CN107406733B - 真空热成型用粘结剂组合物及使用其的真空热成型用装饰薄片 - Google Patents
真空热成型用粘结剂组合物及使用其的真空热成型用装饰薄片 Download PDFInfo
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- CN107406733B CN107406733B CN201680013935.0A CN201680013935A CN107406733B CN 107406733 B CN107406733 B CN 107406733B CN 201680013935 A CN201680013935 A CN 201680013935A CN 107406733 B CN107406733 B CN 107406733B
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- Adhesives Or Adhesive Processes (AREA)
Abstract
本发明提供如下的真空热成型用粘结剂组合物,即,包含聚氨酯聚合物及丙烯酸聚合物,熔融温度与交联温度之差为30℃至60℃。并且,提供如下的真空热成型用装饰薄片,即,包括:粘结层;基材层,形成于上述粘结层的上部;印刷层,形成于上述基材层的上部;以及透明基材层,形成于上述印刷层的上部,上述粘结层由上述真空热成型用粘结剂组合物形成。
Description
技术领域
本发明涉及真空热成型用粘结剂组合物及使用其的真空热成型用装饰薄片。
背景技术
与其它汽车部件相比,现有的汽车内饰材料的设计用部件并不占据很大的比重,但随着消费者需求逐渐变得多样化,并且以各汽车种类实现设计及功能的差别化,也正加速进行针对汽车内饰材料用膜材料的研究和发展。
最近,在汽车装饰用膜材料中,随着包括单纯地提高装饰性、设计性在内的赋予触感性能的需求(needs)的增加,使三维表面装饰工艺的适用范围扩大,并且使用通过真空热成型法来使装饰薄片附着于注塑物的工艺。此时,为了使装饰薄片顺畅地熔敷于内饰材料,需要进行针对如下的粘结层的研究,即,上述粘结层具有优秀的的粘结力,当根据高温高压条件通过调节官能团的反应性来成型时,具有柔韧性,并且可附着于内饰材料。
发明内容
本发明要解决的技术问题
本发明提供如下的真空热成型用粘结剂组合物,即,包含聚氨酯聚合物及丙烯酸聚合物,熔融温度与交联温度之差为30℃至60℃。
并且,本发明提供如下的真空热成型用装饰薄片,即,包括:粘结层;基材层,形成于上述粘结层的上部;印刷层,形成于上述基材层的上部;以及透明基材层,形成于上述印刷层的上部,上述粘结层由上述真空热成型用粘结剂组合物形成。
但是,本发明所要解决的技术问题并不局限于以上所述的问题,本发明所属技术领域的普通技术人员可从以下的记载中明确地理解未提及的其他问题。
技术方案
本发明提供如下的真空热成型用粘结剂组合物,即,包含聚氨酯聚合物及丙烯酸聚合物,熔融温度及交联温度之差为30℃至60℃。
本发明可提供如下的真空热成型用粘结剂组合物,即,上述熔融温度为50℃至90℃,上述交联温度为110℃至150℃。
本发明可提供如下的真空热成型用粘结剂组合物,即,相对于100重量份的上述真空热成型用粘结剂组合物的固体成分,包含1重量份至10重量份的上述丙烯酸聚合物。
本发明可提供如下的真空热成型用粘结剂组合物,即,上述丙烯酸聚合物的重均分子量为200000至800000。
本发明可提供如下的真空热成型用粘结剂组合物,即,相对于100重量份的上述真空热成型用粘结剂组合物的固体成分,包含90重量份至99重量份的上述聚氨酯聚合物。
本发明可提供如下的真空热成型用粘结剂组合物,即,上述聚氨酯聚合物的重均分子量为1000至30000。
本发明可提供如下的真空热成型用粘结剂组合物,即,上述聚氨酯聚合物由异氰酸酯化合物以及多元醇化合物制备而成。
本发明可提供如下的真空热成型用粘结剂组合物,即,上述多元醇化合物包含选自由聚酯类多元醇、内酯类多元醇、聚碳酸酯类多元醇、聚醚类多元醇以及它们的组合组成的组中的一种以上。
本发明可提供如下的真空热成型用粘结剂组合物,即,还包含添加剂,上述添加剂包含选自由粘结性赋予树脂、低分子量化合物、环氧树脂、固化剂、紫外线稳定剂、抗氧化剂、调色剂、加固剂、消泡剂、表面活性剂、增塑剂、发泡剂、有机盐以及它们的组合组成的组中的至少一种。
