CN102159658A - 用于木板的胶层材料和木板 - Google Patents

用于木板的胶层材料和木板 Download PDF

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CN102159658A
CN102159658A CN2009801370056A CN200980137005A CN102159658A CN 102159658 A CN102159658 A CN 102159658A CN 2009801370056 A CN2009801370056 A CN 2009801370056A CN 200980137005 A CN200980137005 A CN 200980137005A CN 102159658 A CN102159658 A CN 102159658A
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layer
glue
film
mape
coupling agent
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S·基祖伦
R·劳迪埃宁
M·布勃
M·辛迪加
S·科波宁
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UPM Plywood Oy
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UPM Kymmene Wood Oy
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Priority claimed from FI20085897A external-priority patent/FI20085897A0/fi
Priority claimed from FI20085898A external-priority patent/FI20085898A0/fi
Application filed by UPM Kymmene Wood Oy filed Critical UPM Kymmene Wood Oy
Publication of CN102159658A publication Critical patent/CN102159658A/zh
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Abstract

本发明涉及用于木板的胶层材料。根据本发明,胶层材料由至少第一膜层(3)形成,并且所述膜包含至少三个膜层,并且至少外膜层含有聚烯烃和偶联剂,所述偶联剂与木材的-OH基团反应,形成自粘特性,使所述胶层材料与所述木材的-OH基团自粘。

Description

用于木板的胶层材料和木板
发明领域
本发明涉及如权利要求1前序中所限定的胶层(glue line)材料和如权利要求18前序中所限定的木板。
发明背景
从现有技术已知各种木板例如胶合板、单板或类似物。
从现有技术已知用于将单板胶合在一起形成木板的各种胶。同样已知的是,例如用聚氨酯胶或酚醛胶将涂层胶合到单板层上面。
从现有技术已知,在单独的加工阶段(working phase)将不同类型的粘合标签或产品说明胶合到木板表面上以提供产品信息。
从US 5243126、US 5654091、EP0782917、WO 9906210和EP 0429253已知不同的木材面板和粘合材料。
专利公开WO 03/033252公开了包含两层的复合材料,其中第一层由高强度纤维和树脂形成,以及第二层是结构覆板(structural sheathing),例如胶合板。高强度纤维选自芳香族聚酰胺纤维、玻璃纤维、聚乙烯纤维、聚乙烯醇纤维、聚芳酯纤维、聚对苯亚基苯并双
Figure BPA00001331364300011
