CN1267256A - 带掩模薄膜的漆膜组件 - Google Patents

带掩模薄膜的漆膜组件 Download PDF

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CN1267256A
CN1267256A CN98808254A CN98808254A CN1267256A CN 1267256 A CN1267256 A CN 1267256A CN 98808254 A CN98808254 A CN 98808254A CN 98808254 A CN98808254 A CN 98808254A CN 1267256 A CN1267256 A CN 1267256A
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paint film
film
paint
mask
layer
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CN1091411C (zh
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C·T·斯卡林
D·V·弗拉特
F·E·杜姆
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3M Co
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    • B32B1/00Layered products having a non-planar shape
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    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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    • B29C37/00Component parts, details, accessories or auxiliary operations, not covered by group B29C33/00 or B29C35/00
    • B29C37/0025Applying surface layers, e.g. coatings, decorative layers, printed layers, to articles during shaping, e.g. in-mould printing
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00Layered products comprising a layer of synthetic resin
    • B32B27/36Layered products comprising a layer of synthetic resin comprising polyesters
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    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00Layered products comprising a layer of synthetic resin
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04Interconnection of layers
    • B32B7/12Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B44DECORATIVE ARTS
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    • B44C1/00Processes, not specifically provided for elsewhere, for producing decorative surface effects
    • B44C1/16Processes, not specifically provided for elsewhere, for producing decorative surface effects for applying transfer pictures or the like
    • B44C1/165Processes, not specifically provided for elsewhere, for producing decorative surface effects for applying transfer pictures or the like for decalcomanias; sheet material therefor
    • B44C1/17Dry transfer
    • B44C1/1733Decalcomanias applied under pressure only, e.g. provided with a pressure sensitive adhesive
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/20Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for coatings strippable as coherent films, e.g. temporary coatings strippable as coherent films