本发明可提供如下的真空热成型用粘结剂组合物,即,上述真空热成型用粘结剂组合物的粘度为800cps至7000cps。
本发明提供如下的真空热成型用装饰薄片,即,包括:粘结层;基材层,形成于上述粘结层的上部;印刷层,形成于上述基材层的上部;以及透明基材层,形成于上述印刷层的上部,上述粘结层由如上所述的真空热成型用粘结剂组合物形成。
本发明可提供如下的真空热成型用装饰薄片,即,上述粘结层的厚度为10μm至50μm。
本发明可提供如下的真空热成型用装饰薄片,即,上述基材层包含选自由聚甲基丙烯酸甲酯(PMMA)、丙烯腈-丁二烯-苯乙烯(ABS)、热塑性聚烯烃(TPO)、聚氯乙烯(PVC)、聚碳酸酯(PC)及它们的组合组成的组中的一种。
本发明可提供如下的真空热成型用装饰薄片,即,在上述粘结层的下部还包括离型膜层。
本发明可提供如下的真空热成型用装饰薄片,即,上述离型膜层包括聚对苯二甲酸乙二醇酯(PET)膜。
本发明可提供如下的真空热成型用装饰薄片,即,利用选自由凹版印刷、柔版印刷、圆网印刷以及它们的组合组成的组中的至少一种方法来形成上述印刷层。
本发明可提供如下的真空热成型用装饰薄片,即,在上述透明基材层的上部还包括压花层。
本发明可提供如下的真空热成型用装饰薄片,即,利用压花工序来形成上述压花层。
有益效果
本发明的真空热成型用粘结剂组合物可通过以规定比率包含特定重均分子量的聚氨酯聚合物及丙烯酸聚合物来使熔融温度与交联温度差达到30℃至60℃,由此减少常温下的热化,并具有高温耐久性。
因此,在具有由上述真空热成型用粘结剂组合物形成的粘结层的装饰薄片中,在通过真空热成型工艺来使上述装饰薄片附着于注塑物的情况下,可实现具有优秀的附着能力及高温耐久性的粘结层,从而可提高所制备的产品的耐久性及表面质感。
并且,可将适用上述粘结层的装饰薄片适用于汽车内饰材料,由此向车厢内赋予优秀的审美感。
附图说明
图1为简要示出本发明一实施例的真空热成型用装饰薄片的截面的图。
图2为简要示出本发明另一实施例的真空热成型用装饰薄片的截面的图。
图3为简要示出用于评价附着性的横切的图。
图4为示出与成型性评价相关的一例的图。
具体实施方式
在研究通过真空热成型工艺来对汽车内饰材料进行装饰的方法的过程中,本发明者们确认到,使粘结剂的成分相互熔融并混合,但上述粘结剂具有约50℃至90℃的第一温度区间及约110℃至150℃的第二温度区间,上述第一温度区间中官能团无法相互反应,在上述第二温度区间中官能团通过化学交联来进行粘结,由此可使粘结剂的熔融温度及交联温度之差达到约30℃至60℃,并具有优秀的高温耐久性,上述粘结剂用于形成在真空热成型工序中使用的装饰薄片的粘结层,由此完成本发明。
以下,参照附图对本发明的实施例进行详细说明,来可使本发明所属技术领域的普通技术人员容易实施本发明。本发明能够以多种不同的实施方式体现,但是,本发明并不限定于在此所进行说明的实施例。
为了明确地说明本发明,在附图中省略与本发明的说明无关的部分,在说明书全文中,对于相同或类似的结构要素赋予相同的附图标记。
在附图中,为了明确表示多层及区域,放大示出了厚度。并且,在附图中,为了便于说明,夸张示出了部分层及区域的厚度。
以下,在基材的上部(或下部)或者基材上(或下)形成任意结构不仅意味着任意结构与上述基材的上部面(或下部面)相接触地形成,还不限定于在上述基材与形成于基材上(或下)的任意结构之间不包括其他结构。
真空热成型用粘结剂组合物
真空热成型工艺是为了装饰汽车、家具等的多种内外饰材料而在注塑物中加工装饰薄片的工艺中的一种。上述真空热成型方法在高温及真空条件下执行,因此,在此过程中重要的问题是需要制备如下的粘结层,即,具有优秀的粘结性,以使上述装饰薄片可顺畅地熔敷于注塑物,并且具有高温耐久性。
在上述真空热成型工艺中,使放置有表面不存在任何图案的注塑物的工作台上升,并在附着装饰薄片之前,进行真空吸尘,然后点燃加热器,由此拉伸装饰薄片。此时,加热器将装饰薄片加热至100℃至150℃的温度,并使形成装饰薄片的粘结层的粘结剂熔融,由此在上升注塑物时可使装饰薄片容易地附着。然后,在使加热器消火后,使放置有注塑物的工作台上升来对装饰薄片进行压接,并且使粘结层交联,由此完成注塑物的表面装饰处理。
