n°2011-321(2011年3月25日公布)。法国的排放等级在JOURNAL OFFICIEL DE LA(JORF no 0111,2011年5月13日,NOR:DEVL1104875A,附件I.D-“Arrêté étiquetage 2011”)中定义。VOC(挥发性有机化合物)排放的等级“A+”包括在28天内甲醛排放小于10ug/m^3的要求。VOC排放的等级“A”包括在28天内甲醛排放<60ug/m^3的要求。
因此必须控制/减少建筑产品的甲醛排放,以最大限度地降低健康风险并符合标准。因此减少建筑产品的甲醛排放是重要的。
还非常希望任何新的或改善的甲醛清除剂或组合物(即配制剂)(i)本身不存在额外的环境或健康和安全问题,包括在制造环境中,以及(ii)与现有的建筑产品制造方案和工艺条件相容,使得可在不必修改现有的建筑产品制造方案和工艺条件的情况下进行甲醛清除剂或组合物(即配制剂)的切换。
JP2009274409A公开了一种包含阻燃剂和甲醛清除剂的表面材料。
CN106346568A公开了一种阻燃复合脲醛树脂。
Ghani,A.等人(2018年6月,Building and Environment 142,doi:10.1016/ j.buildenv.2018.06.020)公开了通过添加胺作为甲醛清除剂来减少脲醛结合的碎料板的甲醛排放。
WO 2006/007168公开了用表面加工配制剂浸渍的纤维纱。
CA2657108(=WO 2008/012113)公开了包含多胺的木材材料用于减少环境空气中的甲醛含量的用途。
US 2010/0190021(US8460761)公开了一种通过用多胺进行处理来减少木材基材料中的甲醛排放的方法。
其他出版物包括EP3415475(US2010282996)、US3702798、US10035913、WO2006104455和WO2019133463。
发明内容
本发明寻求克服一个或多个现有技术缺陷,并提供改善的甲醛清除配制剂。
本发明的概述
根据本发明,提供了一种甲醛清除配制剂,该甲醛清除配制剂包含:
(a)甲醛清除剂(1-90重量%干质量),其中该甲醛清除剂是聚乙烯胺或其共聚物,和/或伯胺官能化的硅烷;
(b)粘结剂和/或交联剂(0-60重量%干质量);
(c)消泡剂(<0.5重量%干质量);
(d)碱(0-50重量%干质量);
(e)阻燃剂(0-96重量%干质量);和
(f)拒斥剂(<2重量%干质量)。
特别地,该甲醛清除剂可以是聚乙烯胺。
该聚乙烯胺可以以除纯聚乙烯胺之外的形式存在。它可例如以共聚物的形式存在,例如聚乙烯胺-聚乙烯醇(PVAm-PVOH)共聚物。
由特定的实施方案(下文)可以看出,(a)甲醛清除剂、(b)粘结剂和/或交联剂以及(c)消泡剂存在于本发明的所有实施方案中(实施例1-7和9)。因此,粘结剂和/或交联剂可以以<=60%的量存在。因此,粘结剂和/或交联剂的量可大于0%且小于或等于60%。
类似地,消泡剂存在于所有实施方案中,并且是以<0.5%的量。因此,消泡剂的量可被表示为大于0%且小于0.5%。
由特定的实施方案可以看出,碱、阻燃剂和拒斥剂各自在一种或多种实施方案中不存在。因此,该配制剂可包含以下物质中的至少之一:
(d)碱(<=50重量%干质量);
(e)阻燃剂(<=96重量%干质量);和
(f)拒斥剂(<2重量%干质量)。
在特别的实施方案中,该配制剂包含碱(<=50重量%干质量)。
在某些实施方案中,存在(d)、(e)和(f)中的两种。因此,在某些实施方案中,该配制剂包含以下物质中的至少两种:
(d)碱(<=50重量%干质量);
(e)阻燃剂(<=96重量%干质量);和
(f)拒斥剂(<2重量%干质量)。
在特别的实施方案中,该配制剂包含碱和阻燃剂。
在某些实施方案中,存在(d)、(e)和(f)中的全部三种。因此,在某些实施方案中,该配制剂包含以下物质中的全部三种:
(d)碱(<=50重量%干质量);
(e)阻燃剂(<=96重量%干质量);和
(f)拒斥剂(<2重量%干质量)。
该配制剂可任选地另外包含以下物质中的一种或多种:
(A)分散剂;
(B)粘度改进剂;和
(C)聚磷酸钠盐(NaPO3)n。
在某些实施方案中,该配制剂包含分散剂(<3重量%干质量)。
在某些实施方案中,该配制剂包含粘度改进剂(<3重量%干质量)。
在某些实施方案中,该配制剂包含聚磷酸钠盐(NaPO3)n(<10重量%干质量)。
在某些实施方案中,该配制剂另外包含颜料。在特别的实施方案中,其包含<5重量%干质量的颜料。颜料可特别用于隐藏或掩盖由例如配制剂的后续加工/使用的热冲击而引起的变色。例如,黑色颜料在某些实施方案中被用于隐藏由配制剂的后续加热而引起的变色。
