CN1671560A - 喷墨印刷的刚性夹层及其制造方法 - Google Patents

喷墨印刷的刚性夹层及其制造方法 Download PDF

Info

Publication number
CN1671560A
CN1671560A CN03818385.4A CN03818385A CN1671560A CN 1671560 A CN1671560 A CN 1671560A CN 03818385 A CN03818385 A CN 03818385A CN 1671560 A CN1671560 A CN 1671560A
Authority
CN
China
Prior art keywords
interlayer
sheet
lamination
ink
image
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.)
Granted
Application number
CN03818385.4A
Other languages
English (en)
Other versions
CN100379578C (zh
Inventor
R·L·史密斯
H·埃尔瓦基尔
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
EIDP Inc
Original Assignee
EI Du Pont de Nemours and Co
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by EI Du Pont de Nemours and Co filed Critical EI Du Pont de Nemours and Co
Publication of CN1671560A publication Critical patent/CN1671560A/zh
Application granted granted Critical
Publication of CN100379578C publication Critical patent/CN100379578C/zh
Anticipated expiration legal-status Critical
Expired - Fee Related legal-status Critical Current

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
    • B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
    • B32B17/1055—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer
    • B32B17/10559—Shape of the cross-section
    • B32B17/10577—Surface roughness
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
    • B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
    • B32B17/10165—Functional features of the laminated safety glass or glazing
    • B32B17/10247—Laminated safety glass or glazing containing decorations or patterns for aesthetic reasons
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
    • B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
    • B32B17/1055—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer
    • B32B17/10743—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer containing acrylate (co)polymers or salts thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
    • B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
    • B32B17/1055—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer
    • B32B17/10761—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer containing vinyl acetal
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41J—TYPEWRITERS; SELECTIVE PRINTING MECHANISMS, i.e. MECHANISMS PRINTING OTHERWISE THAN FROM A FORME; CORRECTION OF TYPOGRAPHICAL ERRORS
    • B41J11/00—Devices or arrangements  of selective printing mechanisms, e.g. ink-jet printers or thermal printers, for supporting or handling copy material in sheet or web form
    • B41J11/0015—Devices or arrangements  of selective printing mechanisms, e.g. ink-jet printers or thermal printers, for supporting or handling copy material in sheet or web form for treating before, during or after printing or for uniform coating or laminating the copy material before or after printing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41J—TYPEWRITERS; SELECTIVE PRINTING MECHANISMS, i.e. MECHANISMS PRINTING OTHERWISE THAN FROM A FORME; CORRECTION OF TYPOGRAPHICAL ERRORS
    • B41J3/00—Typewriters or selective printing or marking mechanisms characterised by the purpose for which they are constructed
    • B41J3/407—Typewriters or selective printing or marking mechanisms characterised by the purpose for which they are constructed for marking on special material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/0041—Digital printing on surfaces other than ordinary paper
    • B41M5/0047—Digital printing on surfaces other than ordinary paper by ink-jet printing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/0041—Digital printing on surfaces other than ordinary paper
    • B41M5/0064—Digital printing on surfaces other than ordinary paper on plastics, horn, rubber, or other organic polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B44—DECORATIVE ARTS
    • B44F—SPECIAL DESIGNS OR PICTURES
    • B44F1/00—Designs or pictures characterised by special or unusual light effects
    • B44F1/06—Designs or pictures characterised by special or unusual light effects produced by transmitted light, e.g. transparencies, imitations of glass paintings
    • B44F1/066—Designs or pictures characterised by special or unusual light effects produced by transmitted light, e.g. transparencies, imitations of glass paintings comprising at least two transparent elements, e.g. sheets, layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M7/00—After-treatment of prints, e.g. heating, irradiating, setting of the ink, protection of the printed stock
    • B41M7/0027—After-treatment of prints, e.g. heating, irradiating, setting of the ink, protection of the printed stock using protective coatings or layers by lamination or by fusion of the coatings or layers

Landscapes

  • Laminated Bodies (AREA)
  • Ink Jet Recording Methods And Recording Media Thereof (AREA)
  • Ink Jet (AREA)

Abstract

本发明涉及一种装饰玻璃叠片，及叠片的制备方法，其中所述叠片包含带印刷图像的刚性夹层，所述印刷图像是经喷墨印刷到夹层的至少一个表面上的。如按照ASTMD5026－95a所测，夹层在0.3Hz和25℃下具有50－1,000MPa(兆帕)的Storage杨氏模数，并且具有少于或等于约0.38mm的有限厚度。