对此,为了提供具有适合于上述真空热成型工序的熔融温度和交联温度物性的粘结层的装饰薄片,本发明提供适合于上述粘结层的真空热成型用粘结剂组合物。
因此,本发明的真空热成型用粘结剂组合物在约50℃至90℃的第一温度区间中使粘结剂的成分熔融并混合,但是官能团并不相互反应,并且仅使溶剂挥发,由此形成粘结层,在约110℃至150℃的第二温度区间中,粘结剂通过化学交联来进行粘结。
本发明提供如下的真空热成型用粘结剂组合物,即,包含聚氨酯聚合物及丙烯酸聚合物,熔融温度及交联温度之差为约30℃至60℃。
具体地,上述熔融温度可以为约50℃至90℃,上述交联温度可以为约110℃至150℃。在使用现有的粘结剂的情况下,在真空热成型过程中,为了满足高温耐久性,在成型时粘结温度越高越好,但是在成型膜的过程中,因高温可损伤膜,并且存在降低加工性的隐患。并且,在真空热成型的过程中,考虑到膜损伤和加工性,若将粘结温度设计成小于110℃,则可导致在高温耐久性测试中减低注塑物与装饰薄片之间的附着力的结果。
为了克服这种问题,可在真空热成型工艺中适用本发明的真空热成型用粘结剂组合物,并通过装饰薄片对注塑物进行表面处理,在此情况下,例如,使在约90℃的温度下熔融的粘结剂在约150℃的温度下进行交联,由此实现在本工序中适合的粘结层。
相对于100重量份的上述真空热成型用粘结剂组合物的固体成分,可包含约1重量份至10重量份的上述丙烯酸聚合物。
上述丙烯酸聚合物可通过聚合丙烯酸酯单体或低聚物而成。此时,作为上述丙烯酸酯单体可使用多种丙烯酸酯单体,例如,可例举1,2-二丙烯酸乙二醇酯、1,12-十二烷基丙烯酸酯、1,4-丁二醇二(甲基)丙烯酸酯、1,6-己二醇二(甲基)丙烯酸酯、新戊二醇二(甲基)丙烯酸酯、聚乙二醇二(甲基)丙烯酸酯、己二酸新戊二醇二(甲基)丙烯酸酯(neopentylglycol adipate dimethacrylate)、羟基新戊酸酯二甲基丙烯酸新戊二醇酯(Hydroxyl pivalic acid neopentyl glycol dimethacrylate)、二环戊烯基二(甲基)丙烯酸酯(dicyclopentenyl dimethacrylate)、己内酯改性二环戊烯基二(甲基)丙烯酸酯、环氧乙烷改性二(甲基)丙烯酸酯、二(甲基)丙烯酰氧乙基异氰酸酯、烯丙基化环己基二(甲基)丙烯酸酯、三环癸二甲醇(甲基)丙烯酸酯、二羟甲基二环戊烷二(甲基)丙烯酸酯或9,9-双[4-(2-丙烯酰氧基乙氧基)苯基]氟(9,9-bis[4-(2-acryloyloxyethoxy)phenyl]fluorine)等、环氧乙烷改性六氢化邻苯二甲酸二(甲基)丙烯酸酯、三环癸二甲醇(甲基)丙烯酸酯、新戊二醇改性三甲基丙烷二(甲基)丙烯酸酯、金刚烷二(甲基)丙烯酸酯(adamantane dimethacrylate)的双官能型丙烯酸酯;三羟甲基丙烷三(甲基)丙烯酸酯、二季戊四醇三(甲基)丙烯酸酯、丙酸改性二季戊四醇三(甲基)丙烯酸酯、季戊四醇三(甲基)丙烯酸酯、环氧丙烷改性三羟甲基丙烷三(甲基)丙烯酸酯、三(甲基)丙烯酰氧基乙基异氰脲酸酯等的三官能型丙烯酸酯;二甘油四(甲基)丙烯酸酯或季戊四醇四(甲基)丙烯酸酯等的四官能型丙烯酸酯;丙酸改性二季戊四醇五(甲基)丙烯酸酯;以及二季戊四醇六(甲基)丙烯酸酯、己内酯改性二季戊四醇六(甲基)丙烯酸酯等的六官能型丙烯酸酯等,但并不限定于此。
相对于100重量份的粘结剂组合物的固体成分,粘结剂包含约1重量份至10重量份的上述丙烯酸聚合物,由此向粘结剂赋予粘结效果,并且可将熔融温度与交联温度之差调节成约40℃的温度。在包含小于1重量份的丙烯酸聚合物的情况下,存在基材无法呈现初始附着性的问题,在包含大于10重量份的情况下,可减少在高温下也可发挥粘结力的聚氨酯聚合物的含量,最终存在在高温下降低粘结剂的粘结力的隐患。
并且,上述丙烯酸聚合物的重均分子量可以为200000至800000。使丙烯酸聚合物的重均分子量维持上述范围,由此可调节粘结剂的熔融及交联温度的范围,并且可提供用于实现优秀的高温耐久性及粘结力的粘结剂。
然后,上述真空热成型用粘结剂组合物包含聚氨酯聚合物,相对于100重量份的上述真空热成型用粘结剂组合物的固体成分,可包含约90重量份至99重量份的上述聚氨酯聚合物。
