CN101479095B - 转移膜、多层片及其制备方法 - Google Patents
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- CN101479095B CN101479095B CN2007800242634A CN200780024263A CN101479095B CN 101479095 B CN101479095 B CN 101479095B CN 2007800242634 A CN2007800242634 A CN 2007800242634A CN 200780024263 A CN200780024263 A CN 200780024263A CN 101479095 B CN101479095 B CN 101479095B
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Abstract
本发明涉及一种用于制备具有优异的耐气候性、抗划伤性和模压性能的装饰用层压片的转移膜、由该转移膜制备的层压片及其制备方法。由于在本发明的转移膜和层压片上形成了包含改性丙烯酸树脂和乙酸乙烯酯的表面处理层,所以其兼具优异的抗划伤性和热压成型性,因此可有效地用于保护和装饰如家用电器、家具和汽车零件的塑料模制品,特别是具有三维复杂形状的模制品。
Description
技术领域
本发明涉及一种用于制备具有优异的耐气候性、抗划伤性和模压性能的装饰用多层片(层压片)的转移膜(transferring film)、由该转移膜制备的层压片及其制备方法。
背景技术
家用电器、家具和汽车内外材料所使用的塑料零件表面需要有如耐化学品性、耐磨性、光泽、图像清晰度、耐气候性和高级外观图案等物理性能。通常,使用如喷涂的方法作为保护和装饰这种塑料模制品表面的方法。
然而,所述涂敷方法通常重复喷涂和干燥3次以上,因此实施该方法存在的问题为需要较长时间。例如,在汽车制造过程中,喷涂工序的时间、设备和成本的重要性占所有工序的三分之一。此外,在喷涂工序中使用的涂料排出对环境有不利影响的挥发性有机化合物(VOC)。因此,需要另外的设备以除去这些化合物。当再循环使用制品时,必须除去表面上的热固性处理层,从而存在的问题为会产生额外花费。
为了克服喷涂工序的上述问题,人们已经尝试了通过将片或膜粘附在塑料零件的表面来进行保护和装饰的方法。最初,将增塑的聚氯乙烯(PVC)用作这种片,之后开发出并使用具有优异耐气候性和拉伸率(drawing rate)的聚偏二氟乙烯膜或者聚偏二氟乙烯树脂与甲基丙烯酸甲酯树脂的复合片(国际公开No.WO 88/07416,美国专利No.5,514,427,国际公开No.WO 99/37479,日本专利公开No.H09-193189,美国专利No.5,108,836等)。
国际公开No.WO 88/07416公开了一种如下制备的片:将作为载体层的聚偏二氟乙烯树脂和甲基丙烯酸甲酯树脂的混合物涂敷到聚酯膜上并干燥该层。然而,在用上述方法制备的片中,增大所包含的聚偏二氟乙烯树脂和甲基丙烯酸甲酯树脂的硬度是受限制的。因此,存在的问题是会降低成品膜表面的抗划伤性。
另外,为了保护和装饰塑料模制品的表面,已经开发出多种层压片。然而,在这些常规的层压片中,当如抗划伤性的硬度性能获得改善时,模压性能通常被劣化。因此,需要开发同时兼具上述两种性能的层压片。
发明内容
技术问题
本发明涉及包括表面处理层的转移膜,所述表面处理层包含改性的丙烯酸树脂和乙酸乙烯酯树脂。
技术方案
由于包含在表面处理层中的成分具有强极性和分子间结合力,所以本发明的转移膜具有优异的表面硬度。另外,本发明的转移膜也具有表面处理层的优异拉伸率和以及当将其用于模制品上时优异的抗划伤性和模压性能,并且甚至在热压成型之后,能防止如产生裂纹的外观损害,因此可有效地用于塑料注射成型制品中。