Description

喷墨印刷的刚性夹层及其制造方法
本申请要求2002年7月31日递交的美国临时申请No.60/400,232的权益。
发明背景
叠片安全玻璃由经能量吸收塑性夹层连接的两薄层玻璃组成，该塑性夹层是聚乙烯醇缩丁醛(PVB)。叠片安全玻璃用于汽车挡风玻璃和建筑物玻璃。建筑师在许多需要的应用中频繁地使用玻璃，例如栏杆、隔墙、地板、门以及吊顶玻璃。用塑化的PVB作为夹层的叠片安全玻璃通常不能满足这些应用对强度和玻璃后破碎的要求。乙烯/甲基丙烯酸共聚物的离聚物(以DuPont的商标Surlyn出售)形成刚性的，比传统PVB夹层更为坚硬和强韧的夹层材料。已经证明采用更坚硬更强韧夹层的叠片安全玻璃具备这些期望的建筑应用所需的强度和玻璃后破碎的要求。
此外，已经发现离聚的乙烯/甲基丙烯酸共聚物夹层表现出比传统PVB夹层大大提高的边缘稳定性。这种提高的边缘稳定性使叠片玻璃(离聚的乙烯/甲基丙烯酸共聚物夹层)能用于诸如淋浴门和外开边缘应用之类的不能使用传统叠片玻璃(带PVB夹层)的应用中。在许多上述的这些应用中(栏杆、隔墙、地板、门、吊顶玻璃以及淋浴门)，可能希望叠片安全玻璃中具有装饰图像。
WO217154 A1、DE29706880、US4968553、US5914178、EP1129844A1以及DE20100717中已经披露了制造叠片装饰玻璃的方法。这些装饰叠片用PVB、PVB/PET/PVB复合物或EVA(乙烯/乙酸乙烯酯共聚物)作为夹层。尽管所得的装饰性安全玻璃叠片可能满足建筑安全标准，但是在例如以上指出的那些期望应用中这些叠片表现并不出色。
此外，这些参考文献中许多也披露了通过丝网印刷法制造装饰叠片玻璃的方法(DE29706880、US4968553、US5914178、EP1129844 A1以及DE20100717)。对于制造装饰性叠片安全玻璃，将图像丝网印刷到夹层上是非常费时和昂贵的方法。喷墨方法则非常灵活；任何数字图像都可以印刷到基底上。采用喷墨印刷技术在叠片安全玻璃的柔性中间层(PVB和聚氨基甲酸酯)上印刷已经披露在WO0218154中。在PVB上直接印刷的几个缺点中包括所有PVB夹层都有粗糙的表面型式(Rz为30-60□m)的事实，提供这种糙面型式是为了使空气能够在如US5455103所述的层压处理期间逃逸。糙面型式会影响图像的与斑点和清晰度相关的品质。而且，聚乙烯醇缩丁醛是一种黏弹性聚合物，会引起带图夹层中低劣的体积稳定性。
相对于其它传统夹层，得自乙烯/甲基丙烯酸共聚物的离聚物的夹层是刚性的，并且例如具有相对于PVB更高的体积稳定性。然而，申请人已经发现在刚性材料上印刷的一个问题是刚性聚合物不能用传统的印刷方法处理。申请人已经发现用传统喷墨印刷机在普通离聚物夹层上喷墨印刷的方法是有问题的，因为乙烯/甲基丙烯酸共聚物的离聚物不够柔韧，不能送进并穿过喷墨印刷机。
发明概述
在一个方面，本发明是一种将图像喷墨印刷到刚性热塑性夹层上的方法，包括步骤：将刚性夹层片送进并使之穿过喷墨印刷机以及在片上喷墨印刷图像，其中如按照ASTM D 5026-95a所测，夹层在0.3Hz和25℃下具有50-1,000MPa(兆帕)的Storage杨氏模数，并且刚性夹层片具有少于或等于约0.38mm的有限厚度。
在另一方面，本发明是热塑性夹层片，在该夹层片的至少一个表面上带有图像，将图像印刷到片上的方法包括步骤：将刚性夹层片送进并使之穿过喷墨印刷机以及在片上喷墨印刷图像，其中如按照ASTM D5026-95a所测，夹层在0.3Hz和25℃下具有50-1,000MPa(兆帕)的Storage杨氏模数，并且刚性夹层片具有少于或等于约0.38mm的有限厚度。
在又一个方面，本发明是一种装饰玻璃叠片，包含至少两片在其间放置有刚性带图夹层片的玻璃，其中带图夹层由包含下列步骤的方法得到：(1)“喷墨”印刷着色油墨到夹层片的至少一个表面上，该夹层片是刚性的乙烯/甲基丙烯酸共聚物的离聚物，厚度小于或等于约0.38mm，如按照ASTM D 5026-95a所测，夹层在0.3Hz和25℃下具有50-1,000MPa(兆帕)的Storage杨氏模数，以得到带图夹层片；和(2)在透明材料片之间层压带图夹层片，以得到装饰叠片。
发明详述