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C37/00Component parts, details, accessories or auxiliary operations, not covered by group B29C33/00 or B29C35/00
    • B29C37/0025Applying surface layers, e.g. coatings, decorative layers, printed layers, to articles during shaping, e.g. in-mould printing
    • B29C37/0028In-mould coating, e.g. by introducing the coating material into the mould after forming the article
    • B29C2037/0042In-mould coating, e.g. by introducing the coating material into the mould after forming the article the coating being applied in solid sheet form, e.g. as meltable sheet
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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    • B29C2791/00Shaping characteristics in general
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    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C51/00Shaping by thermoforming, i.e. shaping sheets or sheet like preforms after heating, e.g. shaping sheets in matched moulds or by deep-drawing; Apparatus therefor
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C51/00Shaping by thermoforming, i.e. shaping sheets or sheet like preforms after heating, e.g. shaping sheets in matched moulds or by deep-drawing; Apparatus therefor
    • B29C51/10Forming by pressure difference, e.g. vacuum
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C51/00Shaping by thermoforming, i.e. shaping sheets or sheet like preforms after heating, e.g. shaping sheets in matched moulds or by deep-drawing; Apparatus therefor
    • B29C51/14Shaping by thermoforming, i.e. shaping sheets or sheet like preforms after heating, e.g. shaping sheets in matched moulds or by deep-drawing; Apparatus therefor using multilayered preforms or sheets
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T156/00Adhesive bonding and miscellaneous chemical manufacture
    • Y10T156/10Methods of surface bonding and/or assembly therefor
    • Y10T156/1002Methods of surface bonding and/or assembly therefor with permanent bending or reshaping or surface deformation of self sustaining lamina
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T156/00Adhesive bonding and miscellaneous chemical manufacture
    • Y10T156/10Methods of surface bonding and/or assembly therefor
    • Y10T156/1002Methods of surface bonding and/or assembly therefor with permanent bending or reshaping or surface deformation of self sustaining lamina