唑纤维(polybenzazole fiber)或碳纤维。
发明目的
本发明的目的是公开一种新型胶层材料、其生产以及所述材料与木板的连接。此外,本发明的目的是公开偶联剂向活性形式的转化,用于形成所述材料以及用于将所述材料连接到木板上。
发明内容
根据本发明的胶层材料和木板以权利要求书中所说明的为特征。
本发明是基于用于木板的胶层材料。根据本发明,胶层材料由至少第一层——其由膜形成——形成,并且所述膜包含至少三个膜层,并且至少外膜层含有聚烯烃和偶联剂,所述偶联剂与木材的的-OH基团反应,形成自粘特性,使胶层材料与木材的-OH基团自粘。
本发明具体是基于具有某些特性和结构的胶层材料。胶层材料的层通过偶联剂,例如通过马来酸酐聚烯烃充分地连接在一起,所述偶联剂优选通过酯化与木材的-OH基团反应,形成自粘特性。胶层材料作为胶层和/或涂层与木板一起使用。
在该背景下,木板指任何木材面板产品、胶合板产品、复合材料产品、梁(beam)、压制面板产品或类似物,它们由许多层,优选单板层,并主要由木材基材料形成,其中所述层被彼此叠放并胶合在一起。此外,木板指任何木材产品或纤维产品。
在该背景下,层指任何材料层,通常指薄材料层。
在一个实施方式中,所述第一层是底层。
在本发明的一个实施方式中,胶层材料包含安排在第一层上的顶层。在本发明的一个实施方式中,顶层是保护层。优选顶层为其它层提供保护。
在本发明的一个实施方式中,胶层材料包含至少一个安排在第一层和顶层之间的中间层。在一个实施方式中,中间层安排在第一层和顶层之间,用于提供受保护的中间层。胶层材料可以包含一个以上中间层。
在本发明的一个实施方式中,胶层材料包含增强纤维。
在本发明的一个实施方式中,胶层材料包含至少一个增强层。在一个实施方式中,胶层材料包含至少两个增强层。在一个优选的实施方式中,偶联剂与增强层或增强纤维的-OH基团反应。
在本发明的一个实施方式中,第一层的膜是含有三个以上膜层的多层膜。
在本发明的一个实施方式中,顶层由膜形成。
在本发明的一个实施方式中,中间层由膜形成。
在本发明的一个实施方式中,膜是2层膜。在一个实施方式中,膜是3层膜。在一个实施方式中,膜是包含三个以上膜层例如3-11个膜层的多层膜。
优选层和膜层通过偶联剂例如通过马来酸酐聚烯烃连接在一起。优选膜是由偶联剂提供的自粘膜,所述偶联剂与其它材料例如天然产品如木材或木材衍生产物中的-OH基团反应。
在本发明的一个实施方式中,膜的至少一层含有偶联剂。
在优选的实施方式中,包括偶联剂的层、膜或膜层也含有聚合物例如聚乙烯或聚丙烯。
在本发明的一个实施方式中,偶联剂选自接枝硅烷、接枝异氰酸酯、接枝环氧基和马来酸酐聚烯烃,例如马来酸酐接枝聚丙烯(MAPP)、马来酸酐接枝共聚物和马来酸酐接枝聚乙烯(MAPE)。
在一个实施方式中,使用的马来酸酐聚烯烃是马来酸酐聚乙烯(MAPE)和/或马来酸酐聚丙烯(MAPP)。优选地,包括马来酸酐聚烯烃的膜层主要由MAPE+PE或MAPP+PP组成。在一个实施方式中,膜含有2-15%w/w的马来酸酐。
在一个实施方式中,偶联剂或偶联剂中的聚烯烃或含有偶联剂的膜接枝有含与聚烯烃反应的官能团的烷氧基硅烷。在一个实施方式中,聚烯烃接枝有可水解乙烯基-单-、-双-、或-三-烷氧基硅烷。在一个实施方式中,乙烯基基团可以被异氰酸酯-或环氧基团取代。烷氧基硅烷醇基团可以是甲基-、乙基-、丙基-或异丙基-基团,并且硅烷可以含有1、2或3个烷氧基基团。在制备偶联材料的过程中已经发生了聚烯烃与乙烯基或其它反应基团的反应,而通过硅烷-基团与木材的反应发生在制备木板的过程中或之后。
优选偶联剂形成共价键、酯键和/或通过与纤维素-OH基团酯化形成共价键。在一个实施方式中,偶联剂通过与材料-OH基团酯化形成共价键。