在一个实施方式中，本发明是一种在刚性夹层上印刷装饰图像的方法。适用于本发明实践中的刚性夹层优选如按照ASTM D 5026-95a所测，在0.3Hz和25℃下具有50-1,000MPa(兆帕)的Storage杨氏模数。传统夹层材料例如传统塑化的PVB通常不具有此范围内的模数。其它传统夹层材料也适于作为喷墨印刷的基底，但使用刚性夹层材料有优势。
刚性、坚硬的夹层，例如那些基于离聚的乙烯/甲基丙烯酸共聚物的夹层，促进了使用更为光滑的表面型式以在层压期间获得可接受的排气，因为刚性夹层的表面型式并不迅速损毁。例如，传统塑化的(柔性的)层压PVB的期望Rz范围为30-60μm，而刚性夹层的Rz容许范围为5至15μm。离聚物夹层的光滑表面型式使得所印刷的图像具有比直接在PVB上印刷的图像更高的清晰度和更少的斑点。
相对于其它传统柔性夹层材料例如柔性PVB，刚性夹层的较高模数能够形成具有与较柔材料相比提高的体积稳定性的夹层。该提高的体积稳定性能改善带图产品的图像稳定性，并使整个过程相对于图像的伸长或收缩更为可靠和可重复。
在刚性夹层上印刷以获得带图的产品可以通过使用水性或溶剂基油墨并采用喷墨印刷技术、以及在两薄片玻璃或其它透明材料之间层压带图刚性夹层来实现。以此方法所获得的叠片具有适宜于安全玻璃应用的粘着性。
在一个优选实施方式中，采用喷墨印刷机将图像印刷到夹层上，该喷墨印刷机装配有压电按需滴出印刷头，例如Spectra或Xaar，选择喷墨印刷机以使刚性夹层保持在床型载体上。
夹层可以是任何能与玻璃粘结的无瑕透明刚性热塑性材料。例如，夹层可以是增塑剂少于30份的PVB片，或离聚物夹层。优选夹层是乙烯/(甲基)丙烯酸共聚物的离聚物，该片的表面粗糙度(Rz)在5与15μm之间，并且夹层的总厚度在0.38与2.29mm之间。
此处所用术语“乙烯/(甲基)丙烯酸”是一种缩写术语，表示包含乙烯和丙烯酸单元或包含乙烯和甲基丙烯酸单元的共聚物。通常认为离聚物是部份中和的乙烯/(甲基)丙烯酸共聚物。根据本发明的实践，适于印刷的夹层例如可以得自乙烯/丙烯酸共聚物离聚物，如那些可从E.I DuPont de Nemours and Company商业获得的离聚物。
在另一个实施方式中，本发明是一种复合带图夹层，该夹层可由包含下列步骤的方法得到：将基底薄膜送进并使之穿过传统喷墨印刷机以及将图像喷墨印刷到基膜的表面上，该基膜如按照ASTM D 5026-95a所测，在0.3Hz和25℃下具有50-1,000MPa(兆帕)的Storage杨氏模数，并且有限厚度少于或等于约0.38mm，然后将该带图薄膜与第二片热塑性夹层材料层压。优选该复合的印刷夹层具有约0.40至约2.29mm的厚度。其它片的厚度可以变动，但是应当至少为0.025mm厚。其它片可以是空白的、或带印刷图像的或带颜色的；可以是透明的、半透明的、不透明的；或者可以是可与印刷基底视觉可区分的。在一个优选的实施方式中，可将该薄层印刷基底与较厚(≥0.76mm)的膜或片例如乙烯/甲基丙烯酸共聚物的离聚物层压以在最终叠片中获得期望的结构特性。层压带图夹层片与较厚聚合物片以形成这样的产品，其带有印在夹层上的图像并具有较厚夹层的特性。
其它片可以是任何能与经印刷的离聚物膜粘结的热塑性夹层材料。例如，较厚膜可以是乙烯共聚物和/或三聚物，例如乙烯/丙烯酸或乙烯/丙烯酸烷基酯的共聚物和乙烯/丙烯酸/丙烯酸烷基酯的三聚物；聚缩醛树脂；聚乙烯醇缩丁醛；聚氨基甲酸酯；聚氯乙烯；或聚酯。
优选印刷基底薄膜具有在约0.025mm至约0.45mm范围内的厚度。更优选印刷基底的厚度为约0.1mm至约0.40mm。最优选印刷基底的厚度为约0.25mm至约0.38mm。优选较厚膜片具有与薄膜厚度相衬的厚度以使夹层片的总厚度在约0.38mm至约2.29mm的范围内。更优选总厚度在约0.60mm至约1.75mm的范围内。最优选夹层的总厚度为约1.14mm至约1.52mm。
本发明的叠片可用在任何使用普通(即，无装饰)叠片玻璃的应用中。然而，除了用作安全玻璃的传统用途外，本发明的叠片还可以用作装饰用品，例如观景窗、装饰柜台、图像制品、带图的店铺橱窗、带公司徽章的展柜、广告介质和/或任何需要透明带图叠片的其它用途。