上述聚氨酯聚合物以使具有活性羟基的乙醇和具有异氰酸酯基的异氰酸酯通过聚合反应来产生反应热的方式形成。可通过包含上述聚氨酯聚合物来向粘结剂赋予成型时被拉长的柔韧性的物性,具体地,相对于100重量份的上述真空热成型用粘结剂组合物的固体成分,包含约90重量份至99重量份的上述聚氨酯聚合物,由此可实现柔韧性和粘结性。若小于或大于上述范围,则存在无法达成柔韧性及高温下的高粘结强度的问题。
并且,上述聚氨酯聚合物的重均分子量可以为约1000至30000,优选地,可以为约3000至10000。本发明的真空热成型用粘结剂组合物可通过包含上述重量范围的聚氨酯聚合物来实现柔韧性及高粘结强度的效果。
上述聚氨酯聚合物可由异氰酸酯化合物、多元醇制备而成。
上述异氰酸酯化合物作为每个分子具有两个以上的异氰酸酯基的化合物,可使用芳香族二异氰酸酯及其的衍生物。作为上述异氰酸酯化合物,可以为选自由甲苯二异氰酸酯、二苯基甲烷二异氰酸酯、改性二苯基甲烷二异氰酸酯、萘二异氰酸酯、苯二异氰酸酯、六亚甲基二异氰酸酯、赖氨酸异氰酸酯、环己烷二异氰酸酯、异佛尔酮二异氰酸酯、二苯甲烷异氰酸酯、二甲苯二异氰酸酯、四甲基苯二甲基二异氰酸酯、降冰片烯二异氰酸酯、三苯甲烷三异氰酸酯、多苯基多亚甲基多异氰酸酯、包含碳二亚胺基的聚异氰酸酯、包含脲基甲酸酯基的聚聚异氰酸酯、包含异氰脲酸酯基的聚异氰酸酯及它们的组合组成的组中的一种以上的化合物,但并不限定于此。
并且,上述多元醇化合物可以为选自由聚酯类多元醇、内酯类多元醇、聚碳酸酯类多元醇、聚醚类多元醇及它们的组合组成的组中的一种以上,更优选地,可以为聚酯类多元醇或聚醚类多元醇。聚酯类多元醇具有优秀的的耐水解性、低温柔韧性、对酸和碱的耐性、电绝缘性等的性质,聚醚类多元醇可赋予柔韧性、高延伸率等的性质。
具体地,虽然并未特别限制聚酯多元醇与聚醚多元醇的重量比,但优选地,可以为1:9至9:1。通过维持上述范围的含量来实现柔韧性、对酸和碱的耐性、高延伸率等的特性。
为了使上述真空热成型用粘结剂组合物通过交联温度区间达到约110℃至150℃,可使用通过阻断剂使异氰酸酯基的一部分或全部阻断的嵌段异氰酸酯固化剂。并且,上述阻断剂可使用己内酰胺(caprolactam)、甲乙酮肟(methyl ethyl ketone oxime)、1,2-吡唑(pyrazole)、二异丙胺(diisopropylamine)或3,5-二甲基吡唑(dimethylpyrazole)等。
为了形成聚氨酯聚合物可添加聚氨酯反应催化剂、聚合引发剂等。上述聚氨酯反应催化剂作为在聚氨酯反应中少量添加的催化剂,其的优选的例子可包括环烷酸铜(copper naphthenate)、环烷酸钴、环烷酸锌、n-月桂酸丁基锡(butyltinlaurate)、三乙胺(tristhylamine)或2-甲基三乙酰胺。
作为上述聚合引发剂的优选的例子,可由二月桂酸二丁基锡(DBTDL)、氢醌(hydroquinone)、氢醌单甲醚、对苯醌、吩噻嗪及它们的混合物形成。根据所使用的催化剂的使用量可对除了反应性之外的反应混合物的流动性、参与形成生成物的表面层的工序的各种事项以及所获得的生成物起到影响,因此优选地,上述聚氨酯聚合物包含约0.01至0.03重量百分比的催化剂。
上述真空热成型用粘结剂组合物还可以包含添加剂,上述添加剂包含选自由粘结性赋予树脂、低分子量化合物、环氧树脂、固化剂、紫外线稳定剂、抗氧化剂、调色剂、加固剂、消泡剂、表面活性剂、增塑剂、发泡剂、有机盐及它们的组合组成的组中的至少一种。
上述真空热成型用粘结剂组合物包含固化剂。上述固化剂在常温下对异氰酸酯基进行阻断,以防止异氰酸酯基(-NCO)和羟基(-OH)或氨基(-NH)发生反应,若受到规定的热量,则是阻断剂解离,并增加(-NCO)的反应性,由此进行固化反应。固化剂的解离温度为100℃以上,优选为110℃至130℃。
上述真空热成型用粘结剂组合物的粘度可以为约800cps至7000cps,优选地,可以为约1000cps至5000cps。可通过维持上述范围的粘度来使上述粘结剂具有优秀的高温耐久性及附着能力,由此可使用于注塑物的表面装饰的装饰薄片以无积压或损伤现象的方式稳定地附着于注塑物。
真空热成型用装饰薄片