如下面的实施例中详细描述的,本发明的配制剂在实现甲醛清除方面特别好。
该甲醛清除配制剂典型地是水性配制剂。
特别的甲醛清除配制剂包括:
磷-氮(P-N)阻燃剂配制剂–这种配制剂包括在实施例1中使用的配制剂。这种配制剂包含:
·甲醛清除剂(1-50重量%干质量),其中该甲醛清除剂是聚乙烯胺;
·粘结剂和/或交联剂(0-20重量%干质量);
·消泡剂(<0.5重量%干质量);
·阻燃剂(50-96重量%干质量),其中该阻燃剂是磷-氮阻燃剂;和
·拒斥剂(<2重量%干质量)。
如上所述,(a)甲醛清除剂、(b)粘结剂和/或交联剂、以及(c)消泡剂存在于所有实施方案中。因此,在这种P-N阻燃剂配制剂的情况下,粘结剂和/或交联剂可以以<=20%的量存在。因此,粘结剂和/或交联剂的量可大于0%且小于或等于20%。类似地,消泡剂以<0.5%的量存在。因此,消泡剂的量可表示为大于0%且小于0.5%。
从实施例1中可以看出,存在粘结剂和/或交联剂,即粘结剂和/或交联剂的量可表示为<=20%。因此,存在大于0%且小于或等于20%的粘结剂和/或交联剂。
在P-N阻燃剂配制剂的某些实施方案中,粘结剂和/或交联剂的量为<=15%(即大于0%且<=15%)。在P-N阻燃剂配制剂的某些实施方案中,粘结剂和/或交联剂的量为<=10%。在P-N阻燃剂配制剂的某些实施方案中,粘结剂和/或交联剂的量为<=8.0%。
在实施例1中,不存在碱。
如下所述,在某些实施方案中,还包含碱,特别是为了防止附聚。
ATH(三水合铝)阻燃剂配制剂-这种配制剂包括在实施例2-6(下文)中使用的配制剂。这种配制剂包含:
·甲醛清除剂(1-50重量%干质量),其中该甲醛清除剂是聚乙烯胺;
·粘结剂和/或交联剂(0-20重量%干质量);
·消泡剂(<0.5重量%干质量);
·碱(0-12.5重量%干质量)
·阻燃剂(50-96重量%干质量),其中该阻燃剂是三水合铝阻燃剂;和
·拒斥剂(<2重量%干质量)。
该配制剂的pH可以在9.5和10.5之间。
在配制剂包含碱的某些实施方案中,甲醛清除剂与碱的干重比在1:1至2:1的范围内。
如上所述,(a)甲醛清除剂、(b)粘结剂和/或交联剂、以及(c)消泡剂存在于所有实施方案中。因此,在ATH阻燃剂配制剂的情况下,粘结剂和/或交联剂可以以<=20%的量存在。因此,粘结剂和/或交联剂的量可大于0%且小于或等于20%。类似地,消泡剂以<0.5%的量存在。因此,消泡剂的量可表示为大于0%且小于0.5%。
在实施例2-6的每一个中,存在粘结剂和/或交联剂,即存在大于0%且小于或等于20%的粘结剂和/或交联剂。
在实施例2-6的每一个中,存在碱,阻燃剂也是如此。因此,在某些实施方案中,存在碱和阻燃剂二者。因此,在某些实施方案中,碱的量可表示为<=12.5%的量,即大于0%且<=12.5%的量。如上所述,阻燃剂的量可表示为50-96%。
在实施例3、4或6中不存在拒斥剂。因此,在ATH配制剂中,拒斥剂是任选的。
PVAm-丙烯酸系配制剂-这种配制剂包括在实施例7中使用的配制剂。这种配制剂包含:
·甲醛清除剂(10-90重量%干质量),其中该甲醛清除剂是聚乙烯胺;
·粘结剂和/或交联剂(0-50重量%干质量);
·消泡剂(<0.5重量%干质量);和
·碱(0-25重量%干质量)。
如上所述,(a)甲醛清除剂、(b)粘结剂和/或交联剂、以及(c)消泡剂存在于所有实施方案中。因此,在PVAm-丙烯酸系配制剂的情况下,粘结剂和/或交联剂可以以<=50%的量存在。因此,粘结剂和/或交联剂的量可大于0%且小于或等于50%。类似地,消泡剂以<0.5%的量存在。因此,消泡剂的量可表示为大于0%且小于0.5%。
从实施例7中可以看出,存在粘结剂和/或交联剂,即粘结剂和/或交联剂的量可表示为<=50%。
在实施例7中,存在碱,即碱的量可表示为<=25%。
因此,包含聚乙烯胺作为甲醛清除剂的实施方案可另外包含碱。在包含聚乙烯胺作为甲醛清除剂的某些实施方案中,它们包含<=25%的量的碱。
甲醛清除剂
典型地,聚乙烯胺(PVAm)具有的重均分子量(Mw)为50,000-800,000g/mol,200,000-600,000g/mol,更典型地为300,000-500,000g/mol,更典型地为约400,000g/mol。
在某些实施方案中,聚乙烯胺的干重百分比在1-60%的范围内,更典型地为1-45%。在某些实施方案中,其在1-30%的范围内。在其他实施方案中,其在5-30%的范围内。在其他实施方案中,其在1-15%的范围内。在某些实施方案中,其在2-11%的范围内。在一些实施方案中,其在2.5-7%的范围内。在一些实施方案中,其在3-5%的范围内。