    • Y10T156/1028Methods of surface bonding and/or assembly therefor with permanent bending or reshaping or surface deformation of self sustaining lamina by bending, drawing or stretch forming sheet to assume shape of configured lamina while in contact therewith
    • Y10T156/1031Methods of surface bonding and/or assembly therefor with permanent bending or reshaping or surface deformation of self sustaining lamina by bending, drawing or stretch forming sheet to assume shape of configured lamina while in contact therewith with preshaping of lamina
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    • Y10T428/31504Composite [nonstructural laminate]
    • Y10T428/3154Of fluorinated addition polymer from unsaturated monomers
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract

一种漆膜组件(20),包括高光泽和DOI的可热成形的漆膜(22)和可热成形的掩模薄膜(24),掩模薄膜可除去地粘附在漆膜(22)上,以便在例如运输和搬运中和随后将漆膜(22)成形和加工(如热成形和/或嵌件模塑)在制品或部件上时更好地保护漆膜(22),同时基本保留漆膜(22)的表面光洁度,尤其是光泽和DOI。掩模薄膜(24)包括层压或用其它方法粘附在漆膜(22)上的聚氨酯层(28),形成掩蔽漆膜(32)。掩模薄膜(24)可与漆膜(22)一起热成形和/或模塑,以便形成可热成形和/或模塑的掩蔽漆膜(32)。当掩蔽漆膜(32)热成形和/或模塑后,掩模薄膜(24)仍能容易地从漆膜(22)上除去。聚氨酯层(28)在操作上是合适的,以便热成形和/或模塑所述掩蔽漆膜(32)并且从所述漆膜(22)上除去所述掩模薄膜(24)后,至少基本保留所述漆膜(22)的高光泽和DOI。

Description

带掩模薄膜的漆膜组件
发明的领域
本发明涉及一种使基片具有装饰特征的面层薄膜,具体地说,本发明涉及用于表面加工物体(如汽车部件)的漆膜,更具体地说,本发明涉及包括可除去地粘合在漆膜上的掩模薄膜的可热成形的漆膜组件,在热成形过程中,该掩模薄膜能基本保持漆膜的表面光洁度,尤其是漆膜的光泽和DOI。
发明的背景
产品最重要的特征之一通常是其外观。汽车制造商特别关心其制造的汽车的外观。通常对例如汽车车身面板、装饰部件、侧视镜护罩(side view mirrorhousing)和类似的汽车部件进行喷漆以获得所需的外观(即颜色和光洁度)。近来,用预制的多层漆膜代替某些外露的汽车部件的喷漆。除了其它优点以外,这种漆膜避免了与漆溶剂蒸发有关的环境问题,并无需额外的喷漆设施和相关设备、烘箱、淤泥处置和辐射控制设备。但是,使用现有的漆膜也有不利之处,尤其在颜色和表面光洁度方面。
这种漆膜通常包括一层具有所需油漆光洁度的装饰层,它通常例如通过热成形(即在加热状态下形成薄膜)而预制。随后将预制的漆膜粘合在所需的部件表面上。当所述部件是塑料的模塑部件时,漆膜通过与该部件的嵌件模塑进行粘合,某些漆膜的装饰层是流延在载体层上而形成的。形成流延装饰层的载体层表面,使之具有装饰层所需的表面光洁度。另外,已报道在制得漆膜后将载体层留在漆膜上,以便在随后的运输和搬运过程中,以及随后在将漆膜施加至部件上时保护该漆膜(即将漆膜热成形成预制的状态,用于粘结在部件上)。
汽车制造商常要求其汽车的油漆表面具有很高的光泽和DOI(即镜像清晰度或似镜面反射),尤其要求具有金属般的油漆光洁度。将装饰层流延在具有高光泽的载体层上使得漆膜具有高的光泽和DOI。但是,一些现有的载体层的热成形性非常有限,从而限制了将漆膜用于平面或轻微凹凸的部件上。带具有改进的热成形性的载体层的漆膜可参见例如Shimanski等的美国专利5,215,826。但是,这些载体层的热成形性仍有局限。此外,即使现有的载体层表现出足够的热成形性用于具体的用途,但是漆膜和载体层热成形后通常观察到漆膜的光泽和DOI明显下降。
因此,需要一种更好的方法在运输和搬运过程中以及随后在将漆膜施加至部件的过程中保护该漆膜(如将漆膜热成形成预制状态用于粘结至部件上),同时基本保留漆膜的表面光洁度,尤其是光泽和DOI。
发明的概述
根据本发明原理,将掩模薄膜可除去地粘结至漆膜上可满足上述要求,从而在运输和搬运过程中,以及随后将漆膜成形和加工(如热成形和/或嵌件模塑)在制品或部件上时能更好地保护漆膜,同时基本保留漆膜的表面光洁度。尤其是光泽和DOI(即镜像清晰度或似镜面反射)。
在本文中,术语“漆膜”包括一种多层的热塑性薄膜,它表面保护和装饰下层物体,它具有足够的挠性以在加工温度下贴合下层物体,并具有一层含一种或多种着色剂的着色层,它可包括一层或多层粘合于它上面的下列各层:透明涂层(位于表面上用于外观和保护)、增强层(位于着色层下面,用于提供强度)、粘合层(如果需要,位于底部用于将漆膜牢固地粘结至下层物体上)和衬里层(在外表面层上,可从该外表面层上除去)。另外,在本文中,高光泽指在20°光泽至少约为60,高DOI指至少具有约60 DOI。