在本发明的一个实施方式中,在偶联材料制备过程中,偶联剂在大于180℃的温度下被活化。偶联材料可以通过共挤出进行制备。其它挤出方法也是可以的。挤出温度在180-200℃之间。在优选的实施方式中,应用了200℃的挤出熔化温度2分钟,这2分钟是足以将偶联剂转化成反应形式的时间。形成的偶联剂含有能够与木材中的-OH基团形成最大量共价键和/或酯键的活化官能团。聚烯烃的熔体指数为≤4g/10min(于190℃/2.16kg下测量),这使在膜形式中反应基团的活化成为可能。
在本发明优选的实施方式中,通过马来酸酐聚烯烃,将层连接在一起。马来酸酐形成共价键,优选通过与纤维素-OH基团酯化形成共价键。
优选马来酸在膜制备过程中转化成马来酸酐。可以通过共挤出聚烯烃和马来酸酐接枝聚烯烃来制备所述膜。其它挤出方法也是可以的。挤出温度在180-200℃之间。在涂覆过程的优选实施方式中,应用了200℃的挤出熔化温度2分钟,这2分钟是足以将偶联剂由马来酸转化成马来酸酐的时间。形成的膜含有能够与木材中的-OH基团形成最大量共价键的活化官能团。在一个实施方式中,在含有马来酸酐聚烯烃的膜或膜层中,马来酸酐转化多于86%,而未转化的马来酸转化少于14%。在一个优选的实施方式中,马来酸酐转化多于92%,而未转化的马来酸转化少于8%。
在本发明的一个实施方式中,顶层和/或中间层含有聚烯烃和偶联剂。
在本发明的一个实施方式中,第一层、中间层和/或顶层含有聚乙烯(PE)、聚丙烯(PP)、高密度聚乙烯(HDPE)、中密度聚乙烯(MDPE)、高分子量聚乙烯(HMWPE)、超高分子量聚乙烯(UHMWPE)、偶联剂,例如马来酸酐聚乙烯(MAPE)或马来酸酐聚丙烯(MAPP)、茂金属产生的聚乙烯(TIE)和/或其衍生物或其组合。层可以包括添加剂和填料。在优选的实施方式中,TIE-材料包括偶联剂。
在本发明的一个实施方式中,第一层、顶层和/或中间层含有聚烯烃,所述聚烯烃具有在0.1-4g/10min范围内的熔体流动指数和在100-140℃范围内的DSC熔化温度。
在一个实施方式中,具有低粘度的聚合物被用于2层膜和3层膜的外层中。在本发明的一个实施方式中,层含有聚烯烃,所述聚烯烃具有在0.3-4g/10min(于2.16kg和190℃下测量)范围内的熔体流动指数(MFI)和在100-140℃范围内的DSC(示差扫描量热法)熔化温度。在一个优选的实施方式中,该聚烯烃用于第一层和顶层的外层中,以改进外表面渗透到木材中。在一个实施方式中,该聚烯烃用于单膜中,以助于中间层与增强材料的粘合。
通过在中间层或中间膜层中使用高分子量的聚合物,可以提高聚合物的抗蠕变性。在一个实施方式中,中间层具有以下结构:MAPE+LDPE/HDPE/LDPE+MAPE、MAPE+LDPE/HDPE/HDPE、MAPE+LDPE/HDPE/MDPE、MAPE+LDPE/HDPE+MAPE/LDPE+MAPE,MAPE+LDPE/MDPE/LDPE+MAPE、MAPE+LDPE/MDPE+MAPE/LDPE+MAPE或MAPP+PP/PP/MAPP+PP。在一个实施方式中,聚合物的分子量为>100000,并且优选在100 000-500 000之间。聚合物的MFI与其分子量负相关,因此具有低MFI(在0.1-1.0g/10min范围内,于21.6kg和190℃下测量)的聚合物具有高分子量。在一个实施方式中,聚乙烯密度影响抗蠕变性,因此用在中间层的聚合物的密度在0.940-0.965g/cm3范围内。
在一个实施方式中,任意聚烯烃膜可以优选以膜体积1-15%的量含有矿物填料,例如PCC或氧化铝。
在一个实施方式中,使用的任意聚烯烃是交联的。通过聚烯烃的交联,可以提高抗蠕变性。此外,通过向层中添加MAPP和/或MAPE偶联剂,可以提高抗蠕变性。
在本发明的一个实施方式中,增强层可以含有不同的增强纤维和聚合物。增强层可以含有编织织物、非编织织物、编织纤维、非编织纤维、取向或非取向纤维材料、有机纤维、玻璃纤维、碳纤维、尼龙66、芳香族聚酰胺、天然纤维,例如亚麻、棉花、粘胶纤维浆或大麻纤维和/或其衍生物或它们的组合。此外,在优选的实施方式中,增强层含有聚烯烃,例如聚乙烯或聚丙烯;偶联剂,例如马来酸酐聚烯烃;和/或TIE,其优选是增强层的支撑材料。聚合物可以是聚烯烃或其共聚物或已知的生物聚合物,如乳酸聚合物、聚葡糖酸酯或多肽。在一个实施方式中,可以用具有比聚乙烯、聚丙烯或其它共聚物熔点高的聚合物来增强胶层材料。