在包含阻燃剂的实施方案中,阻燃剂和甲醛清除剂的总干重百分比可以是至少50%。在某些实施方案中,其为至少60%。在其他实施方案中,其为至少70%。在另外的实施方案中,其为至少80%。在某些实施方案中,其为至少90%。在其他实施方案中,其为至少95%。在某些实施方案中,其为至少96%。
在包含阻燃剂的实施方案中,阻燃剂与甲醛清除剂的干重比可以为至少2:1。其可以为至少3:1。其可以为至少4:1。其可以为至少5:1。其可以为至少10:1。其可以为至少15:1。其可以为至少20:1。其可以为至少25:1。
该配制剂中甲醛清除剂的干重百分比可根据该配制剂的预期用途、特别根据该配制剂被用于其上、其中或与其一起使用(例如向其施加或用在其中)的产品而显著变化。
粘结剂和/或交联剂
粘结剂包括诸如以下这类的物质:苯乙烯-丙烯酸酯共聚物、丙烯酸系化合物(acrylic)、乙烯-乙酸乙烯酯(EVA)、聚乙烯醇(PVOH/PVA)、聚氨酯(PU)、聚酯、聚乙烯吡咯烷酮(PVP)和淀粉衍生物等。水基聚合物乳液或溶液或二者的混合物是特别优选的。示例性的粘结剂是具有硅烷醇官能度的苯乙烯-丙烯酸酯共聚物的水性分散体。
合适的交联剂包括封端异氰酸酯交联剂,例如水基封端多异氰酸酯。
在某些实施方案中,粘结剂和/或交联剂为粘结剂的形式,粘结剂的干重百分比在1-60%的范围内。在某些这样的实施方案中,粘结剂的干重百分比在1-40%的范围内。在其他这样的实施方案中,其在5-35%的范围内。
在替代实施方案中,粘结剂和/或交联剂为交联剂的形式,交联剂的干重百分比在1-10%的范围内。在某些这样的实施方案中,其在2-9%的范围内。在其他这样的实施方案中,其在3-8%的范围内。在其他这样的实施方案中,其在4-7%的范围内。在另外的实施方案中,其在5-6%的范围内。
在一些实施方案中,存在粘结剂和交联剂二者。在某些实施方案中,粘结剂和交联剂的总干重百分比在1-15%的范围内,更典型地为3-12%,更典型地为5-9%。在某些这样的实施方案中,粘结剂与交联剂的干重比在2:1至20:1的范围内。在某些实施方案中,该比率在5:1至15:1的范围内。在其他实施方案中,该比率在8:1至12:1的范围内。在特别的实施方案中,该比率为大约10:1。
从上面对粘结剂和/或交联剂的讨论以及下面的各种特定实施方案可以看出,粘结剂和/或交联剂存在于所有实施方案中。因此,粘结剂和/或交联剂的范围可表示为<=60%。
从(i)粘结剂、(ii)交联剂和(iii)粘结剂加交联剂组合的上述可选范围可以看出,总范围可表示为至少1%的粘结剂和/或交联剂,即粘结剂和/或交联剂以1-60%的范围存在。
消泡剂
消泡剂在本领域中是众所周知的。合适的消泡剂包括(但不限于)基于聚二甲基硅氧烷(PDMS)油和乳液的那些。
在某些实施方案中,存在<0.1%的消泡剂。在某些实施方案中,存在<=0.05%的消泡剂。在某些实施方案中,消泡剂的量为>=0.01%且<0.1%。在某些实施方案中,消泡剂的量为>=0.01%且<=0.05%。在某些实施方案中,存在0.01%-0.02%的消泡剂。
碱
合适的碱对于本领域普通技术人员来说是显而易见的,包括(但不限于)Ca(OH)2、NaOH、KOH、Na2CO3、Mg(OH)2和Na3PO4。特别优选的碱是碳酸钠(Na2CO3)。
在某些实施方案中,碱的干重百分比在0-25%的范围内。因此,在包含碱的实施方案中,其可以以<=25%的量存在。在其它实施方案中,其在0.5-25%的范围内。在其他实施方案中,其在1-20%的范围内。在其他实施方案中,其在1.5-15%的范围内。
在包含碱的实施方案中,聚乙烯胺与碱的干重比可以在1:3至3:1的范围内。其可以在1:2至2:1的范围内。其可以在1:1至2:1的范围内。
碱在防止附聚方面特别有用。希望的是减少、最小化或完全避免附聚,因为它可具有不期望的效果。特别是,当过滤器被用作制造过程的一部分时,它可例如导致过滤器堵塞。类似地,附聚可导致在最终产品中不希望的结构效果(textural effects)/结块。
特别地,附聚可由例如甲醛清除剂与羧基基团和/或三烷氧基硅烷基团反应/对羧基基团和/或三烷氧基硅烷基团具有亲和性而产生。例如,羧基基团可以以聚羧酸钠和柠檬酸的形式存在于配制剂中使用的组分(如ATH阻燃剂或P-N阻燃剂)中存在的分散剂中。
利用不含任何碱的实施例1(下文)的配制剂进行的进一步实验表明,它有附聚的倾向。额外的实验(未详述)表明,向实施例1中使用的配制剂中加入碱(以Na2CO3的形式)防止了附聚的发生。
类似地,利用包含三烷氧基硅烷且无碱的配制剂进行的额外实验发现可发生附聚。向配制剂中引入碱的额外实验已经防止了附聚。
利用实施例2-7或9的配制剂没有观察到附聚。
因此,在某些实施方案中,该配制剂包含碱。