用在本发明实践中的优选油墨是那些能提供适宜的图像品质、耐光性和耐候性组合的印刷图像的油墨。此外，结合有本发明的带图夹层的叠片在各种使用它们的应用中应当具有可接受的粘着特性。由于此处用于印刷的聚合物夹层基底的性质，以及对于在安全玻璃中的粘着性的要求，对适宜油墨的选择并非是任意的。适用于本发明实践的油墨必须也与基底相容以产生令人满意的结果。
用于压电过程的印刷头例如可从Epson、Seiko-Epson、Spectra、XAAR和XAAR-Hitachi获得。用于热喷墨印刷的印刷头例如可从Hewlett-Packard和Canon获得。适宜于连续滴印的印刷头例如可从Iris和Video Jet获得。
适用于本发明实践中的油墨系统中任选地包含粘合剂树脂。优选粘合剂树脂能够改善油墨与片状基底之间的粘着性。用于本发明实践的适宜粘合剂可以包括例如聚乙烯吡咯烷酮/醋酸乙烯酯(PVP/VA)、聚乙烯吡咯烷酮(PVP)和PUR。粘合剂树脂的化合物也可用于本发明实践。其它粘合剂是公知的，也可用于此发明中。
实施例
提供以下实施例以解释说明本发明。实施例并不想以任何方式限制
发明的范围。
实验方法
表面粗糙度，Rz，如ISO-R468所述从10点平均粗糙度测定，并以微米表示。表面粗糙度用Mahr Federal(Providence，RI)表面分析器测量。
尺度稳定性实验：尺度稳定性实验包括将已知尺寸的图像印刷到所测试的基底上。比较离开印刷机的印刷图像的尺寸与数字输入的尺寸。
实施例-将100mm×100mm大小的图像印刷到0.38mm厚的乙烯/甲基丙烯酸离聚共聚物夹层上。在环境条件下印刷之后立即测定图像，精确地为100mm×100mm。在将图像在60℃干燥30分钟后，图像尺寸为100mm×100mm。确定乙烯/甲基丙烯酸离聚共聚物的收缩为0％。
对比例-将300mm×300mm大小的图像印刷到0.76mmPVB上。在环境条件下印刷之后立即测定图像，尺寸为302mm×298mm。在将图像在60℃干燥30分钟后，测定图像尺寸为304mm×294mm。确定0.76mmPVB的收缩为2％。
层压步骤：
在以下实施例中用喷墨印刷机将图像印刷到所处理夹层的每个表面上。在层压带图夹层之前，用75℃烘箱干燥最少16小时，将夹层干燥至含少于0.2％的H2O。为了层压，将一层15mil的空白(不带图)夹层置于带图表面上。将多层结构体除气(通过真空袋或轧辊方法)并采用标准层压条件进行压热处理。
实施例1.
用Epson 3000印刷机将固体黄色印版印刷到0.38mm厚的乙烯/甲基丙烯酸共聚物的离聚物夹层的表面上。所用油墨描述在下表中。如上所述对经印刷的夹层进行层压。
  分散剂   丙烯酸类聚合物颜料Yellow120双丙甘醇单甲基醚
  粘合剂   Khrumbhaar 1717
  溶剂   双丙甘醇甲基醚醋酸酯
  双丙甘醇丙基醚
实施例2.
如实施例1中所述印刷和层压一立体黄色印版。所用油墨描述在下表中：
分散剂   丙烯酸类聚合物颜料Yellow120双丙甘醇单甲基醚
粘合剂   Khrumbhaar 3107
溶剂   双丙甘醇甲基醚醋酸酯
  双丙甘醇丙基醚
实施例3.
如实施例1中所述印刷和层压固体黄色印版。所用油墨描述在下表中：
分散剂   丙烯酸类聚合物颜料Yellow120双丙甘醇单甲基醚
粘合剂   Khrumbhaar 1728
溶剂   双丙甘醇甲基醚醋酸酯
  双丙甘醇丙基醚
实施例4.
如实施例1中所述印刷和层压固体黄色印版。所用油墨描述在下表中：
分散剂   丙烯酸类聚合物颜料Yellow120双丙甘醇单甲基醚
粘合剂   Laropal 80
溶剂   双丙甘醇甲基醚醋酸酯
  双丙甘醇丙基醚
实施例5.
如实施例1中所述印刷和层压固体黄色印版。所用油墨描述在下表中：
分散剂   丙烯酸类聚合物颜料Yellow120双丙甘醇单甲基醚
粘合剂   Laropal 81
溶剂   双丙甘醇甲基醚醋酸酯
  双丙甘醇丙醚
实施例6.
如实施例1中所述印刷和层压固体黄色印版。所用油墨描述在下表中：
分散剂   丙烯酸醚聚合物颜料Yellow120双丙甘醇单甲基醚
粘合剂   Laropal A101
溶剂   双丙甘醇甲基醚醋酸酯
  双丙甘醇丙基醚