附图说明
图1为示意性地描述根据本发明的一个方案的转移膜的横截面视图。
图2为示意性地描述根据本发明的一个方案的层压片的横截面视图。
图3为根据本发明的一个方案制备层压片的工艺流程图。
图4为示意性地描述使用根据本发明的一个方案的层压片作为装饰表面的用途来成型模制品的方法的构成图。
图5为示意性地描述使用根据本发明的另一个方案的层压片作为装饰表面的用途来成型模制制品的方法的构成图。
具体实施方式
下面将详细描述本发明的转移膜。
本发明转移膜中的表面处理层包含改性丙烯酸树脂和乙酸乙烯酯树脂。其厚度优选为3~20μm,但不限于此。
包含在表面处理层中的改性丙烯酸树脂和乙酸乙烯酯树脂用于赋予表面处理层抗划伤性和热压成型性。具体而言,由于高的分子间极性和结合力,所述改性丙烯酸树脂改进表面处理层的硬度并同时改进拉伸率。因此,包含在本发明的转移膜中的表面处理层具有优异的如抗划伤性的硬度性能并且也具有优异的模压性能,并且防止在成型后产生如裂纹的缺陷。可用于本发明中的改性丙烯酸树脂的实例包括选自聚氨酯丙烯酸酯、用胺接枝的丙烯酸酯和用马来酸接枝的丙烯酸酯中的一种或多种,但不限于此。另外,优选地,在表面处理层中,所述改性丙烯酸树脂的含量为15~25重量份,乙酸乙烯酯树脂的含量为5~15重量份。如果各成分的含量偏离上述范围,则不能获得理想的抗划伤性或模压性能,或者可能降低经济效率。
优选地,本发明的表面处理层也进一步包含0.5~1重量份的蜡。所述蜡赋予表面处理层光滑性并因此用于加强抗损害性。如果其含量偏离上述范围,则不能获得理想效果,或者可能降低经济效率。
优选地,本发明的表面处理层也进一步包含0.1~0.5重量份的有机硅树脂。当涂敷表面处理层时,所述有机硅树脂使流平效率高,并且也赋予表面处理层光滑性,因此用于加强抗损害性。
优选地,本发明的表面处理层也进一步包含1~10重量份的硬化剂。所述硬化剂可额外改进表面处理层的硬度。在本发明中可用的硬化剂的实例包括选自如二异氰酸甲酯(methyl diisocyanate)或甲苯胺二异氰酸酯(toluidine diisocyanate)的异氰酸酯化合物、多化合价环氧化合物和活化聚酯(activated polyester)化合物中的一种或多种,但并不限于此。
如图1所示,本发明的转移膜可包括顺序层压在表面处理层13上的载体层11和脱离层(release layer)12,以及在表面处理层13下面形成的粘附层(adhesion layer)14。
所述载体层可由本领域中通常使用的材料组成,对其没有具体限定。组成所述载体层的材料的实例包括软化温度为200℃以上的热塑性树脂膜。由于聚对苯二甲酸乙二醇酯膜或高密度聚丙烯膜具有优异的表面光泽,所以它们是优选的。另外,尽管所述载体层的厚度没有具体限定,但是优选将所述载体层的厚度调节到25~100μm的范围内。
在所述载体层的下面可形成脱离层。同样,对组成该脱离层的材料没有具体限定,并可采用本领域已知的常规材料。这样的实例包括有机硅树脂脱离剂(releasing agent)或三聚氰胺树脂脱离剂。另外,所述脱离层的厚度优选为0.1~0.5μm,但并不限于此。
在所述表面处理层下面形成的粘附层也没有具体限定,其可用本领域中的常规粘合剂组成。所述粘合剂的实例包括基于聚氨酯丙烯酸酯或丙烯酰胺(acryl amine)共聚物树脂的粘合剂。这样的粘合剂是优选的,因为它们在热转移时与上部表面处理层具有优异的粘附力且与如基底片的目标物具有优异的粘附力。
采用上述材料,用本领域的常规方法可制备上述本发明的转移膜。
例如,本发明的转移膜可通过包括以下步骤的方法制备:在基底膜上形成脱离层的第一步骤;将用于形成表面处理层的组合物施加在所述脱离层上并干燥得到的层以形成表面处理层的第二步骤;以及在所述表面处理层上形成粘附层的第三步骤。