因此,在配制剂包含羧酸/聚羧酸的实施方案中,该配制剂可包含碱。类似地,在配制剂包含三烷氧基硅烷的实施方案中,该配制剂可包含碱。
特别地,碱可存在于配制剂中以预先制止可能的附聚。
阻燃剂
合适的阻燃剂包括(但不限于)三水合铝(ATH)和磷氮(P-N)阻燃剂。
拒斥剂
拒斥剂拒水剂和/或拒油剂。合适的拒斥剂包括(但不限于)碳氟化合物和全氟烷基官能化的丙烯酸酯。
分散剂
合适的分散剂包括(但不限于)聚羧酸分散剂,特别是盐溶液,例如聚羧酸分散剂的钠盐溶液。
添加剂
特别地,添加剂可包括聚磷酸钠盐(NaPO3)n。
用途
本发明的甲醛清除配制剂可被用在以下项中(例如被施加到以下项或被包含在以下项中):罩网(特别是非织造罩网)和建筑产品,包括天花板砖,包括保温板、特别是酚醛保温板的板,以及包括木基面板的板和面板,织物,纺织品,并且在其他基材上或被施加到其他基材。
罩网(veils)
根据本发明还提供涂覆有或包含根据本发明的甲醛清除配制剂的非织造罩网。
根据本发明还提供涂覆有或包含氨基硅烷或氨基前体基团官能化的硅烷的非织造罩网。如以下实施例中所示,氨基硅烷是一种有效的甲醛清除剂。氨基硅烷可以是例如包含氨基硅烷和水的甲醛清除配制剂的形式。典型地,氨基硅烷是伯氨基硅烷,即伯胺官能化的硅烷。示例性的氨基硅烷是γ-氨基丙基三乙氧基硅烷(H2NCH2CH2CH2Si(OCH2CH3)3)。
用于建筑产品的非织造罩网在本领域中是众所周知的,并且典型地包含掺和的、随机取向的增强纤维。罩网的纤维组分可以是任意的以下项:金属纤维,陶瓷纤维,矿物纤维,玻璃纤维,碳纤维,石墨纤维,聚合物纤维如芳香聚酰胺、聚酯、聚丙烯酸系化合物、聚酰胺、聚丙烯腈,天然纤维及其组合。特别地,罩网的纤维组分可以是玻璃纤维。罩网可包含20-130g/m^2的纤维。
罩网可包含最高达40g/m^2的甲醛清除剂。它可包含0.5-20g/m^2的甲醛清除剂。它可包含1-15g/m^2的甲醛清除剂。它可包含2-10g/m^2的甲醛清除剂。它可包含3-6g/m^2的甲醛清除剂。如以下实施例中所详述的,使用这些量的甲醛清除剂已经实现了优异的结果。
特别地,罩网可包含5-250g/m^2的甲醛清除配制剂,其中0.5-20g/m^2是甲醛清除剂。
建筑产品
根据本发明还提供建筑产品,该建筑产品在至少一个表面上具有根据本发明的非织造罩网。示例性的建筑产品包括天花板砖,墙板,保温板,石膏板和木基面板。特别地,该建筑产品可在正面和背面中的至少之一上具有根据本发明的非织造罩网。该建筑产品可由诸如玻璃棉、岩棉、石材棉(stone wool)或矿物棉的棉(wool)制成。包括木基面板的产品包括但不限于地砖和家具。天花板砖包括但不限于湿毡板。
在天花板砖(ceiling tile)的情况下,它可在其正面和背面中的至少之一上具有根据本发明的非织造罩网。该天花板砖可包含甲醛释放粘结剂。该天花板砖可由棉(wool)制成。该棉可以是玻璃棉、岩棉、石材棉或矿物棉。
在墙板的情况下,它可在其正面和背面中的至少之一上具有根据本发明的非织造罩网。该墙板可包含甲醛释放粘结剂。该墙板可由棉(wool)制成。该棉可以是玻璃棉、岩棉、石材棉或矿物棉。
在保温板(insulation board)的情况下,它可在其正面和背面中的至少之一上具有根据本发明的非织造罩网。该保温板可以是酚醛泡沫板或矿物棉板。
在木基面板(wood based panel)(WBP)的情况下,它可在其正面和背面中的至少之一上具有根据本发明的非织造罩网,或者被包含在层压板中。
在建筑产品是木基面板的情况下,甲醛清除剂在甲醛清除配制剂中的干重百分比可在10-40%的范围内。在某些这样的实施方案中,其在15-35%的范围内。在其他这样的实施方案中,其在20-30%的范围内。在其中配制剂还包含阻燃剂的某些这样的实施方案中,阻燃剂与甲醛清除剂的干重比可在5:1至2:1的范围内。
在建筑产品是天花板砖或墙板的情况下,甲醛清除剂在甲醛清除配制剂中的干重百分比可在2-11%的范围内。在某些这样的实施方案中,其可在3-6%的范围内。在其中配制剂还包含阻燃剂的某些这样的实施方案中,阻燃剂与甲醛清除剂的干重比可为至少10:1。在某些这样的实施方案中,其为至少15:1。在某些这样的实施方案中,其为至少20:1。在其他这样的实施方案中,其为至少25:1。
在建筑产品是保温板如酚醛保温板的情况下,甲醛清除剂的干重百分比可在1-20%的范围内。在某些实施方案中,其在5-15%的范围内。在特别的实施方案中,其在7.5-12.5%的范围内。在其中配制剂还包含阻燃剂的某些这样的实施方案中,阻燃剂与甲醛清除剂的干重比可在2:1至10:1的范围内。在某些这样的实施方案中,其在3:1至9:1的范围内。在某些这样的实施方案中,其在4:1至8:1的范围内。
