CN106068349A - 通过喷墨制造装饰性层压材料 - Google Patents
通过喷墨制造装饰性层压材料 Download PDFInfo
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- CN106068349A CN106068349A CN201580007510.4A CN201580007510A CN106068349A CN 106068349 A CN106068349 A CN 106068349A CN 201580007510 A CN201580007510 A CN 201580007510A CN 106068349 A CN106068349 A CN 106068349A
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
- B41M5/50—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording
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- 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
- B41M7/009—After-treatment of prints, e.g. heating, irradiating, setting of the ink, protection of the printed stock using thermal means, e.g. infrared radiation, heat
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- B44—DECORATIVE ARTS
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- B44C5/04—Ornamental plaques, e.g. decorative panels, decorative veneers
- B44C5/0469—Ornamental plaques, e.g. decorative panels, decorative veneers comprising a decorative sheet and a core formed by one or more resin impregnated sheets of paper
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING 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
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/10—Printing inks based on artificial resins
- C09D11/106—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C09D11/107—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds from unsaturated acids or derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING 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
- C09D11/00—Inks
- C09D11/30—Inkjet printing inks
- C09D11/32—Inkjet printing inks characterised by colouring agents
- C09D11/322—Pigment inks
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING 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
- C09D11/00—Inks
- C09D11/30—Inkjet printing inks
- C09D11/38—Inkjet printing inks characterised by non-macromolecular additives other than solvents, pigments or dyes
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING 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
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
- C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09D133/08—Homopolymers or copolymers of acrylic acid esters
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Abstract
一种用于制造装饰性层压材料的方法,其包括以下步骤:a)通过将纸基材浸没在热固性树脂浴中用热固性树脂浸渍纸基材;b)在热固性树脂浸渍的纸基材上施用油墨接受层,所述油墨接受层包含无机颜料P和聚合物连结料B,无机颜料与聚合物连结料的重量比P/B大于1.5;c)用一种或多种含有有色颜料C的水性加有颜料的喷墨油墨和/或基于有机溶剂的加有颜料的喷墨油墨在所述油墨接受层上喷射有色图案;和d)将热固性纸热压成装饰性层压材料,其中油墨接受层的无机颜料与有色图案中的喷射有色颜料的重量比P/C大于4.0。
Description
技术领域
本发明涉及使用喷墨技术制造装饰性层压材料。
背景技术
对于不同的应用,凹版印刷、胶印和柔版印刷日益被工业喷墨印刷系统替代,现在已经证实工业喷墨印刷系统在使用中的灵活性,例如可变数据印刷使得生产行程变短且可以得到个性化产品;并且证实其可靠性增强,使得能够结合到生产线中。
喷墨技术也已引起装饰性表面(例如,层压地板)制造商的注意。在图1中所示的制造装饰性板的目前制造方法中,纸制造商(11)将纸卷(12)提供到使用凹版印刷(14)的装饰印刷商(13),以将装饰纸卷(16)输送到地板层压材料制造商(20)的仓库(17)。一些装饰印刷商(13)现在正研究喷墨印刷(15)代替凹版印刷。在多孔装饰纸上轮转凹版印刷一般使用在25℃具有1至2Pa.s粘度的油墨,而喷墨油墨的粘度低得多,通常在25℃约1至15mPa.s,地板层压材料制造商(20)在该仓库(17)储存具有不同装饰性图案的装饰纸卷(16)。根据市场需求,地板层压材料制造商(20)然后在其仓库(17)中选择具有所需装饰性图案的装饰卷(16)。然后浸渍(18)所选的装饰卷(16),并切成用于制造即用型地板层压材料(21)的尺寸(19)。对于特殊地板层压材料的突然大量市场需求,仓库(17)作为缓冲是必要的,因为在新装饰纸卷(16)的定货和交货之间有很长时间延迟。
EP 2431190 A(THEODOR HYMMEN)探讨了一种减小仓库规模和时间延迟的方法,该专利在图1中公开一种生产具有抗磨表面的数字印刷片材、卷材或板形工件(20)的方法,所述方法包括以下步骤:A) 将数字数据集提供到数字印刷装置(1);B) 将可印刷工件(20)提供到印刷装置(1);C) 用印刷装置(1)在可印刷工件(20)上数字印刷至少丙烯酸酯印刷油墨(22),随后将树脂混合物(5,21)提供到经数字印刷的工件;和D) 通过热压(7)使树脂混合物(5,21)固化。由地板层压材料制造商将装饰性纸卷制造结合到其自己的制造过程,可避免时间延迟。虽然基于丙烯酸酯的油墨提供了优异的图像质量,但是在热压成装饰性层压材料时发现在油墨层与含有热固性树脂例如三聚氰胺的保护性层之间的粘着问题。这些粘着问题的原因在于在三聚氰胺的缩聚期间产生的水蒸气不能渗透通过已聚合的丙烯酸酯油墨层。第[0003]段公开了,在高于10 g/m2的高油墨覆盖率(例如深色木层压材料)时,尤其会看到粘着问题。