本发明提供如下的真空热成型用装饰薄片,即,包括:粘结层;基材层,形成于上述粘结层的上部;印刷层,形成于上述基材层的上部;以及透明基材层,形成于上述印刷层的上部,上述粘结层由前述的真空热成型用粘结剂组合物形成。
图1简要示出上述真空热成型用装饰薄片100的截面。参照图1,上述真空热成型用装饰薄片100可以为依次层叠粘结层10、基材层20、印刷层30及透明基材层40的结构。
上述真空热成型用装饰薄片100作为用于对各种内外饰材料的表面进行装饰而使用的部件,能够以真空热成型方法附着于这种内外饰材料。此时,上述粘结层10的结构由前述的粘结剂组合物形成,从而具有适合于真空热成型的熔融温度和交联温度,并且具有优秀的高温耐久性,因此不产生热化,从而也可以顺畅地附着于表面能低的基材。
具体地,上述粘结层10的厚度可以为约10μm至50μm。上述粘结层10的厚度满足上述范围,因此相对具有弯曲的表面也可以呈现优秀的附着性,在真空热成型过程中可容易地实现优秀的粘结性。
在上述真空热成型用装饰薄片100中,在上述粘结层10的上部可包括基材层20。上述基材层20起到上述真空热成型用装饰薄片的中心基材的作用,因此在真空热成型过程中可确保优秀的耐热性,同时可呈现优秀的耐久性。
具体地,上述基材层20可包含选自由聚甲基丙烯酸甲酯(PMMA)、丙烯腈-丁二烯-苯乙烯(ABS)、热塑性聚烯烃(TPO)、聚氯乙烯(PVC)、聚碳酸酯(PC)及它们的组合组成的组中的一种。例如,上述基材层20可包含丙烯腈-丁二烯-苯乙烯(ABS),在此情况下,可同时确保优秀的成型性及耐热性。
上述基材层20的厚度可以为约0.5mm至3mm。可通过使上述基材层的厚度满足上述范围来确保作为中心基材的优秀的耐久性,并在上述装饰薄片的真空热成型过程中可确认优秀的耐热性。
在上述真空热成型用装饰薄片100中,在上述基材层20的上部可包括印刷层30。上述印刷层30可如下地制备,即,可根据需要选择各种原料及印刷方法来形成印刷图案,借助上述装饰薄片可起到直接赋予美学效果的作用。
具体地,可利用选自由凹版印刷、柔版印刷或圆网印刷及它们的组合组成的组中的只要一种方法来形成上述印刷层30。例如,上述基材层20可包含能够实现热成型的聚碳酸酯(PC)、聚对苯二甲酸乙二醇酯(PET)、丙烯腈-丁二烯-苯乙烯(ABS),在此情况下,可利用直接印刷工艺在上述基材层的上部以无基材的损伤的方式形成印刷层,由此,与现有的转印方式相比,可获得因工序的简化而产生的费用减少及不良率减少的效果。
上述印刷层30的厚度可以为约1μm至40μm。可通过使上述印刷层的厚度满足上述范围来呈现鲜明的印刷图案,同时可确保与可以形成于上部的压花层的优秀的相容性。
在上述真空热成型用装饰薄片100中,在上述印刷层30的上部可包括透明基材层40。具体地,上述透明基材层40可以包含聚甲基丙烯酸甲酯(PMMA),但并不限定于此。通过包括上述透明基材层40来保护印刷层30,并且具有提高光泽和耐磨性的效果。
并且,代替上述透明基材层40而可在上述印刷层30上直接涂敷表面处理剂。即,在上述真空热成型用装饰薄片100中,代替上述透明基材层40,还可以在压花层与印刷层30之间包括通过上述表面处理剂的涂敷层。
图2简要示出本发明另一实例的真空热成型用装饰薄片200的截面。
在上述真空热成型用装饰薄片200中,在上述粘结层10的下部还可以包括离型膜层1。上述离型膜层1作为在真空热成型过程中利用上述装饰薄片之前被剥离的层,起到使上述装饰薄片100的流通及运输变得容易的作用。
具体地,上述离型膜层1可包含聚对苯二甲酸乙二醇酯(PET),更具体地,可使用涂敷有硅涂布剂的聚对苯二甲酸乙二醇酯(PET)膜。在此情况下,当在上述离型膜层1上直接形成粘结层10时,可确保优秀的涂敷性及剥离性。
上述离型膜层1的厚度可以为约20μm至100μm。可通过使上述离型膜层1的厚度维持上述范围来使剥离步骤简单,在其上部形成粘结层10的步骤中可确保优秀的加工性。
并且,在上述真空热成型用装饰薄片200中,在透明基材层40的上部还可以包括压花层2。具体地,可利用压花工序来形成上述压花层2。
上述压花层包括借助上述压花团而成的凹面和凸面,从而可向上述印刷层的印刷图案赋予更优秀的美学效果,进而可体现为外部。
以下,为了便于理解本发明,提供优选实施例。但下述的实施例仅为了进一步简单地理解本发明而提出,本发明的内容并不限定于下述实施例。