根据本发明还提供减少建筑产品的甲醛排放的方法,该方法包括将根据本发明的非织造罩网附着到建筑产品的至少一个外表面的步骤。
该至少一个外表面可以是该产品的至少一个主表面,例如前表面,或者前表面和后表面二者。建筑产品的实例是砖(例如天花板砖)和面板和板(例如墙板、天花板和保温板)。
本文用于具体说明包含组分的术语“包含(comprising)”还包括其中不存在其他组分的实施方案。
具体实施方式
现在将仅通过实施例的方式来描述本发明的实施方案。
详细说明
在整个说明书中使用的重量%值基于总干重。
在以下实施例中,根据本发明的甲醛清除配制剂和建筑产品显示出优异的结果。
实施例1
在本实施例中,使用木基面板(WBP)作为甲醛释放源。面板的后侧和边缘用非散发铝带覆盖(“WBP+配方1/x25g 2侧”除外,其中后侧用清除罩网覆盖)。在51L的室中,散发表面为约0.06m^2。考虑到天花板负载因数,甲醛浓度(μg/m^3)在欧洲标准室中估算给出。
在清除罩网上使用的“配方1”清除剂配制剂为:
类别 | 固体(%) | Kg湿 | %干 |
消泡剂 | 0.5% | 2.0 | 0.01% |
PN阻燃剂 | 50.0% | 149.9 | 65.59% |
清除剂(PVAm) | 21.0% | 149.9 | 27.55% |
拒斥剂 | 30.0% | 3.6 | 0.94% |
交联剂 | 45.0% | 15.0 | 5.90% |
样品:
木基面板(WBP):未经覆盖的木材面板(unfaced wood panel)
WBP+NS罩网:木材面板+1个施加到表面上的非清除罩网
WBP+配方1/x12g:木材面板+1个清除罩网(12g/m2添加量,意味着3.3g/m2 PVAm)
WBP+配方1/x25g:木材面板+1个清除罩网(25.7g/m2添加量,意味着7.1g/m2 PVAm)
WBP+配方1/x25g 2侧:木材面板+1个在前侧上的清除罩网+1个在后侧上的清除罩网(两次25.7g/m2添加量,意味着两次7.1g/m2 PVAm),散发表面=0.12m2。
结果:
结果表明,配方1WBP面板中的每一个都比未经覆盖/未经处理的木材面板和非清除罩网具有显著减少的甲醛排放。特别地,WBP+配方1/x25g 2侧产品实现了优异的结果。
进一步的测试表明,WBP+配方1/x25g 2侧产品28天的甲醛排放为<10ug/m^3。
实施例2和3
在本实施例中,使用木基面板作为甲醛释放源。面板的后侧和边缘用非散发铝带覆盖。在51L的室中,散发表面为约0.06m^2。考虑到天花板负载因数,甲醛浓度(μg/m^3)在欧洲标准室中估算给出。
在清除罩网上使用的“配方2”清除剂配制剂(实施例2)为:
组分 | 固体(%) | Kg湿 | Kg干 |
消泡剂 | 0.5% | 8.1 | 0.01% |
ATH阻燃剂 | 68.0% | 322.1 | 69.73% |
碱 | 7.5% | 450.9 | 10.77% |
清除剂(PVAm) | 21.0% | 161.0 | 10.77% |
丙烯酸系粘结剂 | 50.0% | 49.9 | 7.95% |
拒斥剂 | 30.0% | 8.1 | 0.77% |
在清除罩网上使用的“配方3”清除剂配制剂(实施例3)为:
组分 | 固体(%) | Kg湿 | Kg干 |
消泡剂 | 0.5% | 8.1 | 0.01% |
ATH阻燃剂 | 68.0% | 324.7 | 70.28% |
碱 | 7.5% | 454.5 | 10.85% |
清除剂(PVAm) | 21.0% | 162.3 | 10.85% |
丙烯酸系粘结剂 | 50.0% | 50.3 | 8.01% |
样品:
木基面板(WBP):未经覆盖的木材面板
WBP+A:木材面板+1个施加到表面上的清除罩网(配方2,45g/m2添加量,意味着4.9g/m2 PVAm)
WBP+B:木材面板+1个施加到表面上的清除罩网(配方3,45g/m2添加量,意味着4.9g/m2 PVAm)
WBP+NS罩网:木材面板+1个施加到表面上的非清除罩网
结果:
QL=定量限。对于参考室来说,定量限为0.3μg/m^3(SERA甲醛:约0.4ug/m^2.h)。
结果表明,与未经覆盖/未经处理的木材面板和非清除罩网(NS罩网)相比,具有使用配方2和配方3配制剂的罩网的面板具有非常显著减少的甲醛排放。
特别是,由于具有使用配方2和配方3配制剂的罩网的面板的甲醛排放无法量化,并且由于排放率随时间的推移而降低,因此可以得出结论,在28天后,28天的甲醛排放将<10ug/m^3。
实施例4
在本实施例中,甲醛清除剂配制剂如下所示:
组分 | 固体(%) | Kg湿 | Kg干 |
消泡剂 | 0.5% | 5.6 | 0.01% |