第一步骤是在基底膜上形成脱离层的步骤,所述基底膜和脱离层的材料如上所述。形成脱离层的方法没有具体限定,并且该层可通过如棒涂、狭缝挤压式涂布、线棒式涂布(mayer bar coating)、压轧涂布(nipcoating)或凹版涂布(gravure coating)的常规方法形成。
第二步骤是将用于形成表面处理层的组合物施加在如上形成的脱离层上并干燥组合物以形成表面处理层的步骤。用于形成表面处理层的组合物可通过将组成表面处理层的上述各组分溶于溶剂中来制备。
作为制备用于形成表面处理层的组合物的溶剂,优选使用甲苯、甲乙酮和乙酸乙酯的混合溶剂。在本发明中,为了形成表面处理层,采用上述混合溶剂,通过调节各成分的含量可适当调节用于形成表面处理层的组合物的粘度,其中用溶剂调节的组合物的粘度优选为10~200cps。如果粘度小于10cps,则恐怕会产生流挂的缺陷。如果粘度超过200cps,则表观性能降低,因此可能产生涂敷的缺陷。尽管包含在混合溶剂中的各成分的含量没有具体限定,只要将组合物调节至具有上述浓度就可以,但是优选混合溶剂包含25~35重量份甲苯、15~20重量份的甲乙酮和10~15重量份的乙酸乙酯。
采用上述用于形成表面处理层的组合物形成表面处理层的方法没有具体限定。例如,所述方法包括如下方法:将用于形成表面处理层的组合物在脱离层上涂敷3~30μm的厚度并随后在110~150℃的温度下干燥该涂层适当时间。涂敷用于形成表面处理层的组合物的方法也没有具体限定,但是可采用如上所述的形成脱离层所用的涂敷方法。考虑到容易调节厚度,优选采用线棒式涂布或狭缝挤压式涂布。
所述第三步骤是在第二步骤中形成的表面处理层上形成粘附层的步骤。粘附层可通过本领域中的常规方法来形成。例如,所述方法包括如下方法:通过棒涂或线棒式涂布等在表面处理层上涂敷厚度为1~5μm的基于聚氨酯丙烯酸酯或丙烯酰胺聚合物树脂的粘合剂,并随后在100~150℃的温度下干燥该涂层适当时间。
本发明也涉及一种层压片,其包括从根据本发明的转移膜转移的表面处理层。通过经上述转移膜将表面处理层转移到层压片,本发明可赋予层压片优异的抗划伤性以及模压性能。
除了上述转移膜,更具体而言,除了转移膜的表面处理层,本发明的层压片可包括本领域中通常使用的其它层。
例如,如图2所示,本发明的层压片可在表面处理层13上层压保护膜层25并在该表面处理层下面顺序形成粘附层14、透明涂层21、彩色涂层22、粘合剂层(adhesive layer)23和背衬片(backing sheet)层24。如图2所示的层压片仅为本发明的一个方案,其中如果必要,每个层均可被省略,或者可适当添加除了图2中所示的层之外的其它层。
所述保护膜层可用本领域中的常规树脂膜形成。其实例包括聚乙烯膜或聚丙烯膜。
在本发明的层压片中,通过粘附层可在所述表面处理层下面形成透明涂层。包含在上述透明涂层中的材料没有具体限定,可没有任何限定地使用本领域中的常规树脂,但是优选具有耐气候性的树脂。这种树脂的实例包括聚偏二氟乙烯树脂、甲基丙烯酸甲酯树脂或者由聚偏二氟乙烯树脂和甲基丙烯酸甲酯树脂共混或共挤出制备的树脂。另外,所述透明涂层的厚度优选在0.1~200μm的范围内。
在本发明的层压片中,在所述表面处理层下面可进一步形成彩色涂层。所述彩色涂层可用多种油墨和粘合剂树脂的混合物形成。优选地,使用具有优异耐气候性的油墨。
在本发明的层压片中,在所述表面处理层的下面也可进一步形成背衬片层。形成背衬片层的材料没有具体限定。可采用如ABS片的常规片材。优选地,所述背衬片层的厚度在0.1~1mm的范围内。如图2所示,所述背衬片层可通过粘附层粘附,其中所述粘附层可采用本领域已知的多种粘合剂形成。例如,所述粘附层可由丙烯酸树脂、聚氨酯树脂或聚氨酯丙烯酸酯共聚物树脂的粘合剂形成。
本发明涉及制备层压片的方法,其包括以下步骤:
(1)制备耐气候性衬底片;以及
(2)采用根据本发明的转移膜将表面处理层转移到衬底片上。