实施例1
1.粘结剂组合物的制备
1)丙烯酸聚合物的合成
为了使氮气回流以及容易地调节温度,在2L的反应器设置冷却装置,并投入20重量份的丙烯酸-2-乙基己酯(2-EHA)、40重量份的丙烯酸正丁酯(n-BA)、30重量份的丙烯酸异冰片酯(IBOA)、10重量份的丙烯酸-2-羟乙酯(HEA)、作为分子量调节剂的0.05重量份的正十二烷基硫醇的单体混合物,作为溶剂投入甲基乙基酮(MEK),由此制备重均分子量为60万且玻璃转化温度为-26℃的丙烯酸聚合物。
2)聚氨酯聚合物的合成
为了使氮气回流以及容易地调节温度,在2L的反应器设置冷却装置,并使900g的聚丙二醇(polypropylene glycol)、500g的马来酸酐、500g的无水富马酸发生聚合反应。若完成聚合反应,则通过添加甲基乙基酮(MEK)来降低粘度。向上述化合物中中投入0.5摩尔的二甲苯二异氰酸酯(xylene diisoeyanate)和巴辛顿公司(Baxenden)的嵌段异氰酸酯BI7990,由此合成一液型聚氨酯聚合物。
使95重量份的上述聚氨酯聚合物和5重量份的上述丙烯酸聚合物进行配合来制备粘结剂组合物。
2.真空热成型用装饰膜的制备
在0.15mm厚度的丙烯腈-丁二烯-苯乙烯(ABS)基材层的上部通过凹版印刷方法形成20μm厚度的印刷层。在上述印刷层的上部形成10μm厚度的聚甲基丙烯酸甲酯(PMMA)透明基材层,在上述透明基材层的上部通过紫外辐射压印方法形成压花层。另一方面,准备50μm厚度的聚对苯二甲酸乙二醇酯(PET)离型膜层,在上述离型膜层的上部涂敷在上述实施例及比较例中所制备的粘结剂组合物,由此制备35μm厚度的粘结层。然后,对上述基材层的下部进行热贴合,以使上述粘结层附着,由此完成了真空热成型用装饰薄片的制备。
实施例2
除了通过使90重量份的上述聚氨酯聚合物和10重量份的丙烯酸聚合物进行配合来制备粘结剂组合物以外,以与上述实施例1相同的方法制备装饰薄片。
比较例1
除了通过使80重量份的上述聚氨酯聚合物和20重量份的上述丙烯酸聚合物进行配合来制备粘结剂组合物以外,以与上述实施例1相同的方法制备装饰薄片。
比较例2
除了通过使100重量份的上述聚氨酯聚合物进行配合来制备粘结剂组合物以外,以与上述实施例1相同的方法制备装饰薄片。
比较例3
除了在聚氨酯合成过程中使用巴辛顿公司(Baxenden)的嵌段异氰酸酯BI7990以及在完成制备后使90重量份的上述聚氨酯聚合物和10重量份的上述丙烯酸聚合物进行配合来制备粘结剂组合物以外,以与上述实施例1相同的方法制备装饰薄片。
实验例
以下述方法进行评价,并将结果示出在表1。
1)剥离力评价
以25mm×20cm(水平×垂直)的大小对真空热成型用装饰薄片进行裁剪来制造试片。然后,去除上述试片的离型膜,在以施加了130℃的热量的压膜机对丙烯腈-丁二烯-苯乙烯基材面进行压膜后,在完成附着30分钟后的时点上使用拉力试验机而在300mm/min的剥离速度及180°的剥离角度的条件下检测剥离力。
2)高温耐久性评价
在实施例及比较例中所制备的真空热成型用装饰薄片中去除离型膜后,通过真空热成型方法制备样品。在高温耐久性的评价中,在烘箱中以80℃的温度放置300小时左右的通过真空热成型方法制备的样品,观察成型品和上述装饰片的边缘部分的收尾以及是否鼓包,并根据下述基准进行评价。
评价基准
○:未观察到鼓包现象
×:观察到鼓包现象
3)附着性评价
根据JISK5600-5-6进行附着性评价。如附图所示,对实施例及比较例的试片的表面进行横切。然后,以柔软的刷子清洗表面,在坚固地附着规定的胶带(JISZ1522)后,朝向一侧的90°的角度强拉胶带来去除。根据下述基准进行判定(参照图3)。
评价基准
○:受到横切(Cross-cut)影响而无剥离损伤。
△:受到横切影响而剥离5-15%。
×:受到横切影响而全部剥离。
4)成型性评价
成型条件:以150℃的膜实测温度的条件下进行真空热成型。确认在弯曲的部分是否完整地成型,评价从成型品和膜的边缘部分是否向内侧完整地卷入(参照图4)。
成型例
评价基准
○:在弯曲的部分完整地成型。边缘部分向内侧完整地卷入。
×:未完整地成型,边缘部分的卷入也不足。
表1