在一个实施方式中,增强层与中间层安排在一起,例如在中间层旁边。在一个实施方式中,增强层安排在第一层和中间层之间。在一个实施方式中,增强层安排在中间层和顶层之间。在一个实施方式中,增强层安排在两个中间层之间。在一个实施方式中,交替的增强层和中间层结构由多达4个中间层和5个增强层形成。
在一个实施方式中,通过将增强纤维共挤出到支撑聚合物中而形成增强层。
通过增强纤维可以提高聚合物的抗蠕变性。同时可以充分提高弯曲强度。
根据纤维长度和挤出条件,在挤出过程中加载到聚合物的纤维或多或少被定向。如最终产品所要求的,放置于两个膜之间的织物在结构上可以被定向。
在一个实施方式中,胶层材料的至少一个膜层含有偶联剂。在一个实施方式中,膜的所有膜层均含有偶联剂。在一个实施方式中,膜的外膜层含有偶联剂。
在本发明优选的实施方式中,通过偶联剂,将层连接在一起并且将胶层材料附着到单板表面上。偶联剂通过酯化在两个层或膜或材料之间形成共价键。通过在外膜层中使用低粘度(MFI 0.3-4g/10min,于2.16kg和190℃下测量)和100-130℃DSC熔化温度的聚合物使更好地渗透到木材中,可以进一步提高粘合。马来酸聚烯烃可以用于所有膜层中,其对于0.1mm厚的膜是有利的,并且对于<0.1mm的较薄的膜是必需的。
在聚合物处于熔融状态时在热压(标准或连续压制)过程中通过施用剪切例如滚动、振动或旋转,可以增进膜渗透到木材中。剪切会导致粘度下降。
优选地,第一层和第三层渗透到多孔增强层中,形成坚固的复合层压板。
在一个实施方式中,至少一个膜层由热塑材料形成。
层、膜或膜层可以由石油化学原材料和可再生原材料制成。此外,可以使用生物塑料材料,优选具有超过180℃或超过190℃处理温度的生物基聚合物(bio-based polymer)。
在一个实施方式中,胶层材料包含RFID-识别器或RF-标签。在一个实施方式中,胶层材料包含导电材料,例如碳纤维或细金属纤维。导电层用于台面(table tops)上或用于加热目的。RFID-识别器、RF-标签或导电材料可以放置在中间层或增强层中。
层或层的至少一个膜层可以被印刷、涂漆和/或着色。
在一个实施方式中,所述层的所有膜层基本上由相同的材料形成。在可选的实施方式中,所述层的至少一个膜层由不同于其它膜层的材料形成。
胶层材料的层厚度可以根据膜材料的特性和木板的应用而变化。
相容性试剂可以加入到任意层中,以使不同的聚合物彼此粘附。当不同的聚合物被共挤出时,增强层中需要相容性试剂来连接不同的材料。
此外,本发明是基于木板,所述木板包含如上所限定的根据本发明的胶层材料。
根据本发明的木板可以包含不同厚度的单板层。单板层的厚度可以变化。单板层可以安排在期望的位置,即以期望的顺序交叉地或纵向地安排。
可以使用本身已知的设备和方法制作木板。叠放单板、将它们连接在一起以及制作木板过程中的其它常规步骤可以以本领域本身已知的任何方式进行。
在一个实施方式中,胶层材料安排在木板的单板之间。在一个实施方式中,胶层材料作为涂层安排在木板上。在优选的实施方式中,已经通过偶联剂将胶层材料与木板连接在一起。
在一个实施方式中,每个单板之间的胶层材料包含增强纤维。在一个实施方式中,一个或更多个单板之间的胶层材料包含纤维,但其它胶层仅由聚烯烃基膜组成。在一个实施方式中,纤维膜被安排来替代单板原料。这在纤维膜提供增加的强度和等于或大于单板的弯曲特性时尤是如此。
将本发明的胶层材料安排在单板或木板表面上可以如下进行:例如使用热压技术、挤出技术、膜技术、辊涂布技术(roll application technique)、筒涂布技术(cylinder application technique)、涂层和多层涂层涂布技术、所有本身已知的技术、其组合或相应的技术。例如使用热压技术可以将单板连接在一起。