EP 1857511 A (AGFA)公开了基于溶剂的喷墨油墨,该喷墨油墨包含具有至少250分子量的聚亚烷基二醇二烷基醚且其适用于通过单程喷墨印刷制造装饰性层压材料。
水性喷墨油墨也已经用于通过单程喷墨印刷制造装饰性层压材料。例如,在Palis辊对辊(Palis roll-to-roll)单程印刷系统中(http://www.palis-digital.com/en/portfolio/sp-drucker.html),水性喷墨油墨在具有专门的油墨接受层的纸基材上印刷。
为了获得良好的图像质量,该基于溶剂的喷墨油墨或水性喷墨油墨印刷在能够吸收存在于喷墨油墨中的大多数水和有机溶剂的未浸渍纸上。用基于溶剂的喷墨油墨或水性喷墨油墨印刷的装饰纸随后用热固性树脂浸渍并切成纸片待热压成装饰性层压材料。
在制造具有木装饰性图案的装饰性层压材料时,通常在热压期间将木粒纹压到装饰性层压材料中。已经发现,非常难以将木粒纹与木装饰性图案对齐,原因是用基于溶剂的喷墨油墨或水性喷墨油墨印刷的装饰纸的尺寸不稳定性。
因此,仍需要使用喷墨技术和三聚氰胺树脂作为耐磨涂层的制造装饰性表面的改进方法。
发明概述
为了解决上述问题,本发明的优选实施方案已经通过如权利要求1所限定的制造装饰性表面的方法实现。
发现通过将水性或基于溶剂的加有颜料的喷墨油墨喷射在以P/B的特定比率含有无机颜料P和聚合物连结料B的油墨接受层上并控制油墨接受层的无机颜料P的干重与通过该加有颜料的油墨喷射的有色颜料C的干重的比率P/C获得优异的图像质量和粘着性。油墨接受层存在于完全浸渍的基础纸上。首先浸渍随后喷墨印刷的优势在于经喷墨印刷纸的尺寸稳定性,使得木粒纹能够以与喷墨印刷的木色图案完美对齐的方式压印。
本发明的另一个主要优势效果是简单得多的装饰性层压材料的制造过程,这可通过比较图1和图2直接看到,该比较表明,本发明不再需要中间装饰印刷公司(13)或仓库(17)。在地板层压材料制造商(20)的内部印刷允许最大灵活性。装饰性有色图案设计的改变可在制造中快速引入,从而也使对装饰印刷公司(13)供应的依赖性最大限度地减小。也不再有要与装饰印刷公司(13)交涉的最小购买量。内部印刷使得快速适应市场潮流和增加产品种类而无显著经济损失。
由喷墨代替凹版印刷也有很多优点。不再有必要储存凹版印刷辊。另外,与通常可能花费多达5小时调整的凹版印刷中的耗时颜色匹配问题比较,喷墨能够容易地再现颜色。这也直接说明,使用喷墨的较短的印刷运行时间比凹版印刷成本有效得多。
树脂浸渍可导致主要纸损失。如果首先浸渍纸,然后喷墨印刷,则经济损失最大限度地减小,因为要扔掉较少数字印刷品。
通过以下说明,本发明的其他优点和实施方案将变得显而易见。
附图简述
图1显示制造装饰性板的现有技术生产方法,其中纸制造商(11)将纸卷(12)提供到使用凹版印刷(14)或喷墨印刷(15)的装饰印刷商(13),以将装饰纸卷(16)输送到地板层压材料制造商(20)的仓库(17)。根据市场需求,地板层压材料制造商(20)在他的仓库(17)中选择不同装饰卷之一,以浸渍(18)并切成一定尺寸(19),待用于热压并修整成即用型地板层压材料(21)。
图2显示制造装饰性板的生产方法,其中纸制造商(11)直接将纸卷(12)提供到地板层压材料制造商(20),制造商(20)浸渍(18)纸卷(12),切成一定尺寸(19),以用于喷墨印刷(15),然后热压并修整成即用型地板层压材料(21)。切成一定尺寸(19)和喷墨印刷(15)的次序也可以相反,即,在切成片之前在经浸渍纸卷上印刷。
图3显示装饰性板(30)的横截面,所述装饰性板(30)包括具有槽(32)和榫(33)的芯层(31),该芯层(31)的顶侧层压有装饰性层(34)和保护性层(35),且背侧层压有平衡层(36)。
图4显示装饰性板(30)的横截面,所述装饰性板(30)具有用于机械连接的榫(33)和槽(32),而不需要胶水。
图5显示良好图像质量的技术性有色图案的照片。