ATH阻燃剂 | 68.0% | 658.8 | 89.25% |
碱 | 7.5% | 110.0 | 1.64% |
清除剂(PVAm) | 21.0% | 74.8 | 3.13% |
丙烯酸系粘结剂 | 50.0% | 59.9 | 5.96% |
这样,清除剂(即配制剂)被添加到罩网中,如下所示:
清除剂(g/m2) | 4.38 |
总添加量(包括清除剂)(g/m2) | 140 |
实施例5
在本实施例中,甲醛清除剂配制剂如下所示:
组分 | 固体(%) | Kg湿 | Kg干 |
消泡剂 | 0.5% | 5.6 | 0.01% |
ATH阻燃剂 | 68.0% | 654.4 | 88.21% |
碱 | 7.5% | 109.3 | 1.62% |
清除剂(PVAm) | 21.0% | 74.4 | 3.10% |
丙烯酸系粘结剂 | 50.0% | 59.5 | 5.90% |
拒斥剂 | 30.0% | 9.9 | 0.59% |
交联剂 | 45.0% | 6.5 | 0.58% |
这样,清除剂(即配制剂)被添加到罩网中,如下所示:
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实施例6
在本实施例中,甲醛清除剂配制剂如下所示:
组分 | 固体(%) | Kg湿 | Kg干 |
消泡剂 | 0.5% | 12.7 | 0.02% |
ATH阻燃剂 | 68.0% | 580.8 | 93.41% |
碱 | 7.5% | 90.7 | 1.61% |
清除剂(PVAm) | 21.0% | 65.3 | 3.25% |
丙烯酸系粘结剂 | 50.0% | 14.5 | 1.72% |
这样,清除剂(即配制剂)被添加到罩网中,如下所示:
清除剂(g/m2) | 3.67 |
总添加量(包括清除剂)(g/m2) | 113 |
实施例7
组分 | 固体(%) | Kg湿 | Kg干 |
消泡剂 | 0.5% | 67.3 | 0.21% |
碱 | 7.5% | 480.6 | 22.24% |
清除剂(PVAm) | 21.0% | 346.1 | 44.85% |
丙烯酸系粘结剂 | 50.0% | 106.0 | 32.70% |
这样,清除剂被添加到罩网中,如下所示:
清除剂(g/m2) | 4.48 |
总添加量(包括清除剂)(g/m2) | 10 |
实施例8(参考实施例)
在本实施例中,使用木基面板作为甲醛释放源。面板的背(后)侧和边缘用非散发铝带覆盖。在51L的室中,散发表面为约0.06m^2。考虑到天花板负载因数,甲醛浓度(μg/m^3)在欧洲标准室中估算给出。
在清除罩网上使用的“配方4”清除剂配制剂为:
组分 | 固体(%) | Kg湿 | Kg干 |
清除剂(氨基硅烷) | 58.0% | 100 | 100.000% |
加入水以达到适用于施用方法和所需干添加量的组合物(即配制剂)。
样品:
木基面板(WBP):未经覆盖的木材面板
WBP+配方4:木材面板+1个清除罩网(纯清除剂,9g/m^2添加量,意味着9g/m^2清除剂)
结果
结果表明,与参考WBP相比,具有使用氨基硅烷的罩网的面板实现了良好的结果。这表明氨基硅烷适合用作甲醛清除剂。
实施例9
在本实施例中,甲醛清除剂配制剂如下所示:
组分 | 固体(%) | Kg湿 | Kg干 |
消泡剂 | 0.5% | 26.0 | 0.01% |
ATH阻燃剂 | 60.0% | 3392.0 | 87.53% |
碱 | 15.0% | 350.0 | 2.26% |
清除剂(PVAm) | 21.0% | 340.0 | 3.07% |
丙烯酸系粘结剂 | 50.0% | 272.0 | 5.85% |
拒斥剂 | 30.0% | 50.0 | 0.65% |
交联剂 | 45.0% | 33.0 | 0.64% |
与参考WBP相比,获得了改善的甲醛清除结果。
在不背离本发明的范围和精神的情况下,对本领域技术人员来说,本发明的所描述的实施方案的各种修改和变化将是显而易见的。尽管已经结合特定的实施方案描述了本发明,但应当理解,如所要求保护的发明不应当过度地局限于这样的特定实施方案。事实上,本领域技术人员显而易见的对所描述的实施本发明的模式的各种修改旨在被本发明覆盖。
Claims (18)
1.甲醛清除配制剂,包含:
(a)甲醛清除剂(1-90重量%干质量),其中该甲醛清除剂是聚乙烯胺或其共聚物,和/或伯胺官能化的硅烷;
(b)粘结剂和/或交联剂(<=60重量%干质量);和
(c)消泡剂(<0.5重量%干质量);
以及以下物质中的至少之一:
(d)碱(<=50重量%干质量);