本发明的胶层材料可以被预层压,以使处理更容易和更经济。
偶联剂例如马来酸聚合物廉价且无毒,并且它们形成不易水解的化学键。限定的偶联剂容易作为胶层来使用。在木材上的粘合极好。
单板层之间的纤维膜提高了建筑应用的弯曲强度。具有增强纤维的中间层也提高对射弹或极限载荷的抗性。
根据本发明的胶层材料和木板适于各种应用。这些类型的材料和产品可以与不同的结构,例如门、窗户保护罩、车辆地板和振动改变结构一起使用。
附图说明
下面,参考附图1a、1b、2和3,通过详细的实施方式对本发明进行描述,其中
图1a、1b和2显示了根据本发明的胶层材料;
图3显示了用于制作本发明胶层材料的方法;和
图4显示了ATR光谱学结果。
发明详述
图1a和1b公开了本发明的胶层材料结构。胶层材料是纤维-聚合物层压板。
顶层(1)由3层膜形成,其为PE/PE/MAPE+PE、MAPE+PE/PE/MAPE+PE、MAPE+PE/HDPE/MAPE+PE、MAPE+PE/MAPE+PE/MAPE+PE、MAPE+PE/MDPE/MAPE+PE、MAPE+PE/HMWPE/MAPE+PE、MAPE+PE/UHMWPE/MAPE+PE、MAPP+PP/PP/MAPP+PP、MAPP+PP/MAPP+PP/MAPP+PP、PP/MAPP+PP/MAPP+PP、PP/PP/MAPP+PP、PP/TIE/MAPE+PE、PA/TIE/MAPE+PE、PET/TIE/MAPE+PE或MAPP+PP/TIE/MAPE+PE。顶层的厚度为0.05-1mm。
中间层(4)由3层膜形成,其为MAPE+PE/PE/MAPE+PE、MAPE+PE/HMWPE/PE、MAPE+PE/HDPE/MAPE+PE、MAPE+PE/MAPE+PE/MAPE+PE、MAPP+PP/PP/MAPP+PP、MAPE+PE/HDPE+MAPE/MAPE+PE、MAPE+PE/MDPE+MAPE/MAPE+PE、MAPE+PE/UHMWPE+MAPE/MAPE+PE、MAPE+PE/MDPE+MAPE/MAPE+PE、MAPE+PE/MDPE/MAPE+PE、MAPE+PE/HMWPE/MAPE+PE、MAPE+PE/UHMWPE/MAPE+PE、MAPP+PP/MAPP+PP/MAPP+PP、PP/TIE/MAPE+PE或MAPP+PP/TIE/MAPE+PE。顶层的厚度为0.05-1mm。
增强层(2)由亚麻、大麻、粘胶纤维素、棉、聚乙烯醇、尼龙66、芳香族聚酰胺或玻璃纤维形成。此外,增强层可以包括PE、PP、MAPE、MAPP和/或TIE。增强层与中间层的外表面连接。增强纤维材料的熔点超过中间层聚烯烃的熔点。增强层的厚度为至少0.05-1mm,但可以更厚。增强材料可以由PE/PE+Fibres+MAPE/MAPE+PE、PP/PP+Fibres+MAPP/MAPP+PP、PP/TIE+Fibres/MAPE+PE、MAPE+PE/PE+Fibres+MAPE/MAPE+PE、MAPP+PP/PP+Fibres+MAPP/MAPP+PP组成。
中间层(4)和增强层(2)的组合可以由多达9层的增强层/中间层组成。
底层(3)由3层膜形成,其为MAPE+PE/PE/MAPE+PE、MAPE+PE/MAPE+PE/MAPE+PE、MAPE+PE/HDPE/MAPE+PE、MAPE+PE/MDPE/MAPE+PE、MAPE+PE/HMWPE/MAPE+PE、MAPE+PE/UHMWPE/MAPE+PE、MAPP+PP/PP/MAPP+PP、MAPP+PP/TIE/MAPE+PE或MAPP+PP/MAPP+PP/MAPP+PP。底层的厚度为0.1-1mm。
中间层夹在顶层和底层之间。所有层均为自粘膜并包括马来酸酐聚烯烃,如MAPE和/或MAPP。增强层(2)夹在顶层(1)和中间层(4)或交替的中间层(4)之间。最终增强层(2)夹在中间层(4)和底层(3)之间。中间层(4)和增强层(2)的组合可以由3-9个层(2)和层(4)的交替层组成。