Claims (22)

1.将图像喷墨印刷到刚性热塑性夹层上的方法，包括步骤：将刚性夹层片送进并使之穿过喷墨印刷机以及在片上喷墨印刷图像，其中如按照ASTM D 5026-95a所测，夹层在0.3Hz和25℃下具有50-1,000MPa(兆帕)的Storage杨氏模数，并且刚性夹层片具有少于或等于约0.38mm的有限厚度。
2.权利要求1的方法，其中夹层或是乙烯/(甲基)丙烯酸共聚物离聚物，或是PVB，该PVB基于夹层片的重量，每100份含少于30份的增塑剂。
3.权利要求2的方法，其中夹层是是乙烯/(甲基)丙烯酸共聚物离聚物。
4.权利要求3的方法，进一步包括将带图夹层片与不带图的第二夹层片层压的步骤，以形成复合带图夹层，其中复合夹层的总厚度在约0.40mm至约2.29mm的范围内。
5.权利要求4的方法，其中刚性夹层的带图表面是与第二夹层片的表面接触的表面。
6.权利要求5的方法，其中第二夹层片是乙烯/(甲基)丙烯酸共聚物离聚物。
7.权利要求6的方法，其中第二夹层片具有约0.76mm至约1.13mm的厚度。
8.一种获得装饰叠片的方法，包括步骤：
(1)“喷墨”印刷着色油墨到夹层片的至少一个表面上，该夹层片是刚性的乙烯/甲基丙烯酸共聚物的离聚物，厚度小于或等于约0.38mm，如按照ASTM D 5026-95a所测，夹层在0.3Hz和25℃下具有50-1,000MPa(兆帕)的Storage杨氏模数，以得到带图夹层片；和
(2)在透明材料片之间层压带图夹层片，以得到装饰叠片。
9.权利要求8的方法，其中刚性夹层包含粗糙化的表面，其层压前的粗糙度(Rz)为约5μm至约15μm。
10.权利要求9的方法，其中将刚性带图夹层与一层或多层其它夹层片层压以形成总厚度为约0.40mm至约2.29mm的复合夹层。
11.权利要求10的方法，其中其它夹层片包含热塑性聚合物，选自聚合物：PVB、PET、PUR、PC、PVC、乙烯/(甲基)丙烯酸共聚物离聚物、乙烯/(甲基)丙烯酸/丙烯酸烷基酯三聚物。
12.权利要求11的方法，其中用按需滴出(DOD)喷墨印刷方法印刷图像。
13.权利要求12的方法，其中DOD方法是压电方法。
14.权利要求12的方法，其中DOD方法是热喷墨印刷法。
15.权利要求11的方法，其中用连续滴出喷墨印刷法印刷图像。
16.由权利要求8的方法得到的装饰叠片。
17.权利要求16的叠片，其中将带图夹层与至少一层其它夹层的至少一层附加片层压以形成复合带图夹层，其中至少一层附加夹层片具有足够的厚度以使复合夹层的总厚度落在约0.40mm至约2.29mm的范围内，并进一步将复合带图夹层与至少一片玻璃层压。
18.权利要求17的叠片，其中复合夹层的总厚度在约0.6mm至约1.75mm范围内。
19.权利要求18的叠片，其中复合夹层的总厚度在约1.14mm至约1.52mm范围内。
20.一种热塑性夹层片，在该夹层片的至少一个表面上带有图像，将图像印刷到片上的方法包括步骤：将刚性夹层片送进并使之穿过喷墨印刷机以及在片上喷墨印刷图像，其中如按照ASTM D 5026-95a所测，夹层在0.3Hz和25℃下具有50-1,000MPa(兆帕)的Storage杨氏模数，并且刚性夹层片具有少于或等于约0.38mm的有限厚度。
21.权利要求20的夹层，其中夹层的表面粗糙度为约5μm至约15μm。
22.权利要求21的夹层，其中印刷图像之后在60℃干燥30分钟后，图像尺寸的变化不超过图像初始尺寸的±1％。
CNB038183854A 2002-07-31 2003-07-31 喷墨印刷的刚性夹层及其制造方法 Expired - Fee Related CN100379578C (zh)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US40023202P 2002-07-31 2002-07-31
US60/400,232 2002-07-31