(e)阻燃剂(<=96重量%干质量);和
(f)拒斥剂(<2重量%干质量)。
2.根据权利要求1所述的甲醛清除配制剂,包含碱(<=50重量%干质量)。
3.根据权利要求2所述的甲醛清除配制剂,包含0.5-25重量%干质量的碱。
4.根据前述权利要求中任一项所述的甲醛清除配制剂,任选地另外包含以下物质中的至少之一:
(A)分散剂;
(B)粘度改进剂;和
(C)聚磷酸钠盐(NaPO3)n。
5.根据前述权利要求中任一项所述的甲醛清除配制剂,另外包含颜料。
6.根据前述权利要求中任一项所述的甲醛清除配制剂,其中其是水性配制剂。
7.根据前述权利要求中任一项所述的甲醛清除配制剂,其中该阻燃剂选自:三水合铝(ATH)和磷氮(P-N)阻燃剂。
8.根据前述权利要求中任一项所述的甲醛清除配制剂,其中其包含:
·甲醛清除剂(1-50重量%干质量),其中该甲醛清除剂是聚乙烯胺;
·粘结剂和/或交联剂(<=20重量%干质量);
·消泡剂(<0.5重量%干质量);
·阻燃剂(50-96重量%干质量),其中该阻燃剂是磷-氮阻燃剂;和
·拒斥剂(<2重量%干质量)。
9.根据权利要求1-7中任一项所述的甲醛清除配制剂,其中其包含:
·甲醛清除剂(1-50重量%干质量),其中该甲醛清除剂是聚乙烯胺;
·粘结剂和/或交联剂(<=20重量%干质量);和
·消泡剂(<0.5重量%干质量);
以下物质中的至少之一:
·碱(<=12.5重量%干质量)
·阻燃剂(50-96重量%干质量),其中该阻燃剂是三水合铝阻燃剂;和
·拒斥剂(<2重量%干质量)。
10.根据权利要求1-7中任一项所述的甲醛清除配制剂,其中其包含:
·甲醛清除剂(10-90重量%干质量),其中该甲醛清除剂是聚乙烯胺;
·粘结剂和/或交联剂(<=50重量%干质量);
·消泡剂(<0.5重量%干质量);和
·碱(<=25重量%干质量)。
11.根据前述权利要求中任一项所述的甲醛清除配制剂,其中聚乙烯胺(PVAm)具有的重均分子量(Mw)在50,000-800,000g/mol的范围内。
12.涂覆有或包含根据前述权利要求中任一项所述的甲醛清除配制剂的非织造罩网。
13.涂覆有或包含氨基硅烷的非织造罩网。
14.根据权利要求12或13所述的非织造罩网,其中该罩网是玻璃纤维非织造罩网。
15.建筑产品,该建筑产品在至少一个表面上具有根据权利要求12-14中任一项所述的非织造罩网。
16.根据权利要求15所述的建筑产品,其中该建筑产品由选自玻璃棉、岩棉、石材棉和矿物棉的棉制成。
17.根据权利要求15或16所述的建筑产品,其中该建筑产品选自天花板砖、墙板、保温板和木基面板。
18.减少建筑产品的甲醛排放的方法,该方法包括将根据权利要求12-14中任一项所述的非织造罩网附着到该建筑产品的至少一个外表面上的步骤。
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EP20208236 | 2020-11-17 | ||
EP20208236.8 | 2020-11-17 | ||
PCT/IB2021/060647 WO2022107012A1 (en) | 2020-11-17 | 2021-11-17 | Formaldehyde-scavenging formulation |
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CN116529080A true CN116529080A (zh) | 2023-08-01 |
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US (1) | US20240002683A1 (zh) |
EP (1) | EP4247639A1 (zh) |
JP (1) | JP2023549560A (zh) |
KR (1) | KR20230109653A (zh) |
CN (1) | CN116529080A (zh) |
CA (1) | CA3201963A1 (zh) |
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US3702798A (en) | 1969-08-14 | 1972-11-14 | Owens Corning Fiberglass Corp | Vitreous fibers bonded with a thermoset resin including two organo-silicon compounds |