本发明的步骤(1)是制备将要将转移膜的表面处理层转移到其上的衬底片的步骤。制备衬底片的方法没有具体限定。根据衬底片的结构,用本领域中的常规方法可制备所述片。例如,如果该衬底片包括透明涂层、彩色涂层和背衬片层,则其可通过在透明涂层上顺序形成彩色涂层及粘附层并随后层压背衬片来制备。在上述每一步骤中使用的材料如上所述。
本发明的步骤(2)是在步骤(1)中制备的耐气候性衬底片上层压转移膜以转移表面处理层的步骤。层压转移膜的方法没有具体限定,并且可采用本领域中已知的方法。
所述层压方法的实例如下:
首先,在预热辊上将在步骤(1)中制备的耐气候性衬底片预热到100~150℃的温度,并随后在加热鼓上将其加热到160~175℃的温度以使其软化。随后,将用红外线加热器等加热到130~160℃的温度下的转移膜的粘附层对应地粘附在所述衬底片的透明涂层上,并通过橡胶辊和钢辊之间以层压转移膜和衬底片。由此,步骤(2)可通过这种工艺进行。
本发明的制备方法可进一步包括在转移的表面处理层上层压保护膜的步骤。如果在转移膜上形成有载体层,则在脱除该层之后层压保护膜。因为在载体层下面形成了脱离层,所以可容易地脱除载体层。在脱除载体层之后形成保护层的方法的实例包括层压如聚乙烯膜或聚丙烯膜的保护膜的方法,其中将压敏粘合剂用层压辊涂敷到一面上。
本发明也涉及包括根据本发明的层压片的注射成型制品。
如上所述,本发明的转移膜和用该转移膜组成的层压片具有优异的耐气候性、模压性能和抗划伤性。因此,本发明的层压片可有利地用于装饰家用电器、家具、汽车等多种模制品。另外,当本发明的层压片是通过注射熔融树脂制备的塑料模制品时,可以使用它而不会限制模制品的使用用途。特别是,如果模制品的表面形成为如三维曲线的复杂形状,则其显示更优异的性能。
在所附的图4和图5中,描述了将根据本发明的一个方案的层压片用于注射成型制品的表面装饰的方法。
具体而言,如图4所示,将根据本发明的层压片20置于模具32上。接着,采用常规的真空成型法用加热板31等在180~250℃的温度下使所述片预成型。然后,如图5所示,将层压片20***装备有上部模具41和底部模具42的注射机中,并将熔融树脂44通过注射孔43注入。通过这种注射成型,本发明的层压片可用于表面装饰。
参照根据本发明的实施例和不是根据本发明的比较实施例,下面将更详细地描述本发明。但是,本发明的范围并不限于下面所示的实施例。
实施例1:转移膜(1)的制备
在作为基底层的50μm厚的聚对苯二甲酸乙二醇酯膜的上面涂敷厚度为0.1μm的有机硅树脂脱离剂以形成脱离层。接着,采用线棒式涂布机,在所述脱离层的上面涂敷厚度为10μm的用于形成表面处理层的粘度为50cps的组合物,该组合物包含20重量份的改性丙烯酸树脂、10重量份的乙酸乙烯酯树脂、0.5重量份的蜡、0.3重量份的有机硅树脂、25重量份的甲苯、17重量份的甲乙酮和13重量份的乙酸乙酯,并随后将其在120℃的温度下干燥以形成表面处理层。采用线棒式涂布机在如此形成的表面处理层上涂敷厚度为2μm的丙烯酰胺共聚物树脂粘合剂,并将其在120℃下干燥以制备转移膜。
实施例2:转移膜(2)的制备
除了用粘度为50cps,包含20重量份的改性丙烯酸树脂、10重量份的乙酸乙烯酯树脂、5重量份的二异氰酸甲酯、0.5重量份的蜡、0.3重量份的有机硅树脂、25重量份的甲苯、17重量份的甲乙酮和13重量份的乙酸乙酯的组合物作为形成表面处理层的组合物之外,用与上述实施例1相同的方法制备转移膜。
实施例3:转移膜(3)的制备
除了将包含在用于形成表面处理层的组合物中的二异氰酸甲酯换为多化合价环氧化合物之外,用与实施例2相同的方法制备转移膜。
实施例4:衬底片的制备
采用耐气候性丙烯酸油墨,在作为透明涂层的100μm厚的聚偏二氟乙烯树脂-甲基丙烯酸甲酯树脂挤出膜上形成彩色涂层。接着,在上述彩色涂层上形成聚氨酯丙烯酸酯共聚物树脂粘附层,并且向其层压作为背衬片的0.4mm厚的ABS片以制备耐气候性衬底片。
实施例5:层压片(1)的制备