图6显示恶劣图像质量的技术性有色图案的照片。
图7显示图5中的照片的更详细的部分。
图8显示图6中的照片的更详细的部分。
发明详述
定义
术语“烷基”是指对于烷基中的各种数目的碳原子所有可能的变体,即,甲基;乙基;对于3个碳原子:正丙基和异丙基;对于4个碳原子:正丁基、异丁基和叔丁基;对于5个碳原子:正戊基、1,1-二甲基-丙基、2,2-二甲基丙基和2-甲基-丁基等。
除非另外规定,否则取代或未取代的烷基优选为C1至C6烷基。
除非另外规定,否则取代或未取代的烯基优选为C1至C6烯基。
除非另外规定,否则取代或未取代的炔基优选为C1至C6炔基。
除非另外规定,否则取代或未取代的芳烷基优选为包含一、二、三或更多个C1至C6烷基的苯基或萘基。
除非另外规定,否则取代或未取代的烷芳基优选为包含苯基或萘基的C1至C6烷基。
除非另外规定,否则取代或未取代的芳基优选为苯基或萘基。
除非另外规定,否则取代或未取代的杂芳基优选为由一、二或三个氧原子、氮原子、硫原子、硒原子或其组合替代的五或六元环。
术语“取代的”,例如,在取代的烷基中,指烷基可被此基团中正常存在的原子(即,碳和氢)以外的原子取代。例如,取代的烷基可包括卤素原子或硫醇基。未取代烷基只含碳和氢原子。
除非另外规定,否则取代的烷基、取代的烯基、取代的炔基、取代的芳烷基、取代的烷芳基、取代的芳基和取代的杂芳基优选被一个或多个选自甲基、乙基、正丙基、异丙基、正丁基、异丁基和叔丁基、酯、酰胺、醚、硫醚、酮、醛、亚砜、砜、磺酸酯、磺酰氨、-Cl、-Br、-I、-OH、-SH、-CN和-NO2的取代基取代。
制造装饰性层压材料的方法
根据本发明的用于制造装饰性层压材料的方法包括以下步骤:a) 通过将纸基材浸没在热固性树脂浴中用热固性树脂浸渍纸基材;b) 在热固性树脂浸渍的纸基材上施用油墨接受层,所述油墨接受层包含无机颜料P和聚合物连结料B,无机颜料与聚合物连结料的重量比P/B大于1.5;c) 用一种或多种含有有色颜料C的水性加有颜料的喷墨油墨和/或基于有机溶剂的加有颜料的喷墨油墨在所述油墨接受层上喷射有色图案;和d) 将热固性纸热压成装饰性层压材料,其中油墨接受层的无机颜料P与有色图案中的喷射有色颜料C的重量比P/C大于4.0。
在用于制造装饰性层压材料的方法的一个优选实施方案中,步骤d)包括将凸纹压印在装饰性层压材料中。
装饰性表面的纸首先用热固性树脂浸渍,随后在其上进行喷墨印刷。在一个实施方案中,所述热固性树脂浸渍的纸首先喷墨印刷,然后切成片。在一个优选的实施方案中,该实施方案也示于图2,热固性树脂浸渍的首先切成片,然后进行喷墨印刷。在后者中,由于切割误差的财务损失被最小化,。
在用于制造装饰性层压材料的方法的一个优选实施方案中,由所述一种或多种水性加有颜料的喷墨油墨和/或基于有机溶剂的加有颜料的喷墨油墨喷射的有色颜料的干重为至少0.30 g/m2,更优选至少0.50 g/m2,最优选至少0.60 g/m2。这样的高有色颜料覆盖率能够获得深色图像,例如深色木层压材料。
在用于制造装饰性层压材料的方法的一个优选实施方案中,所述油墨接受层具有不超过10 g/m2、优选不超过6 g/m2且最优选2-5 g/m2的总干重。如果油墨接受层的干厚度较高,则在粘着测试期间油墨接受层中的破裂会发生。
在用于制造装饰性层压材料的方法的一个优选实施方案中,所述热固性树脂选自基于三聚氰胺-甲醛的树脂、基于脲-甲醛的树脂和基于苯酚-甲醛的树脂,最优选所述热固性树脂为基于三聚氰胺-甲醛的树脂。
所述加有颜料的喷墨油墨可由一个或多个印刷头将小液滴以受控方式通过喷嘴喷到相对于印刷头移动的基材上。
喷墨印刷系统的优选印刷头为压电头。压电喷墨印刷是基于施加电压时压电陶瓷换能器的移动。施加电压改变印刷头中压电陶瓷换能器的形状,从而产生空隙,然后用油墨填充空隙。当再次去除电压时,陶瓷膨胀到其初始形状,将油墨滴从印刷头喷出。然而,根据本发明的制造方法不限于压电喷墨印刷。可使用其他喷墨印刷头,且包括各种类型,如连续型。
喷墨印刷头一般跨移动的受墨表面以横向前后扫描。通常喷墨印刷头在返回的途中不印刷。为了得到高面积产出,优选使用双向印刷。