Publications (2)

Publication Number Publication Date
CN1671560A true CN1671560A (zh) 2005-09-21
CN100379578C CN100379578C (zh) 2008-04-09

Family

ID=31188669

Family Applications (1)

Application Number Title Priority Date Filing Date
CNB038183854A Expired - Fee Related CN100379578C (zh) 2002-07-31 2003-07-31 喷墨印刷的刚性夹层及其制造方法

Country Status (9)

Country Link
US (1) US7232213B2 (zh)
EP (1) EP1525099B1 (zh)
JP (1) JP2005534527A (zh)
CN (1) CN100379578C (zh)
AU (1) AU2003257995B2 (zh)
CA (1) CA2494057A1 (zh)
DE (1) DE60312338T2 (zh)
MX (1) MXPA05001118A (zh)
WO (1) WO2004011271A1 (zh)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103402759A (zh) * 2010-12-29 2013-11-20 法国圣戈班玻璃厂 通过借助于双织物网屏的丝网印刷制备印刷层合玻璃板的方法
CN110740862A (zh) * 2017-05-15 2020-01-31 康宁公司 具有有机油墨装饰和高抗冲击性的层压体

Families Citing this family (29)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20070087137A9 (en) 2003-06-26 2007-04-19 Elwakil Hamdy A Decorative laminated safety glass
CN1842414A (zh) * 2003-08-07 2006-10-04 纳幕尔杜邦公司 利用硬质夹层的装饰层压安全玻璃及其制备方法
DE602005016785D1 (de) * 2004-03-02 2009-11-05 Du Pont Mehrschichtdekorsicherheitsglas
US20070172636A1 (en) * 2005-12-30 2007-07-26 Smith Rebecca L Decorative sheets having enhanced adhesion and laminates prepared therefrom
US8101267B2 (en) 2005-12-30 2012-01-24 E. I. Du Pont De Nemours And Company Multilayer polymeric laminates and high strength laminates produced therefrom
US7625627B2 (en) 2005-12-30 2009-12-01 E.I. Du Pont De Nemours And Company Decorative polyvinyl butyral solar control laminates
GB0600022D0 (en) * 2006-01-03 2006-02-08 Pilkington Plc Glazings
US20080206504A1 (en) * 2007-02-28 2008-08-28 Richard Allen Hayes Decorative Safety Glass
US20080233377A1 (en) * 2007-03-19 2008-09-25 Smith Rebecca L High contrast high strength decorative sheets and laminates
US20080233371A1 (en) * 2007-03-19 2008-09-25 Richard Allen Hayes Decorative safety glass
US20080280076A1 (en) * 2007-05-11 2008-11-13 Richard Allen Hayes Decorative safety glass
JP2011522828A (ja) 2008-06-04 2011-08-04 シナジー ファーマシューティカルズ インコーポレイテッド 胃腸障害、炎症、癌、およびその他の障害の治療のために有用なグアニル酸シクラーゼのアゴニスト
GB2469094A (en) * 2009-04-01 2010-10-06 Jeremy Town Decorative panel
FR2962363B1 (fr) * 2010-07-07 2013-01-04 Saint Gobain Structure feuilletee pour la visualisation d'informations
FR2964447B1 (fr) * 2010-09-02 2012-08-24 Saint Gobain Vitrage feuillete eclairant a diodes electroluminescentes et sa fabrication
US9616097B2 (en) 2010-09-15 2017-04-11 Synergy Pharmaceuticals, Inc. Formulations of guanylate cyclase C agonists and methods of use
DE102011004500A1 (de) * 2011-02-22 2012-08-23 Bayerische Motoren Werke Aktiengesellschaft Verfahren zur Herstellung einer bedruckten Fahrzeug-Verbundscheibe
JP6499591B2 (ja) 2013-02-25 2019-04-10 シナジー ファーマシューティカルズ インコーポレイテッド 結腸洗浄において用いるためのグアニル酸シクラーゼ受容体アゴニスト
WO2014151206A1 (en) 2013-03-15 2014-09-25 Synergy Pharmaceuticals Inc. Agonists of guanylate cyclase and their uses
US9486494B2 (en) 2013-03-15 2016-11-08 Synergy Pharmaceuticals, Inc. Compositions useful for the treatment of gastrointestinal disorders
WO2015084902A1 (en) 2013-12-06 2015-06-11 Corning Incorporated Methods for forming patterns in thin glass laminate structures
US10780674B2 (en) 2015-02-19 2020-09-22 Agp America S.A. Obscuration having superior strength and optical quality for an automotive laminate
US9623634B2 (en) 2015-02-19 2017-04-18 Agp America S.A. Obscuration having superior strength and optical quality for a laminated automotive windshield
US10710340B2 (en) 2015-02-19 2020-07-14 Agp America S.A. Obscuration having superior strength and optical quality for an automotive laminate