本发明另一方面提供一种漆膜组件,它包括具有高光泽和DOI的可热成形的漆膜。希望漆膜还可以例如通过嵌件模塑进行模塑。希望漆膜可热成形成精确的细节(即可纵深地(deeply)热成形以贴合严重凹凸的表面)。漆膜包括着色涂层。漆膜还宜包括透明的涂层来覆盖着色涂层。透明涂层和着色涂层可以任何合适的方式形成并粘结在一起。例如,它们可各自挤出或流延而成。它们可以单独形成并层压或用其它方法粘结在一起,或者可以将一种涂层涂覆在另一种涂层上(例如将一种涂层挤出、流延或喷涂在另一种涂层上)。含有聚氨酯层(例如流延或挤出的聚氨酯层)的可热成形的掩模薄膜被层压或用其它方式粘合在漆膜上,形成掩蔽漆膜。聚氨酯层不一定仅含聚氨酯。掩模薄膜可与漆膜一起热成形,形成可热成形的掩蔽漆膜。掩蔽漆膜热成形后,掩模薄膜仍能容易地从漆膜上除去。掩模薄膜还宜能与漆膜一起模塑,形成模塑的掩蔽漆膜。掩蔽漆膜模塑后,可容易地将掩模薄膜从模塑的漆膜上除去。对于带透明涂层的漆膜,掩模薄膜的聚氨酯层宜粘合在透明涂层上。聚氨酯层在加工上是合适的,以便在掩蔽的漆膜热成形和/或模塑后并且从漆膜上除去掩模薄膜后,至少能基本保留漆膜,尤其是具有透明涂层的漆膜的高光泽和DOI。
漆膜宜包括承载层或增强层,它粘合或用其它方式粘结在着色涂层的背面,向漆膜提供结构支承。这种承载层宜能粘合(例如通过模塑)在作为制品或部件的一部分或全部的基片(如模塑的塑料壳)上。
在热成形和/或模塑掩蔽漆膜的过程中,认为掩模薄膜宜在操作上适合于拉伸(即伸长)与漆膜基本相同的程度。还认为伸长的掩蔽漆膜的掩模薄膜宜具有记忆(即从伸长状态回复的程度),在加热后(如热成形和/或模塑后)当掩蔽漆膜冷却时该记忆与漆膜的记忆基本相同或相似。在热成形和/或模塑温度下,掩模薄膜的强度还宜至少与掩蔽漆膜的漆膜部分相同或者更强,同时经加热冷却后不明显回复(recovery)。
掩模薄膜宜能牢固地粘结在漆膜上并保持与其的粘合,在掩蔽薄膜的搬运过程中、加工前和加工过程中(如热成形和/或模塑)不明显脱开,同时在加工后仍能容易地从漆膜上除去。
漆膜可包括含金属薄片的着色涂层。特别好的是本发明掩模薄膜能保持含这种着色涂层的漆膜的高光泽和DOI。在热成形时,具有含金属薄片的着色涂层的漆膜看来更容易失去其光泽和DOI。漆膜和掩模薄膜可一起形成或单独形成。宜单独形成漆膜和掩模薄膜,使漆膜的一个表面具有高的光泽和DOI光洁度,使掩模薄膜在一个侧面具有高光泽的光洁度,并将漆膜和掩模薄膜的光洁一面对置并相互接触而将其层压在一起。
本发明另一方面是提供一种制造漆膜组件的方法。该方法包括下列步骤:形成具有高光泽和DOI的漆膜;形成含聚氨酯层的掩模薄膜;将掩模薄膜粘附在漆膜上,形成可热成形和/或可模塑的掩蔽漆膜,其中掩模薄膜容易从漆膜上除去。聚氨酯层在操作上是合适的,使得在热成形和/或模塑掩蔽漆膜并除去掩模薄膜后,漆膜至少基本保持其原来的高光泽和DOI。在粘附步骤前,本发明方法可包括单独形成漆膜和掩模薄膜的步骤。
在形成步骤中,宜在漆膜上和掩模薄膜上形成光洁的表面,在粘附步骤中,宜包括将漆膜的光洁表面和掩模薄膜的光洁表面层压在一起,制成掩蔽漆膜。所述单独形成步骤可包括形成漆膜的步骤,例如,用水或溶剂将漆膜流延在高光泽的基片(如衬里)表面,以便在漆膜上形成具有高光泽和DOI的光洁表面。所述单独形成步骤还可包括形成掩模薄膜的步骤,例如,用液体(即水或溶剂)将聚氨酯层流延在另一个基片(如衬里或漆膜)的高光泽表面上,以便在聚氨酯层上形成具有高光泽的光洁表面。当用于流延聚氨酯层的基片不是漆膜时,在粘附步骤前从一个基片上取下漆膜,而从另一个基片上取下聚氨酯层。粘附步骤包括将漆膜的光洁表面和聚氨酯层的光洁表面层压在一起,形成掩蔽漆膜。当要形成的漆膜包括透明涂层时,形成漆膜的步骤包括在基片表面上形成透明涂层,以便在具有光泽的透明涂层上形成光洁表面,该表面使漆膜具有高光泽和DOI。
本发明方法可包括将掩蔽漆膜热成形成所需形状并从漆膜上除去掩模薄膜的步骤。本发明方法还可包括将掩蔽漆膜热成形成所需形状,将掩蔽漆膜粘合在基片上,并除去掩模薄膜的步骤。另外,本发明方法可包括将掩蔽漆膜热成形成所需的形状,将掩蔽漆膜嵌件模塑成模塑塑料部件,并从漆膜上除去掩模薄膜的步骤。
附图简述
图1是根据本发明原理的漆膜组件的剖面图;
图2是固定在衬里上的本发明掩模薄膜的剖面图;
图3是固定在衬里上的本发明漆膜的剖面图;
图4是将漆膜和掩模薄膜层压在一起形成掩蔽漆膜的方法的示意图;
图5A-5F在热成形法的各个阶段,本发明热成形阳模和掩蔽漆膜片的剖面图;
图6A-6E是嵌件模塑的各阶段本发明嵌件模具和掩蔽漆膜或漆膜预制片的剖面图;
图6F是具有半球形部分的本发明热成形和嵌件模塑的漆膜组件的剖面图;
图7A-7G是嵌件模塑的各阶段本发明嵌件模具和掩蔽漆膜片的剖面图,其中掩蔽漆膜是嵌件模塑形成的。
图8A-8F是热成形方法的各阶段本发明热成形阴模和掩蔽漆膜片的剖面图。
发明的详细描述
虽然本文通过具体实例描述本发明,但是本领域的普通技术人员容易地得知在不偏离本发明精神的情况下,可对其进行各种改进、重排和替换。因此本发明的范围仅受所附的权利要求书限定。
参见图1,本发明漆膜组件20包括可热成形的漆膜22和掩模薄膜24。漆膜的上表面26具有高的光泽和DOI(即镜像清晰度)。表面26在20°的光泽度宜至少约为60并宜至少约60 DOI。掩模薄膜24包括具有高光泽表面30的聚氨酯层28。聚氨酯层28的高光泽表面30粘附在漆膜22的高光泽/DOI表面26上,并能容易地从该表面上除去,以形成可热成形的掩蔽漆膜32。掩模薄膜24的表面30在20°光泽度宜至少约为60。
参见图2,掩蔽薄膜24宜包括粘附于聚氨酯层28背面(即粘附在与表面30相反的一面)的增强层34,为的是到时候能更容易地从漆膜22上除去掩模层24。没有增强层34,聚氨酯层28会被撕裂并呈片状从热成形和/或模塑的漆膜22上被撕下。使用增强层34可使掩模薄膜24更容易被整片除去。使用流延在剥离衬里或载体38的高光泽表面36上的聚氨酯分散液可获得满意的结果。令人满意的可流延聚氨酯混合物及其组成的例子将在下面详细描述。衬里38的表面36宜具有可能的最高光洁度,使得聚氨酯层28的表面30具有这样高的光泽。发现聚氨酯层28的厚度宜约为0.6-1.6mil。为了降低起泡的可能性,发现聚氨酯层28的厚度更好不超过约1.2mil。