至少一个膜层或一个层可以包括添加剂和/或填料。至少一个膜层或一个层可以被着色、涂漆和/或印刷。
图2公开了本发明的第二胶层材料结构。通过共挤出形成胶层材料,以便将聚合物膜层和具有增强纤维和聚合物的增强层共挤出,形成增强的胶层膜材料。
胶层材料可以由a)MAPE+PE(1)/PE+纤维+MAPE(2)/MAPE+PE(3);b)MAPP+PP(1)/PP+纤维+MAPP(2)/MAPP+PP(3);或c)MAPP+PP(1)/Tie+纤维(2)/MAPE+PE(3)组成。在这些优选的组成中,马来酸聚烯烃用于所有3个层中。外层提供与木材的粘合,而中间层将纤维包封在聚合物中。所有层的厚度在0.05-1mm之间。
此外,用于测试的木板根据图3进行制备。作为木板,可以使用胶合板、刨花板、高密度或中等密度纤维板或一些其它含有木材或其它植物纤维的压制的和胶合的板。
马来酸聚烯烃通常含有聚烯烃量的2-15%的马来酸。在挤出时,马来酸部分或全部转化成马来酸酐。如果其在任何情况下都提高产品的使用,聚合物膜也可以是可交联的。马来酸膜于120-170℃温度下被压制到木材表面以及其它膜和层上。为了包括塑料熔体流动,热压温度被设置为高于聚合物融化温度20-50℃很重要。顶层可以通过乙烯基-硅烷水解方法或电子束(EB)照射而交联。每个聚合物膜也可以含有高达聚合物体积30%的填料,如PCC(沉淀碳酸钙)或氧化铝等。
当在挤出机中混合时,纤维含量按体积计可以从1到40%。大于40%可能导致脆性材料。单独安排在聚合物膜层之间的纤维可以为20-120g/m2
通过热压以本身已知的方式可以将胶层材料安排在木板的单板上。
从试验中发现,本发明的材料是适合用作木板中胶层或涂层的胶层材料。
实施例1
在该实施例中,测试了本发明的增强胶层材料和增强材料。
表1显示了改性热塑膜的拉伸强度(EN789)和弹性模量(MOE)。从最大力的10-40%计算MOE。十字头(cross-head)距离为10mm,样品大小为50×250mm。辐射敏感膜在辐射之后具有更好的拉伸强度特性。通过辐射处理而交联聚乙烯似乎轻微地损害了膜的机械性能。将被期望的聚合物密度对聚合物的硬度有显著影响。
表1
Figure BPA00001331364300081
MI为聚合物的熔体流动指数。其是对熔体粘度的测量,但它是真正的粘度的倒数。
表2显示了不同纤维材料的拉伸强度(EN789)和弹性模量(MOE)。从最大力的10-40%计算MOE。十字头距离为10mm,样品大小为50×250mm。辐射敏感膜在辐射之后具有更好的拉伸强度特性。材料具有变化的机械性能。具有最佳拉伸特性的材料并不一定是具有最高MOE的材料。亚麻材料(编织)具有最高的拉伸强度特性,而玻璃纤维非编织材料具有最佳MOE。
表2
Figure BPA00001331364300091
表3显示了不同Colback S90(非编织合成聚合物)层压材料的拉伸强度(EN789)和弹性模量(MOE)。所述层压材料由底膜和顶膜(详述于表5中)以及Colback S90亚麻材料中间层组成。从最大力的10-40%计算MOE。十字头距离为10mm,样品大小为50×250mm。辐射敏感膜在辐射之后具有更好的拉伸强度特性。材料具有变化的机械性能。所有膜层中Profillin亚麻和HDPE的层压材料提供了MOE值与桦木单板相似的层压材料。
表3
Figure BPA00001331364300092
表4显示了重叠单亚麻纤维的结果。目的是发现临界重叠长度(10mm、15mm、20mm、25mm)。从表4看清楚的是,最小重叠长度为20mm,因为强度和硬度从10mm-20mm线性增加,然后在20mm之后呈平稳状态。
表4
  纤维重叠距离(mm)   MOE(N/mm2)   TS(N/mm2)
  10   8122   67.7
  15   10158   76.1
  20   11813   108.3