CO2017008445A1 (es) 2016-12-29 2018-01-31 Agp America Sa Oscurecimiento con resistencia y calidad óptica superiores para un laminado para automotores
JP2020531394A (ja) 2017-08-25 2020-11-05 クラレイ ユーロップ ゲゼルシャフト ミット ベシュレンクテル ハフツングＫｕｒａｒａｙ Ｅｕｒｏｐｅ ＧｍｂＨ 着色されたフレームを有する中間膜層を含む合わせガラス
KR20210123347A (ko) 2019-02-04 2021-10-13 쿠라라이 유럽 게엠베하 허리케인 저항성 음향 글레이징
US20230382087A1 (en) 2020-09-28 2023-11-30 Kuraray Europe Gmbh Glass laminates with reduced creep at elevated temperature
US20230182449A1 (en) * 2021-12-10 2023-06-15 Chang Chun Petrochemical Co., Ltd. Polymer film

Family Cites Families (27)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4303718A (en) * 1980-06-09 1981-12-01 Monsanto Company Printing ink formulations
US4868581A (en) * 1985-12-20 1989-09-19 Cannon Kabushiki Kaisha Ink-receiving composite polymer material
EP0254187A3 (de) 1986-07-21 1989-07-26 Siemens Aktiengesellschaft Pigmentierter Lack für Schreibsysteme
US4968553A (en) * 1988-09-16 1990-11-06 Claudio Cesar Graphic architectural glass
FR2706446B1 (fr) * 1993-06-18 1995-08-25 Saint Gobain Vitrage Int Vitrage feuilleté comportant un motif apparent.
US5455103A (en) * 1994-01-24 1995-10-03 Monsanto Company Rough-surfaced interlayer
US6248804B1 (en) * 1997-02-27 2001-06-19 Acushnet Company Ultraviolet and or/ visible light curable inks with photoinitiators for game balls, golf balls and the like
US6500495B2 (en) * 1997-02-27 2002-12-31 Acushnet Company Method for curing reactive ink on game balls
US6013330A (en) * 1997-02-27 2000-01-11 Acushnet Company Process of forming a print
DE29706880U1 (de) 1997-04-16 1997-05-28 Vegla Vereinigte Glaswerke Gmbh, 52066 Aachen Dekoratives Verbundglas
EP1105287B1 (en) 1998-05-14 2006-10-11 E.I. Du Pont De Nemours And Company Glass laminates for threat resistant window systems
JP4062857B2 (ja) 1999-04-16 2008-03-19 コニカミノルタホールディングス株式会社 インクジェット記録シート
US6432519B1 (en) * 1999-04-16 2002-08-13 Konica Corporation Ink jet recording sheet
WO2000074945A1 (fr) * 1999-06-04 2000-12-14 Daicel Chemical Industries, Ltd. Composition de resine destinee a une feuille d'enregistrement par jet d'encre et feuille realisee a l'aide de cette composition
DE20100717U1 (de) 2000-02-18 2001-04-05 Glas Engels Gmbh Verbundkörper aus einer mehrschichtigen Anordnung
EP1129844A1 (en) 2000-02-29 2001-09-05 Brevet 2000 Holding S.A. Composite stratified decorated panel from glass and/or transparent plastics
AU5339001A (en) * 2000-04-14 2001-10-30 Du Pont Multilayer, co-extruded, ionomeric decorative surfacing
DE10032683A1 (de) * 2000-07-05 2002-01-17 Clariant Gmbh Farbmittelmischung
WO2002018154A1 (en) 2000-09-01 2002-03-07 Digiglass Pty. Ltd. Image carrying laminated material
US20030124296A1 (en) * 2000-10-26 2003-07-03 Smith Charles Anthony Glass laminates for threat resistant window systems
US20030049415A1 (en) * 2001-03-12 2003-03-13 Pedginski James J. Film constructions and methods
CA2494021A1 (en) * 2002-07-31 2004-02-05 E. I. Du Pont De Nemours And Company Polyvinylbutyral interlayer sheet with improved adhesion to glass and a process for preparing same
US20070087137A9 (en) * 2003-06-26 2007-04-19 Elwakil Hamdy A Decorative laminated safety glass
US7041163B2 (en) * 2003-03-28 2006-05-09 E.I. Du Pont De Nemours And Company Non-aqueous inkjet ink set
US20070071955A9 (en) * 2002-08-20 2007-03-29 Elwakil Hamdy A Decorative laminated safety glass
US7122077B2 (en) * 2003-03-28 2006-10-17 E. I. Du Pont De Nemours And Company Inkjet ink set and method of using same
CN1842414A (zh) * 2003-08-07 2006-10-04 纳幕尔杜邦公司 利用硬质夹层的装饰层压安全玻璃及其制备方法