如上述表1所示,可知与上述比较例1、2、3相比,上述实施例的装饰薄片具有优秀的成型性、高温耐久性、附着性及剥离力。尤其,在未包含丙烯酸聚合物的比较例2的粘结剂的情况下,呈现出所有物性明显降低的现象。并且,在未使用嵌段异氰酸酯的比较例3的情况下,交联温度非常低,物性也被降低。因此,通过以本发明的范围包含聚氨酯聚合物及丙烯酸聚合物来形成熔融温度与交联温度之差为30℃以上的粘结剂,由此可实现优秀的高温耐久性、成型性、附着性及剥离力。
附图文字的说明
100、200:真空热成型用装饰薄片
10:粘结层
20:基材层
30:印刷层
40:透明基材层
1:离型膜层
2:压花层
Claims (12)
1.一种真空热成型用粘结剂组合物,其特征在于,包含聚氨酯聚合物以及丙烯酸聚合物,熔融温度以及交联温度之差为30℃至60℃,
i)上述熔融温度为50℃至90℃,上述交联温度为110℃至150℃,
ii)相对于100重量份的上述粘结剂组合物的固体成分,包含5重量份至10重量份的上述丙烯酸聚合物并且包含90重量份至95重量份的上述聚氨酯聚合物,
iii)其中上述聚氨酯聚合物由异氰酸酯化合物以及多元醇化合物制备而成,并且上述异氰酸酯化合物包含嵌段异氰酸酯。
2.根据权利要求1所述的真空热成型用粘结剂组合物,其特征在于,上述丙烯酸聚合物的重均分子量为200000至800000。
3.根据权利要求1所述的真空热成型用粘结剂组合物,其特征在于,上述聚氨酯聚合物的重均分子量为1000至30000。
4.根据权利要求1所述的真空热成型用粘结剂组合物,其特征在于,上述多元醇化合物包含选自由聚酯类多元醇、内酯类多元醇、聚碳酸酯类多元醇、聚醚类多元醇以及它们的组合组成的组中的一种以上。
5.一种真空热成型用装饰薄片,其特征在于,
包括:
粘结层;
基材层,形成于上述粘结层的上部;
印刷层,形成于上述基材层的上部;以及
透明基材层,形成于上述印刷层的上部,
上述粘结层由权利要求1至4中任一项所述的真空热成型用粘结剂组合物形成。
6.根据权利要求5所述的真空热成型用装饰薄片,其特征在于,上述粘结层的厚度为10μm至50μm。
7.根据权利要求5所述的真空热成型用装饰薄片,其特征在于,上述基材层包含选自由聚甲基丙烯酸甲酯、丙烯腈-丁二烯-苯乙烯、热塑性聚烯烃、聚氯乙烯、聚碳酸酯以及它们的组合组成的组中的一种。
8.根据权利要求5所述的真空热成型用装饰薄片,其特征在于,在上述粘结层的下部还包括离型膜层。
9.根据权利要求8所述的真空热成型用装饰薄片,其特征在于,上述离型膜层包括聚对苯二甲酸乙二醇酯膜。
10.根据权利要求5所述的真空热成型用装饰薄片,其特征在于,利用选自由凹版印刷、柔版印刷、圆网印刷以及它们的组合组成的组中的至少一种方法来形成上述印刷层。
11.根据权利要求5所述的真空热成型用装饰薄片,其特征在于,在上述透明基材层的上部还包括压花层。
12.根据权利要求11所述的真空热成型用装饰薄片,其特征在于,利用压花工序来形成上述压花层。
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KR1020150030955A KR101981937B1 (ko) | 2015-03-05 | 2015-03-05 | 진공 열 성형용 접착제 조성물 및 이를 적용한 진공 열 성형용 데코레이션 시트 |
KR10-2015-0030955 | 2015-03-05 | ||
PCT/KR2016/001673 WO2016140452A2 (ko) | 2015-03-05 | 2016-02-19 | 진공 열 성형용 접착제 조성물 및 이를 적용한 진공 열 성형용 데코레이션 시트 |
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US (1) | US10344193B2 (zh) |
EP (1) | EP3266846A4 (zh) |
JP (1) | JP6657246B2 (zh) |
KR (1) | KR101981937B1 (zh) |
CN (1) | CN107406733B (zh) |
TW (1) | TWI696678B (zh) |
WO (1) | WO2016140452A2 (zh) |