WO2006007168A1 (en) | 2004-06-18 | 2006-01-19 | Owens Corning | Fibrous veil impregnated with surface finish formulation |
RU2007140370A (ru) | 2005-04-01 | 2009-05-10 | Акцо Нобель Коатингс Интернэшнл Б.В. (Nl) | Способ снижения выделения альдегида из продуктов на основе древесины |
AU2007206994B2 (en) | 2006-01-17 | 2011-02-10 | Basf Se | Method for the reduction of formaldehyde emissions in wood materials |
PL2049598T3 (pl) | 2006-07-27 | 2010-12-31 | Basf Se | Zastosowanie materiałów drzewnych zawierających poliaminę do obniżania zawartości formaldehydu w powietrzu otoczenia |
FR2924719B1 (fr) | 2007-12-05 | 2010-09-10 | Saint Gobain Isover | Composition d'encollage pour laine minerale comprenant un monosaccharide et/ou un polysaccharide et un acide organique polycarboxylique, et produits isolants obtenus. |
JP5225750B2 (ja) | 2008-05-19 | 2013-07-03 | 旭化成建材株式会社 | 難燃フェノール樹脂発泡体積層板とその製造方法 |
GB201412706D0 (en) | 2014-07-17 | 2014-09-03 | Knauf Insulation And Knauf Insulation Ltd | Improved binder compositions and uses thereof |
CN106346568A (zh) | 2016-08-29 | 2017-01-25 | 南宁市创锦胶合板有限责任公司 | 采用阻燃复合脲醛树脂生产全桉木胶合板的方法 |
EP3732037A1 (en) | 2017-12-26 | 2020-11-04 | Cytec Industries Inc. | Fire retardant veil for use in composite materials |
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- 2021-11-17 CN CN202180077437.3A patent/CN116529080A/zh active Pending
- 2021-11-17 CA CA3201963A patent/CA3201963A1/en active Pending
- 2021-11-17 MX MX2023005753A patent/MX2023005753A/es unknown
- 2021-11-17 US US18/252,758 patent/US20240002683A1/en active Pending
- 2021-11-17 WO PCT/IB2021/060647 patent/WO2022107012A1/en active Application Filing
- 2021-11-17 JP JP2023529935A patent/JP2023549560A/ja active Pending
- 2021-11-17 EP EP21814908.6A patent/EP4247639A1/en active Pending
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CA3201963A1 (en) | 2022-05-27 |
WO2022107012A1 (en) | 2022-05-27 |
MX2023005753A (es) | 2023-08-02 |
US20240002683A1 (en) | 2024-01-04 |
JP2023549560A (ja) | 2023-11-27 |
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