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103402759A (zh) * 2010-12-29 2013-11-20 法国圣戈班玻璃厂 通过借助于双织物网屏的丝网印刷制备印刷层合玻璃板的方法
CN110740862A (zh) * 2017-05-15 2020-01-31 康宁公司 具有有机油墨装饰和高抗冲击性的层压体
CN110740862B (zh) * 2017-05-15 2023-01-10 康宁公司 具有有机油墨装饰和高抗冲击性的层压体
US12109781B2 (en) 2017-05-15 2024-10-08 Corning Incorporated Laminate having organic ink decoration and high impact resistance

Also Published As

Publication number Publication date
US7232213B2 (en) 2007-06-19
AU2003257995A1 (en) 2004-02-16
US20050285920A1 (en) 2005-12-29
DE60312338D1 (de) 2007-04-19
CA2494057A1 (en) 2004-02-05
MXPA05001118A (es) 2005-04-28
AU2003257995B2 (en) 2008-05-22
DE60312338T2 (de) 2007-11-29
JP2005534527A (ja) 2005-11-17
EP1525099B1 (en) 2007-03-07
WO2004011271A1 (en) 2004-02-05
CN100379578C (zh) 2008-04-09
EP1525099A1 (en) 2005-04-27

Similar Documents

Publication Publication Date Title
CN100379578C (zh) 喷墨印刷的刚性夹层及其制造方法
US8002938B2 (en) Decorative laminated safety glass
EP1539487B1 (en) Decorative laminated safety glass
CN1842414A (zh) 利用硬质夹层的装饰层压安全玻璃及其制备方法
AU2006332747B2 (en) Decorative sheets having enhanced adhesion and laminates prepared therefrom
TW470760B (en) Polyester film for decorative plate
US20070172637A1 (en) Decorative sheets having enhanced adhesion and penetration resistant laminates prepared therefrom
KR20130037670A (ko) 비pvc 필름 및 비pvc 필름 라미네이트
US20050271865A1 (en) Decorative laminated safety glass
KR100818696B1 (ko) Ｃｐｐ필름을 사용한 시트의 제조방법 및 그에 의해 제조된시트
KR200432304Y1 (ko) Ｏｐｐ 필름을 사용한 시트
JP4144260B2 (ja) 切削性向上化粧シート
WO2024162476A1 (ja) 画像担持積層体、その製造方法、合わせガラス用中間膜、及び合わせガラス
CN117162628A (zh) 装饰膜结构体
KR20140088358A (ko) 인쇄효과 및 표면특성이 우수한 장식용 경면 시트 및 그 제조방법

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant
CF01 Termination of patent right due to non-payment of annual fee
CF01 Termination of patent right due to non-payment of annual fee

Granted publication date: 20080409

Termination date: 20210731