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KR102542711B1 (ko) * | 2017-04-13 | 2023-06-12 | 오지 홀딩스 가부시키가이샤 | 가식 성형용 점착 시트 |
KR102314948B1 (ko) * | 2018-11-23 | 2021-10-21 | 주식회사 엘지화학 | 윈도우 데코 필름용 점착 시트 및 이를 포함하는 윈도우 데코 필름 |
KR102296592B1 (ko) * | 2018-11-23 | 2021-09-01 | 주식회사 엘지화학 | 윈도우 데코 필름용 점착 시트 및 이를 포함하는 윈도우 데코 필름 |
CN109705756A (zh) * | 2018-12-21 | 2019-05-03 | 江苏杰立胶粘材料科技有限公司 | 一种印刷泡棉胶带及其生产工艺 |
KR102376882B1 (ko) * | 2021-02-10 | 2022-03-21 | (주)이녹스첨단소재 | 디스플레이용 점착 시트 |
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- 2015-03-05 KR KR1020150030955A patent/KR101981937B1/ko active IP Right Grant
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2016
- 2016-02-19 CN CN201680013935.0A patent/CN107406733B/zh not_active Expired - Fee Related
- 2016-02-19 WO PCT/KR2016/001673 patent/WO2016140452A2/ko active Application Filing
- 2016-02-19 US US15/555,908 patent/US10344193B2/en not_active Expired - Fee Related
- 2016-02-19 EP EP16759088.4A patent/EP3266846A4/en not_active Withdrawn
- 2016-02-19 JP JP2017546671A patent/JP6657246B2/ja not_active Expired - Fee Related
- 2016-03-02 TW TW105106405A patent/TWI696678B/zh not_active IP Right Cessation
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Also Published As
Publication number | Publication date |
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TWI696678B (zh) | 2020-06-21 |
WO2016140452A3 (ko) | 2016-10-27 |
KR20160108702A (ko) | 2016-09-20 |
EP3266846A4 (en) | 2018-01-17 |
JP2018512477A (ja) | 2018-05-17 |
US20180051195A1 (en) | 2018-02-22 |
KR101981937B1 (ko) | 2019-05-28 |
US10344193B2 (en) | 2019-07-09 |
TW201632602A (zh) | 2016-09-16 |
EP3266846A2 (en) | 2018-01-10 |
JP6657246B2 (ja) | 2020-03-04 |
WO2016140452A2 (ko) | 2016-09-09 |
CN107406733A (zh) | 2017-11-28 |
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