在预热辊上将在实施例4中制备的衬底片(厚度:0.5mm)预热至130℃,并随后在加热鼓上加热到175℃以使其软化。同时,用红外线加热器将在实施例1中制备的转移膜(1)加热至150℃。接着,将加热的转移膜(1)的粘附层对应地置于软化了的衬底片的透明涂层处,并使其通过橡胶辊和钢辊之间以层压转移膜和衬底片。随后,将转移膜(1)的基底层脱除以便将转移膜(1)的表面处理层转移。接着将一面涂敷了压敏粘合剂的作为保护膜的聚乙烯膜粘附在表面处理层的上面以制备层压片。
实施例6:层压片(2)的制备
除了采用在实施例2中制备的转移膜(2)之外,用与实施例5相同的方法制备层压片。
实施例7:层压片(3)的制备
除了采用在实施例3中制备的转移膜(3)之外,用与实施例5相同的方法制备层压片。
比较实施例1
采用耐气候性丙烯酸油墨,在作为透明涂层的100μm厚的聚偏二氟乙烯树脂-甲基丙烯酸甲酯树脂复合膜的上面形成彩色涂层。接着,在其上形成为聚氨酯丙烯酸酯共聚物树脂的粘附层,并随后向其层压作为背衬片的0.4mm厚的ABS片以制备衬底片。
比较实施例2
除了用100μm厚的甲基丙烯酸甲酯树脂膜作为透明涂层之外,用与上述比较实施例1相同的方法制备衬底片。
比较实施例3
除了用100μm厚的聚氯乙烯(PVC)树脂膜作为透明涂层之外,用与上述比较实施例1相同的方法制备衬底片。
对于上述制备的实施例5~7和比较实施例1~3,用以下所指出的方法测定表面硬度和裂纹的产生。
1、表面硬度
除去层压在层压片的表面处理层上的保护膜层之后,在500g的负荷下用铅笔硬度测试仪测量表面硬度。在测量中,H表示硬的程度。当它的数目增加,程度***。另外,B表示软的程度。当它的数目增加,程度***。
2、加热后在拉伸时裂纹的产生
除去层压在层压片的表面处理层上的保护膜层之后,将其加热到90℃并采用拉力试验机以50mm/分钟的速度拉伸至200%。此时,测量裂纹的产生。如果产生了裂纹,则这种情况用“O”表示。如果未产生裂纹,则这种情况用“X”表示。
用上述方法测量的结果在下面的表1中示出。
表1
如上面的表1所示,根据实施例5~7的层压片的测量结果是H或2H,其具有优异的表面硬度。特别是,如果形成表面处理层的组合物包含硬化剂,则它们显示更优异的表面硬度。另外,当它们被加热和拉伸时,未产生如裂纹的缺陷。因此,可以证实在加热时其具有优异的拉伸率。
然而,比较实施例1~3的层压片具有较差的B或2B的表面硬度。由于没有任何表面处理层而仅有透明涂层的表面硬度较软,所以可以预计抗划伤性降低。
工业实用性
如上所述,由于本发明的转移膜和层压片中形成了包含改性丙烯酸树脂和乙酸乙烯酯的表面处理层,所以其兼具优异的抗划伤性和热压成型性。因此,本发明的层压片可有效地用于保护和装饰如家用电器、家具和汽车零件的塑料模制品,特别是具有三维复杂形状的模制品。
Claims (16)
1.一种转移膜,其包括含有改性丙烯酸树脂和乙酸乙烯酯树脂的表面处理层,
其中,所述改性丙烯酸树脂为选自聚氨酯丙烯酸酯、用胺接枝的丙烯酸酯和用马来酸接枝的丙烯酸酯中的一种或多种;
所述表面处理层中的改性丙烯酸树脂的用量为15~25重量份,所述表面处理层中的乙酸乙烯酯树脂的用量为5~15重量份。
2.权利要求1所述的转移膜,其中所述表面处理层的厚度为3~20μm。
3.权利要求1所述的转移膜,其中所述表面处理层进一步包含0.5~1重量份的蜡。
4.权利要求1所述的转移膜,其中所述表面处理层进一步包含0.1~0.5重量份的有机硅树脂。
5.权利要求1所述的转移膜,其中所述表面处理层进一步包含1~10重量份的硬化剂。
6.权利要求5所述的转移膜,其中所述硬化剂为选自异氰酸酯化合物、多化合价环氧化合物和活化聚酯化合物中的一种或多种。
7.权利要求1所述的转移膜,其中将其下形成有脱离层的载体层进一步层压在所述表面处理层上。
8.一种层压片,其包括从根据权利要求1~7中的任一项所述的转移膜转移过来的表面处理层。