另一种优选的印刷方法是通过“单程印刷方法”,这种印刷方法可用覆盖受墨表面整个宽度的页宽喷墨印刷头或多个交错喷墨印刷头进行。在单程印刷方法中,喷墨印刷头通常保持静止,而将基材表面在喷墨印刷头下输送。
在用于制造装饰性层压材料的方法的一个优选实施方案中,油墨的喷射以单程喷墨印刷模式进行。
装饰性层
所述装饰性层包括热固性树脂浸渍的纸和通过喷墨印刷在其上的有色图案。优选的装饰性层为在油墨接受层中包括有色图案的喷墨印刷的热固性树脂浸渍的纸,所述油墨接受层包含无机颜料P和聚合物连结料B,无机颜料与聚合物连结料的重量比(P/B比率)大于1.5,其中油墨接受层的无机颜料P与有色图案中的喷射有色颜料C的重量比(P/C比率)大于4.0,且其中所述油墨接受层基本不含热固性树脂。
在一个优选的实施方案中,所述包含无机颜料和聚合物连结料的油墨接受层具有大于3.0、优选3.5或更高的无机颜料与连结料的重量比P/B。
在印刷有色图案或其至少一部分之前,纸已经提供有树脂。该措施改进了纸的稳定性。在这种情况下,由于树脂的提供造成的膨胀或收缩的至少一部分在喷墨印刷之前发生。提供有树脂的纸在施用油墨接受层之前且在喷墨印刷之前干燥,优选到10%或更小的残余湿度。在这种情况中,纸层的膨胀或收缩的最重要部分被中和。具有该尺寸稳定性的优势特别在需要凸纹与印好的装饰之间的一致性的情形中观察到,如在EP 1290290 A(FLOORING IND)中。在施用油墨接受层之前干燥提供有热固性树脂的纸的另一个优势在于,在油墨接受层中不存在或基本不存在热固性树脂。在油墨接受层中热固性树脂的存在会使喷墨印刷图像的油墨渗出变劣。
装饰性板如地板在芯层的一侧具有装饰性层,在芯层的另一侧具有平衡层。然而,装饰性层可施用于芯层的两侧。后者在用于家具的层压板的情况下特别合乎需要。在这种情况下,优选还将保护性层施用在存在于芯层两侧的两个装饰性层上。
装饰性层压材料
装饰性层压材料优选为刚性或柔性板,但也可以为柔性基材卷。在一个优选的实施方案中,装饰性层压材料选自厨房板、地板、家具板、天花板和墙板。
优选的装饰性层压材料包含热压有芯层和保护性层的如上所述的P/B比率大于1.5的油墨接受层和P/C比率大于4.0的有色图案的喷墨印刷的热固性树脂浸渍的纸,其中所述装饰性层压材料选自地板、厨房板、家具板和墙板。在一个更优选的实施方案中,所述装饰性层压材料包括能够实现少胶水机械连接的榫和槽。
装饰性板(30),由图3中也具有榫和槽(33,32)的地板图示说明,优选至少包括芯层(31)和装饰性层(34)。为了使装饰性层(34)的有色图案抗磨,可在装饰性层(34)顶上施加保护性层(35)。也可在芯层(31)的相对侧施加平衡层(36),以限制或防止装饰性板(30)可能的弯曲。平衡层、芯层、装饰性层还有优选的保护性层组装成装饰性板优选在优选DPL过程(直接压力层压)的相同压制处理中进行。
在装饰性板的一个优选实施方案中,使榫和槽形状(分别为图3中的33和32)铣成使它们相互滑入的单独装饰性板的侧部。在地板的情况下,榫和槽接合保证牢固的地板结构,并保护地板,防止湿气渗透。
在一个更优选的实施方案中,装饰性板包括使它们相互咬合的特殊形状的榫和槽(例如分别为图4中的33和32)。其优势是不需胶水容易组装。得到良好机械接合所必需的榫和槽的形状为层压地板领域所熟知,也例示于EP 2280130 A(FLOORING IND)、WO 2004/053258(FLOORING IND)、US 2008010937(VALINGE)和US 6418683(PERSTORP FLOORING)。
榫和槽形状尤其优选用于地板和墙板,但在家具板的情况下,由于家具门和抽屉正面的审美原因,优选不存在这些榫和槽形状。然而,可将榫和槽形状用于与家具的其他板咬合在一起,如US 2013071172(UNILIN)说明。
装饰性层压材料,尤其装饰性板,可进一步包括吸音层,如US 8196366(UNILIN)所公开。
在一个优选的实施方案中,装饰性板为抗静电分层板。使装饰性板抗静电的技术在装饰性层压材料领域熟知,如EP 1567334 A(FLOORING IND)示例说明。