  25   12643   111.9
表5显示了不同的单亚麻和黄麻纤维层压材料的拉伸强度(EN789)和弹性模量(MOE  )。层压材料由底膜和顶膜(2%MAPE+MI-0.3PE/MI-0.3PE/3%MAPE+MI-0.3PE)以及黄麻或亚麻纤维中间层组成。从最大力的10-40%计算MOE。十字头距离为10mm,样品大小为50×250mm。辐射敏感膜在辐射之后具有更好的拉伸强度特性。很清楚,在两种纤维类型的机械性能开始降低之前,50%纤维含量为极限。除此之外,黄麻具有较好的总机械性能,这是由于与较亚麻相比其较好的连续长度。
表5
Figure BPA00001331364300101
表6显示了各种纤维增强层压涂层的泰伯磨损(taber)(EN14354)和抗冲击性(SS 839123)结果。层压材料由底膜和顶膜(2%MAPE+MI-0.3PE/MI-0.3PE/3%MAPE+MI-0.3PE)以及中间层(详述于表6中)组成。很清楚,涂层提高了耐磨性(泰伯磨损结果)和抗冲击性。
表6
Figure BPA00001331364300111
表7显示了含有增强黄麻和亚麻胶层的面板的弯曲强度和硬度。酚箔(phenol foil)被用作参考值。使用5mm桦木胶合板,其中增强黄麻和亚麻层压材料在每个单板之间。层压材料由底膜和顶膜(3%MAPE+MI-0.2HDPE/3%MAPE+MI-0.2HDPE/3%MAPE+MI-0.2HDPE)以及详述于表7的中间层组成。热压在下列条件下进行:150℃温度,0.5N/mm2以及90秒。很清楚,黄麻和亚麻纤维之间弯曲强度和硬度差异很小。根据分析,在纵向方向上,50%单纤维增强箔层压材料的强度和硬度(三点弯曲强度和弯曲模量)与单桦木单板大致相同。当没有使用纤维时,酚粘接的胶合板更好。这表明基体润湿纤维的重要性。
表7
表8显示了含有增强亚麻胶层的面板的弯曲强度和硬度。酚箔被用作参考值。使用7层桦木胶合板,其中增强亚麻层压材料用在胶合板的两个外单板任一侧之间。层压材料由底膜和顶膜(3%MAPE+MI-0.2HDPE/3%MAPE+MI-0.2HDPE/3%MAPE+MI-0.2HDPE)以及详述于表8的中间层组成。热压在下列条件下进行:140℃温度,1.7N/mm2和580秒。
表8
Figure BPA00001331364300121
从试验中发现,本发明的材料是适合用作木板中胶层或涂层的增强胶层材料。
实施例2
在该实施例中,测试了本发明胶层材料的稳定性。
表9至11和图4显示了马来酸向马来酸酐的转化,以及在马来酸酐被转化成活性状态之后其对胶层强度和膜稳定性的影响,以及朝向内的极性基团的接触角。
表9显示了在不同挤出温度下在马来酸酐接枝聚乙烯(Fusabond MB-226DE)膜2%MAPE+PE/PE/2%MAPE+PE的膜制备过程中向马来酸酐的转化。
表9
Figure BPA00001331364300122
从表9的结果看明显的是,在185℃的温度下3分钟,马来酸大部分转化成马来酸酐,因而可以认为,在聚合物处于熔体约2-3分钟的挤出过程中,>185℃的挤出温度是足够的,但优选>190℃。在煮沸后涂层胶层强度和木材破坏百分比处于与Wisa Multi-wall(0.4N/mm2,80-90%木材破坏)相似的水平,这也支持马来酸向马来酸酐的转化在>185℃的温度下是足够的。
一旦马来酸转化成马来酸酐,知道在足够湿气被吸收和马来酸酐转化回马来酸之前膜将保持在活性状态多久是重要的。含有活化材料的膜处于条件(湿度65%和温度23℃)下1个月、3个月、6个月和12个月。通过ATR-FTIR光谱学来分析膜。
图4和表10显示了比较200℃挤出2-3分钟的膜中(表9)马来酸酐的ATR光谱学结果,明显的是,足够的马来酸转化成马来酸酐,因而挤出温度和处理时间是足够的。图4显示了表10中示出的3种不同膜的ATR-FTIR光谱(45度锗ATR元件)。
表10