对于下面描述的例举的聚氨酯层28,使用聚酯材料制造衬里38可获得令人满意的结果。具有高光泽表面的可接受的聚酯衬里38可例如通过流延在镀铬辊上并进行双轴取向以获得高的拉伸强度而制得。衬里38也能容易地从聚氨酯层28上除去,使得分离表面30和36不会造成聚氨酯表面30的光泽度明显下降。
掩模薄膜24的聚氨酯层28宜是未交联的(即是纯热塑性的)。即便如此,聚氨酯层28稍许交联也是可接受的,只要在热成形和/或模塑掩蔽漆膜32的过程中掩模薄膜24仍能与漆膜22一起伸长。未交联的用作层28的流延聚氨酯材料的一个例子包括胶乳分散液状的聚氨酯树脂,它以NeoRez R 9679的商品名购自ICI Resins US,of Wilmington,MA。该聚氨酯胶乳分散液树脂混有常用的溶剂,如乙酸丁酯(dibutyl acetate)和/或丁基卡必醇。该例举的聚氨酯材料还包括有助于均匀湿润的表面活性剂(Triton GR-7M,购自UnionCarbide Danbury Connecticut)、降低掩模薄膜24和漆膜22之间粘性(即有助于除去掩模薄膜24)的两种液态硅氧烷(BYK310和BYK307,购自BYK ChemieUSA of Wallingford,Connecticut)和检查添加剂(Levcophor B-302,购自Clariant Corporation of Charlotte,North Carolina),这种添加剂在黑光下会变白,以检验是否存在掩模薄膜24。
第一种例举的聚氨酯层28是如下形成的:将3000g聚氨酯树脂NeoRez R9676与6.0g表面活性剂Triton GR-7M和3.0g UV着色剂Leucophor B302预混。随后,将9.0g液态硅氧烷BYK301和3.0g液态硅氧烷BYK 307混入210g溶剂乙酸丁酯中。接着使用高剪力混合机将液态硅氧烷与溶剂的混合物缓慢地加入聚氨酯树脂预混物中制得聚氨酯层材料。加入所有材料后,混合机运转约10分钟。将该组合物静置(left covered)约24小时以除去空气。使一片0.06mm厚的高光泽光滑聚酯载膜通过刮刀涂覆机,将聚氨酯层刮刀涂覆在该聚氨酯载膜的高光泽表面上,形成湿涂层厚度为0.15mm的涂层。将该湿涂层在烘箱中在66℃放置2分钟、在93℃放置2分钟并在149℃放置1分钟进行干燥。形成的聚氨酯层28的标称厚度为0.03mm。聚氨酯层28可单独用作掩模薄膜24,或者它可用一层或多层其它层进行增强。
第二种例举的聚氨酯层28是根据上述制备第一种例举的层28的方法制得的,但是使用2,790.0gNeoRez R 9679、6.0g Triton GR-7M、9.0g BYK 301、3.0g BYK 307、3.0g Leucophor B-302和189.0g溶剂丁基卡必醇。当混合在一起时,聚氨酯材料、乙酸丁酯和丁基卡必醇的任何一种组分应分别以非常慢的速度加入,以防止混合物震动而聚结。
适合于液态流延成层28的聚氨酯材料的另一个例子包括上述NeoRez R9676聚氨酯树脂和合适的交联剂,例如ICI Resins US制的名为NeoCryl CX-100的交联剂。这种例举的聚氨酯材料还包括上述表面活性剂Triton GR-7M;以及常用的溶剂丁基卡必醇,例如Union Carbide Corporation制的丁基卡必醇。如有必要,检查添加剂Leucophor B-302可加入该批可交联的聚氨酯材料中。
第三种例举的有些交联的聚氨酯层28可如下制得:将90.79重量%聚氨酯树脂NeoRez R 9676与0.18重量%表面活性剂Triton GR-7M预混在一起。接着,用高剪力混合机将9.03重量%的溶剂丁基卡必醇缓慢地加入聚氨酯树脂预混物中。全部物料加入后,使混合机再运转一段时间。就在形成聚氨酯层之前,混入1.20重量%交联剂NeoCryl CX-100。将该组合物静置适当的时间以除去空气。使一片高光泽光滑的聚酯载膜通过刮刀涂覆机,将聚氨酯材料刮刀涂覆在聚酯载膜的高光泽表面上,形成合适的湿涂层厚度,以获得所需的干涂层厚度。随后在烘箱中干燥该湿涂层。
认为聚氨酯层28可通过液态(即水性或溶剂)流延或挤出(如吹塑薄膜挤出)而制得。挤出层28可粘附(如层压)在漆膜上。认为这种流延或挤出聚氨酯层28可由单种聚氨酯树脂、聚氨酯共聚物或聚氨酯聚合物合金制得。
适合于形成任选的增强层34的聚合物材料的一个例子是溶剂流延的聚氯乙烯(PVC)分散液,它包括Geon Corporation of Avon,Ohio制的名为Geon 178的PVC树脂粉;Velsicol Corporation of Chattanooga,Tennessee制的名为Admex 770的聚合物增塑剂;Witco of Grennwich,Connecticut制的名为Nuostab V-1923的热稳定剂;和常用的溶剂石油溶剂油(mineral spirits)、二异丁基酮和混合二甲苯。
一种例举的增强层34可如下制得:制备4.04g石油溶剂油、7.63g二异丁基酮和10.78g混合二甲苯的溶剂混合物。接着向该混合物中加入18.72g聚合物增塑剂Admex 770和2.67g热稳定剂Nuostab V-9123。随后使用高剪力混合机将56.16g PVC树脂Geon 178缓慢加入溶剂混合物中以分散该树脂,随后混合一小时以形成均匀的组合物用于制造增强层34。接着用刮刀将增强层组合物直接涂覆在承载于聚酯载体38上的聚氨酯层28上,形成湿涂层厚度为0.076mm。将湿的掩模薄膜24在烘箱中于66℃放置1分钟、于93℃放置1分钟、于149℃放置1分钟并于204℃放置1分钟进行干燥。形成的增强层34厚度约为0.038mm,形成的掩模薄膜的厚度为0.068mm。