9.权利要求8所述的层压片,其进一步包括层压在所述表面处理层上的保护膜。
10.权利要求8所述的层压片,其进一步包括在所述表面处理层下面形成的透明涂层。
11.权利要求10所述的层压片,其中所述透明涂层为聚偏二氟乙烯树脂、甲基丙烯酸甲酯树脂、聚偏二氟乙烯树脂和甲基丙烯酸甲酯树脂的共混树脂或者聚偏二氟乙烯树脂和甲基丙烯酸甲酯树脂的共挤出树脂。
12.权利要求8所述的层压片,其进一步包括在所述表面处理层下面形成的彩色涂层。
13.权利要求12所述的层压片,其中所述彩色涂层含有耐气候性油墨和粘合剂树脂的混合物。
14.一种制备层压片的方法,其包括以下步骤:
(1)制备耐气候性衬底片;以及
(2)使用根据权利要求1~7中任一项所述的转移膜将表面处理层转移到衬底片上。
15.权利要求14所述的方法,其中所述耐气候性衬底片通过在透明涂层上顺序形成彩色涂层和粘附层并层压背衬片来制备。
16.一种注射成型制品,其包括权利要求8所述的层压片。
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US20050103350A1 (en) * | 2003-10-28 | 2005-05-19 | Marian Henry | Method of safely turning supine patient on to his or her side |
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KR101139260B1 (ko) * | 2009-09-14 | 2012-05-15 | 전상길 | 열전사 시트 |
TWI386311B (zh) * | 2009-12-30 | 2013-02-21 | Sipix Chemical Inc | 加飾成型元件以及易清潔膜片 |
KR20120012016A (ko) * | 2010-07-30 | 2012-02-09 | (주)엘지하우시스 | 자동차 내장재용 인서트 시트 및 그 제조 방법 |
KR101294397B1 (ko) * | 2010-11-24 | 2013-08-08 | (주)엘지하우시스 | 엠보 유지가 우수한 장식 시트 제조 방법 |
KR101417247B1 (ko) * | 2012-02-08 | 2014-07-08 | (주)엘지하우시스 | 탄성질감이 부여된 인몰드 전사필름 및 그 제조방법 |
KR101500036B1 (ko) * | 2012-08-27 | 2015-03-18 | (주)엘지하우시스 | 샌드위치 패널용 심재 및 이의 제조방법, 이를 포함하는 샌드위치 패널 |
CN110154299B (zh) * | 2018-01-31 | 2021-05-14 | 广州金兰标识制品有限公司 | 一种双层透光无泡材料的制备方法 |
IT201800005818A1 (it) * | 2018-05-29 | 2019-11-29 | Processo per decorare superfici di elettrodomestici, in particolare piccoli elettrodomestici | |
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DE102020113705A1 (de) | 2020-05-20 | 2021-11-25 | Lisa Dräxlmaier GmbH | Verfahren zum herstellen eines bauteils und bauteil |
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