Figure BPA00001331364300131
结果显示,马来酸酐的量没有变化,以及图4中与膜-4相似的光谱产生在每个月后,共12个月。这表明在被聚乙烯包绕时马来酸酐是长期稳定的。这是由于聚乙烯的低吸水性,以及在固体状态下马来酸基团将不在聚合物表面而是朝向内因而被遮蔽的事实。只有在聚合物处于熔体时,马来酸基团才朝向外。亲水基团朝向内的理论得到表11中接触角结果的支持。表11显示了通过悬滴法对不同的活化3层共挤出膜测量的接触角(后退接触角和前进接触角)和表面自由能。使用两种测试液体,二碘甲烷(DIM)和水。将马来酸聚合物膜与含有其它极性基团(EVA)的膜进行比较。
表11
Figure BPA00001331364300132
根据本发明的胶层材料和木板在其不同的实施方式中均适用于不同类型的应用。
本发明的实施方式并不限于介绍的实施例,而是许多变化在所附权利要求书的范围内都是可能的。

Claims (20)

1.用于木板的胶层材料,特征在于所述胶层材料由至少第一层(3)形成,所述第一层由膜形成,并且所述膜包含至少三个膜层,并且至少外膜层含有聚烯烃和偶联剂,所述偶联剂与木材的-OH基团反应,形成自粘特性,使所述胶层材料与所述木材的-OH基团自粘。
2.根据权利要求1所述的材料,特征在于所述胶层材料包含安排在所述第一层(3)上的顶层(1)。
3.根据权利要求2所述的材料,特征在于所述胶层材料包含至少一个安排在所述第一层(3)和所述顶层(1)之间的中间层(4)。
4.根据权利要求1至3中任意一项所述的材料,特征在于所述胶层材料包含增强纤维(2)。
5.根据权利要求4所述的材料,特征在于所述胶层材料包含至少一个增强层(2)。
6.根据权利要求1至5中任意一项所述的材料,特征在于所述第一层(3)的膜是含有三个以上膜层的多层膜。
7.根据权利要求2所述的材料,特征在于所述顶层(1)由膜形成。
8.根据权利要求3所述的材料,特征在于所述中间层(4)由膜形成。
9.根据权利要求7或8所述的材料,特征在于所述膜是两层膜。
10.根据权利要求7或8所述的材料,特征在于所述膜是三层膜。
11.根据权利要求1至10中任意一项所述的材料,特征在于所述顶层(1)和/或中间层(4)含有聚烯烃和所述偶联剂。
12.根据权利要求1至11中任意一项所述的材料,特征在于所述偶联剂选自马来酸酐聚烯烃。
13.根据权利要求12所述的材料,特征在于在所述膜制备过程中,马来酸转化成马来酸酐,以便马来酸酐转化多于86%以及未转化的马来酸转化少于14%。
14.根据权利要求1至13中任意一项所述的材料,特征在于所述第一层(3)、顶层(1)和/或中间层(4)含有聚乙烯、聚丙烯、高密度聚乙烯、中密度聚乙烯、高分子量聚乙烯、超高分子量聚乙烯、马来酸酐聚乙烯、马来酸酐聚丙烯、茂金属产生的聚乙烯或其组合。
15.根据权利要求1至14中任意一项所述的材料,特征在于所述第一层(3)、顶层(1)和/或中间层(4)含有聚烯烃,所述聚烯烃具有在0.1-4g/10min范围内的熔体流动指数和在100-140℃范围内的DSC熔化温度。
16.根据权利要求1至15中任意一项所述的材料,特征在于所述增强层(2)含有聚烯烃、偶联剂、茂金属产生的聚乙烯、编织织物、非编织织物、编织纤维、非编织纤维、取向纤维材料、非取向纤维材料、有机纤维、玻璃纤维、碳纤维、尼龙66、芳香族聚酰胺、天然纤维、棉花、粘胶纸浆、大麻纤维或其组合。
17.根据权利要求1至16中任意一项所述的材料,特征在于通过共挤出制备所述膜,并且挤出温度在180-200℃之间,以在所述膜制备过程中激活所述偶联剂。
18.木板,特征在于所述木板包含根据权利要求1至17中任意一项所述的胶层材料。
19.根据权利要求18所述的木板,特征在于所述胶层材料安排在所述木板的单板之间。
20.根据权利要求18或19所述的木板,特征在于所述胶层材料安排在所述木板的表面上。
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