参见图3,漆膜22的一个实例包括粘合在着色涂层42上的透明涂层40。可用任何合适的方法制得透明涂层40和着色涂层42并将其粘结在一起。例如,它们可各自通过挤出或流延制得。可将其单独形成并层压或用其它方法粘结在一起;或者可将一层涂覆在另一层上(如将一层挤出、流延或喷涂在另一层上)。发现漆膜22宜包括粘结在着色涂层42背面的增强层44。用热塑性含氟聚合物分散在丙烯酸树脂的合金中制得的透明涂层40可获得令人满意的结果。例如,透明涂层40可以是聚偏二氟乙烯(PVDF)作为单独的相分散在聚甲基丙烯酸甲酯(PMMA)基质或聚甲基丙烯酸乙酯(PEMA)基质中的分散体。透明涂层40可以是分散液流延并干燥在衬里或载体48的表面46上,以使漆膜22具有高光泽/DOI的表面26。如上述聚酯衬里38那样,使用聚酯制得的衬里48可获得令人满意的结果。衬里48还必须能从透明涂层40上除去,结果不明显影响漆膜表面26的光泽和DOI。还发现宜将PVDF在PMMA中的分散液通过分散液流延在透明涂层40上来形成着色涂层42。可使用任何合适的方法使层42具有颜色,包括在流延至透明涂层40上以前,将金属颜色的颗粒或薄片混入PVDF/PMMA分散液中。
尽管无需对本发明进行如此限定,但是发现用分散在PMMA中的PVDF的分散液流延制得的透明涂层40要好于用PVDF在PMMA中的溶液流延制得的相似透明涂层。这种分散液流延的透明涂层40通常比相似的溶液流延层40便宜。如本文所述,发现在热成形和/或模塑掩蔽漆膜32的过程中,使用本发明掩模薄膜24能使PVDF/PMMA分散液流延的透明涂层40保持高的光泽,从而使形成的漆膜22保持高的光泽和DOI。发现在不存在本发明掩模薄膜24时进行热成形和/或模塑,具有PVDF/PMMA分散液流延的透明涂层40的这种漆膜22的光泽和DOI会明显下降。具有溶液流延的PVDF/PMMA透明涂层的漆膜的例子可参见PCT申请No.PCT/US88/00991(国际公布号WO 88/07416),它的国际申请日为1988年3月25日,国际公布日为1988年10月6日。
其它漆膜的例子可参见1997年9月30日提交的美国专利申请08/941,751,它是1996年9月16日提交的题为“漆膜及其制造方法和在物体,如汽车部件中的应用”的美国专利申请08/716,681(现已放弃)的继续申请,该申请转让给本发明同一受让人。其它漆膜的例子可参见1989年3月7日授权的美国专利4,810,540、1990年6月5日授权的美国专利4,931,324、1990年7月24日授权的美国专利4,943,680和1993年6月1日授权的美国专利5,215,826。与美国专利5,215,826不同,本发明掩模薄膜24的高光泽表面30是通过一层聚氨酯层形成的。另外,与美国专利5,215,826公开的内容相比,本发明掩蔽漆膜32能更深地热成形,用于更凹凸不平的部件。
可使用增强层44以使漆膜22具有额外的强度。使用热塑性烯烃(TPO)或丙烯腈-丁二烯-苯乙烯共聚物(ABS)制得的挤出增强层44可获得令人满意的结果。发现宜用例如由聚氨酯粘合剂(PUR)(如湿固化的PUR粘合剂)制成的粘合剂层50将增强层44粘结在着色涂层42的背面上。粘合剂层50可以例如逆辊涂覆或刮刀涂覆在着色涂层42上。为提高粘合剂层50的粘结强度,可对着色涂层42和增强层44的表面52和54分别进行电晕处理。
一种例举的漆膜22包括透明涂层40,它是通过将PVDF在PMMA或PEMA中的分散液液态流延在PET载体48的高光泽表面46上,随后将湿涂覆的层40干燥至约1.9mil的干厚度而制得的。接着将着色涂层42流延在干的透明涂层40上。该着色层是将带着色剂的PVDF在PMMA中的分散液流延在透明涂层40的背面(即与表面26相反的一面)而制得的。着色的涂层42应如此施涂,即干燥后其厚度约为1.5mil。对由TPO或ABS制得的厚约17mil的挤出的增强层44的表面进行电晕处理,并用厚度约0.3mil的PUR粘合剂层50将其粘结在着色涂层42经电晕处理的背面上。
参照图4,可将掩模薄膜24和漆膜22粘附在一起制得漆膜组件20的掩蔽漆膜32。开始时,从漆膜22上除去衬里48,从掩模薄膜24上除去衬里38。接着将掩模薄膜24的高光泽表面30和漆膜22的高光泽/DOI表面26可剥离地粘结在一起。形成这种可剥离粘结的一种方法是将薄膜22和24层压在一起。在一种例举的层压方法中,将漆膜22和掩模薄膜24从各自的供料辊56和58上拉出,并使之通过在橡胶辊62和钢辊64之间形成的热辊隙60。钢辊64用常规方法加热。在漆膜22和掩模薄膜24层压在一起之前除去衬里48和38。薄膜24在供料辊58上时衬里38宣留在掩模薄膜24上。接着在掩模薄膜24到达辊隙60之前从掩模薄膜24上剥离衬里38并将衬里缠绕在卷辊66上。可在漆膜22缠卷在供料辊56上以前除去衬里48。或者,漆膜22可带着衬里48缠绕在辊56上。随后在漆膜22和掩模薄膜24层压在一起之前剥离衬里48并将其缠绕在卷辊68上(如图4所示)。
使橡胶辊62表面上的硬度计读数约为70Shore A、热辊64使辊隙60的温度约为160-230°F、辊62和64之间的压力约为100-110psi、并且使薄膜22和24的移动速度约为3-20英尺/分钟可获得令人满意的结果。
在漆膜22和掩模薄膜24层压在一起以后,将形成的掩蔽漆膜32缠绕在另一个卷辊70上以便随后加工(如热成形和/或模塑加工)。或者,可随后对掩蔽漆膜32进行在线加工(如热成形),而非缠卷在辊70上,开卷。随后再加工。
参见图5A-5F,可将掩蔽漆膜32预成形(如用热成形法)成将要形成的最终制品或部件所要求的形状或外形(如汽车侧面模塑物、侧镜护罩、保险杠、挡泥板等)。可使用工业中已知的常规技术热成形本发明掩蔽漆膜32。一般来说,这种热成形方法包括从卷70上开卷掩蔽漆膜32,并使漆膜32通过常规的热成形设备72。热成形设备72包括真空成形阳模74和合适的加热装置(如从上部加热漆膜32的红外加热器)以软化掩蔽漆膜32。将加热的漆膜32置于阳模74上。多个真空孔76穿过阳模74用于在模具和漆膜之间形成真空,并将加热的漆膜32朝下吸在模具74上,直至软化的漆膜32贴合阳模74的外表面或形状。当掩蔽漆膜32完全热成形成所需的形状后(见图5),将预制的漆膜32从模具74上取下,冷却或使之空气冷却。此时,可将掩模薄膜24从此刻预制的掩蔽漆膜32上取下,或者留在原地,与漆膜22一起进行随后加工(如模塑)。
如有必要,可例如用标准的切割模头78修整掉预制掩蔽漆膜32的多余薄膜32(图中用两边的切割边缘表示)。这种切割模头78可以是热成形设备72的一部分,以便在热成形步骤后自动进行修整加工。或者,可使用切割模头78手工或自动地离线进行修整加工。较佳的是切割模头78可仅部分修整预制的掩蔽漆膜32,其余的用手工修整,而非全部用这种切割模头78进行修整。在随后加工(如嵌件模塑)预制的漆膜22前需要除去掩模薄膜24时,可采用上述两步修整法。发现用剪刀剪去要修整的部分漆膜32可有助于除去掩模薄膜24。用剪刀剪切会使掩模薄膜24明显脱离漆膜22,从而容易抓住该掩模薄膜。一旦抓住掩模薄膜24后,能容易地将其从漆膜22上剥离。
参见图8A-8F,除了使用真空成形阳模74以外,热成形设备72可包括真空成形阴模80,该阴模包括真空孔76用于将加热的掩蔽漆膜32朝下吸入模腔82。认为使用真空成形阴模80热成形掩蔽漆膜32,能低成本地有效地形成漆膜32。通常,使用多个模具74和/或80来热成形掩蔽漆膜32的给定部分或给定片。用这种方法,可在掩蔽漆膜32的多个位置同时进行热成形,每个热成形部分适合于覆盖一个制品或部件。认为使用阴模80而非阳模74能在单位面积的掩蔽漆膜32上形成更多数量的热成形部分83(见图8E和8F)。由于更多部分的掩蔽漆膜32得到利用,可减少修整掉的边角料。
可使用无论哪一类型的模具74或80来热成形掩蔽漆膜32,漆膜32相对模具74或80放置,使得除去掩模薄膜24后,漆膜22的高光泽/DOI表面26构成要制造的制品或部件的外表面或露出表面。通常,当用图5A-5F的阳模热成形掩蔽漆膜32时,并且漆膜32用于覆盖制品或部件总体上凸起的部分时,掩模薄膜24位于掩蔽漆膜32与真空成形模具74不接触的那一侧。当使用阴模成形模具80热成形掩蔽漆膜32时,并且漆膜32用于覆盖制品或部件总体上凸起的部分时,放置掩蔽漆膜32,使掩模薄膜24位于与模具80接触的那一侧。当将掩蔽漆膜32热成形用于制品或部件的凹形部分时,则掩模薄膜24的放置方向与上述对于各种模具74和80时的放置方向相反。当随后的加工包括嵌件模塑时,则通常将带有或不带有掩模薄膜24(即薄膜24留在原位或被除去)的预制掩蔽漆膜32修整成其最终的形状(如人工修整和/或用切割模头78修整(见图5F和8F)),使之适配在模具84中(见图6A-6E)。
在下面参照图6A-6E的描述中,除非另有说明,否则所有涉及掩蔽漆膜32的描述均适用于带有或不带有掩模薄膜24的漆膜32。典型的嵌件模塑装置84包括两个半模86和88,在两者的中间形成模腔90。当半模86和88分开时,将预成形的漆膜32置于两个半模86和88之间。宜将预制的漆膜32贴住两个半模86(如图所示)或88中的一个放置。随后闭合模具84,在预制漆膜32后面的模腔90部分通过注射孔92填充入所需的塑料材料。注射的塑料材料粘附在漆膜32上。固化后,塑料材料形成漆膜22的基片94。形成的漆膜组件20可构成要制造的制品或部件的一部分或全部。冷却基片94和漆膜32后,开启模具84,取出漆膜组件20。
除非掩蔽漆膜32被预制成与模具84(如半模86)具有基本上相同的形状细节,否则预制漆膜32难以适配在模具84中。与现有技术公开的这些漆膜相比,本发明掩蔽漆膜32尤其适合热成形成精确的细节。具体地说,根据漆膜32的哪一面将注射塑料,认为本发明掩蔽漆膜32可热成形以匹配膜腔95或模芯96的形状,如图6A-6E那样(其中模腔95或模芯96具有矩形即立方体的结构)。可成功地热成形本发明掩蔽漆膜32,使得半圆即半球状的部分98(见图6F)匹配具有这种形状的模腔或模芯。
参见图7A-7G,代替如上所述的预制掩蔽漆膜32(见图5A-5F和8A-8F)以及随后嵌件模塑预制的漆膜32(见图6A-6F),宜将掩蔽漆膜32同时形成并模塑。也就是说,掩蔽漆膜32可完全在模具内加工。在这种模具内加工的说明性例子中,一部分预先裁下的掩蔽漆膜32被放入模具84的半模86和88之间。可将该掩蔽漆膜部分32的外周部分100(如外边缘)相对半模86和88固定就位。例如,可将外周边缘100夹在或用其它方法固定在阴半模86上。将该掩蔽漆膜部分32置于半模86和88之间,闭合模具84。当闭合模具84时,模芯96与掩蔽漆膜32接触,将漆膜32推入半模86的模腔95。当模芯96移入模腔95时,掩蔽漆膜32开始被拉伸(即伸长)。模具84闭合后(将图7D),通过注射开孔92向模腔90中填充入熔融的聚合物材料。当模腔90充满聚合物材料时,迫使此刻部分成形的掩蔽漆膜32形成其最终的形状,与模腔95的外形相一致(见图7E)。如有必要,可在半模86上形成注射开孔92,并且可填充模腔90,以迫使部分成形的漆膜32与模芯96的外形相一致。一旦聚合物材料固化成基片94,开启模具84并取出形成的漆膜组件20。形成的漆膜组件20可包括不带背衬基片94的外周部分100。如有必要,可修整该外周部分或用任何合适的方式(如手工和/或切割模头78)将其除去。
这种模具内加工方法及其设备的一个例子公开在1996年3月7日提交的题为“漆膜及其制造方法和在物体,如汽车部件上的应用”的美国专利申请08/612,209,该申请转让给了本申请的受让人。
为了在模塑过程中有助于防止空气夹持在掩模薄膜24和可适用的半模(如图6A-6E和7A-7G所示的半膜86)之间,宜使聚氨酯层28和衬里38的表面30和34分别具有纹理。此时聚氨酯层28带纹理的一侧向层28和可适用的半模之间逸出的空气提供通道。这要求聚氨酯层28的另一侧(即在层28流延过程中暴露在空气中的一侧)层压在漆膜22的表面26上。通常,流延时暴露在空气中的聚氨酯层28的那一侧具有高的光泽。
从上面本发明原理的描述和详细描述的方法,本领域的普通技术人员可容易地领会本发明的各种变化。因此,本发明的范围仅受所附的权利要求书及其等同内容的限制。

Claims (22)

1.一种漆膜组件(20),它包括:
具有高光泽和DOI的可热成形的漆膜(22);和
可热成形的掩模薄膜(24),它包括粘附在所述漆膜(22)上并可容易地从漆膜上除去的聚氨酯层(28),以便形成可热成形的掩蔽漆膜(32),所述掩模薄膜(24)能容易地从所述漆膜(22)上除去,所述聚氨酯层(28)在操作上是合适的,以便在热成形所述掩蔽漆膜(32)并且从所述漆膜(22)上除去所述掩模薄膜(24)后,至少基本保留所述漆膜(22)的高光泽和DOI。
2.如权利要求1所述的漆膜组件(20),其特征在于所述掩模薄膜(24)包括流延的水性聚氨酯层(28)。
3.如权利要求1所述的漆膜组件(20),其特征在于在热成形所述掩蔽漆膜(32)的过程中,所述掩模薄膜(24)在操作上适合于拉伸与所述漆膜(22)基本相同的程度,并且热成形后当所述掩蔽漆膜(32)冷却时,所述掩模薄膜(24)的回复程度与所述漆膜(22)的回复程度基本相似。
4.如权利要求1所述的漆膜组件(20),其特征在于在热成形过程中,所述掩模薄膜(24)的强度至少与所述漆膜(22)相同,并且经加热冷却后,不具有明显的记忆。
5.如权利要求1所述的漆膜组件(20),其特征在于所述掩模薄膜(24)能牢固地粘结在所述漆膜(22)上并保持与其的粘结,在掩蔽薄膜(24)的热成形过程中不明显脱开,同时在热成形后仍能容易地从所述漆膜(22)上除去。
6.如权利要求5所述的漆膜组件(20),其特征在于所述掩模薄膜(24)能牢固地粘结在所述漆膜(22)上并在所述掩蔽漆膜(32)的模塑过程中保持与漆膜(22)的粘结,同时在模塑后仍能容易地从所述漆膜(22)上除去。
7.如权利要求1所述的漆膜组件(20),其特征在于所述漆膜(22)包括含金属薄片的着色涂层(42)。
8.如权利要求1所述的漆膜组件(20),其特征在于所述漆膜(22)和所述掩模薄膜(24)各自单独形成,所述漆膜(22)的一侧具有高光泽和DOI光洁度,所述掩模薄膜(24)的一侧具有高光泽光洁度,并且所述漆膜(22)和掩模薄膜(24)以光洁表面对置的方式层压在一起。
9.如权利要求1所述的漆膜组件(20),其特征在于所述漆膜组件(20)包括上面粘结所述漆膜的基片(94)。
10.如权利要求9所述的漆膜组件(20),其特征在于所述基片(94)是模塑的塑料制品。
11.一种漆膜组件(20)的制造方法,该方法包括下列步骤:
形成具有高光泽和DOI的漆膜(22);
形成含聚氨酯层的掩模薄膜(24);和
将掩模薄膜(24)粘附在漆膜(22)上,形成可热成形的掩蔽漆膜(32),并且掩模薄膜(24)可容易地从漆膜(22)上除去,
其中聚氨酯层(28)在操作上是合适的,使得在热成形掩蔽漆膜(32)并除去掩模薄膜(24)后,漆膜(22)至少基本保持其原来的高光泽和DOI。
12.如权利要求11所述的方法,其特征在于它还包括在所述粘结步骤前单独形成漆膜(22)和掩模薄膜(24)的步骤。
13.如权利要求12所述的方法,其特征在于在所述形成步骤中在漆膜(22)上形成光洁的表面(26),在掩模薄膜(24)上形成光洁的表面(30),所述粘附步骤包括将漆膜(22)的所述光洁表面(26)和所述掩模薄膜(24)的所述光洁表面(30)层压在一起,制成掩蔽漆膜(32)。
14.如权利要求12所述的方法,其特征在于所述单独形成步骤包括:
在一片具有高光泽和DOI的基片(48)的一个表面(46)上形成漆膜(22),以便在漆膜(22)上形成具有高光泽和DOI的光洁表面(26);
在具有高光泽和DOI的另一个基片(38)的表面(36)上形成聚氨酯层(28),以便在聚氨酯层(28)上形成具有高光泽和DOI的光洁表面(30);
在粘附步骤前从一个基片(48)上取下漆膜(22),并从另一个基片(38)上取下聚氨酯层(28),
所述粘附步骤包括将漆膜(22)的光洁表面(26)和聚氨酯层(28)的光洁表面(30)层压在一起,形成掩蔽漆膜(32)。
15.如权利要求14所述的方法,其特征在于形成的漆膜(22)包括透明涂层(40),并且形成漆膜(22)的步骤包括在一片基片(48)的表面(46)上形成透明涂层(40),以便在具有光泽和DOI的透明涂层(40)上形成光洁表面(26)。
16.如权利要求12所述的方法,其特征在于形成的掩模薄膜(24)包括流延的聚氨酯层(28)。
17.如权利要求12所述的方法,其特征在于所述方法包括下列步骤:
将掩蔽漆膜(32)热成形成所需形状;和
从漆膜(22)上除去掩模薄膜(24)。
18.如权利要求12所述的方法,其特征在于所述方法包括下列步骤:
将掩蔽漆膜(32)热成形成所需形状;
将掩蔽漆膜(32)粘合在基片(94)上;和
从漆膜(22)上除去掩模薄膜(24)。
19.如权利要求12所述的方法,其特征在于所述方法包括下列步骤:
将掩蔽漆膜(32)热成形成所需的形状;
将掩蔽漆膜(32)嵌件模塑成模塑塑料部件;和
从漆膜(22)上除去掩模薄膜(24)。
20.如权利要求12所述的方法,其特征在于形成的漆膜(22)包括含金属薄片的着色涂层(42)。
21.如权利要求1所述的漆膜组件(20),其特征在于所述漆膜(22)包括层压在透明涂层(40)上的着色涂层(42),所述透明涂层(40)可剥离地粘附在所述掩模薄膜(24)上。
22.如权利要求11所述的方法,其特征在于形成的漆膜(22)包括层压在透明涂层(40)上的着色涂层(42),所述将掩模薄膜(24)粘附在漆膜(22)上的步骤包括将透明涂层(40)和掩模薄膜(24)粘附在一起,并且掩模薄膜(24)可容易地从透明涂层(40)上除去。
CN98808254A 1997-08-18 1998-08-13 带掩模薄膜的漆膜组件及其制造方法 Expired - Lifetime CN1091411C (zh)

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