装饰性层压材料的顶表面,即,至少保护性层,优选提供有匹配有色图案的凸纹,例如,木印品中的木粒纹、裂纹和结节。完成这种凸纹的压印技术是公知的,并由例如EP1290290 A(FLOORING IND)、US 2006144004(UNILIN)、EP 1711353 A(FLOORING IND)和US2010192793(FLOORING IND)所公开。
最优选通过将数字压印板压在装饰性工件或叠垒的装饰性工件的顶层来形成凸纹。
数字压印板是这样的一块板,其包括可通过将数字压印版压在装饰性工件或叠垒的装饰性工件的顶层用于在装饰性工件上形成凸纹的隆起。该隆起为固化的喷墨液滴,该液滴由喷墨印刷设备喷射,且最优选为UV固化喷墨液滴。隆起优选通过在已经固化或pin-固化喷墨液滴上方印刷并固化喷墨液滴形成。该板优选通过使用金属或硬塑料使其为刚性。
数字压印板的一个备选物可为数字压印圆筒,数字压印圆筒为包含隆起的圆筒,以通过将该数字压印圆筒压在装饰性工件或叠垒的装饰性工件的顶层并旋转在装饰性工件上形成凸纹。在数字压印圆筒上的隆起为固化的喷墨液滴,该液滴由喷墨印刷设备喷射,且最优选为UV固化喷墨液滴。该隆起优选通过在已经固化或pin-固化喷墨液滴上方印刷并固化喷墨液滴形成。
在一个优选的实施方案中,装饰性板以长方体条的形式制造。其尺寸可有很大变化。优选板具有超过1米的长度和超过0.1米的宽度,例如,板可以为约1.3米长和约0.15米宽。根据一个特殊实施方案,板的长度超过2米,且宽度优选为约0.2米或更宽。这些板的印刷优选不含重复。
芯层
芯层优选由木基材料制成,例如颗粒板、MDF或HDF(中密度纤维板或高密度纤维板)、定向碎料板(OSB)等。也可使用合成材料板或由水硬化的板(例如,水泥板)。在一个特别优选的实施方案中,芯层为MDF或HDF板。
芯层也可至少从用热固性树脂浸渍的多张纸片或其他载体片材组装,如WO 2013/050910(UNILIN)所公开。优选的纸片包括由化学制浆法(也称为牛皮纸浆制法)得到的所谓的牛皮纸,如US 4952277(BET PAPERCHEM)所公开。
在另一个优选的实施方案中,芯层为基本由木纤维组成的通过缩聚胶水粘合的板材料,其中缩聚胶水占板材料的5至20%重量,并得到来自循环木的至少40%重量木纤维。适合实例由EP 2374588 A(UNILIN)公开。
也可用合成芯层代替木基芯层,如US 2013062006(FLOORING IND)公开的那些芯层。在一个优选的实施方案中,芯层包括泡沫合成材料,如泡沫聚乙烯或泡沫聚氯乙烯。
其他优选芯层及其制造由US 2011311806(UNILIN)和US 6773799(DECORATIVESURFACES)所公开。
芯层厚度优选为2-12mm,更优选5-10mm。
纸基材
装饰性层和优选的保护性层(如果存在)和/或平衡层包括纸作为基材。
纸优选具有小于150g/m2的重量,因为较重纸片难以用热固性树脂浸渍整个厚度。不考虑在其上提供的树脂,所述纸层具有50-130g/m2的纸重,且优选为70-130g/m2的纸重。纸重不能太高,因为否则充分浸渍纸所需的树脂量会太高,并且在压制操作中可靠地进一步处理印刷纸变得不可行。
优选纸片具有根据Gurley方法(DIN 53120) 8-25秒的孔隙率。这种孔隙率甚至使大于150g/m2的重片材能够容易地用相对较高量树脂浸渍。
具有高孔隙率的适合纸片及其制造也由US 6709764(ARJO WIGGINS)公开。
用于装饰性层的纸优选为白纸,并且可包含一种或多种增白剂,如二氧化钛、碳酸钙等。存在增白剂有助于掩蔽芯层上的色差,色差可对有色图案产生不合需要的颜色效果。
或者,用于装饰性层的纸可为包含一种或多种有色染料和/或有色颜料的形成一定厚度的(bulk)色纸。除了掩蔽芯层上的颜色差异外,使用有色纸还减小印刷有色图案所需的喷墨油墨的量。例如,为了减小所需喷墨油墨的量,可用浅棕色或灰色纸印刷木纹作为有色图案。
在一个优选的实施方案中,将未漂白牛皮纸用于装饰性层中的微棕色纸。牛皮纸具有低木质素含量,这得到高拉伸强度。牛皮纸的优选类型是具有高孔隙率的40至135g/m2的吸收性牛皮纸,由优良均匀性的洁净低κ硬木牛皮纸制成。
如果保护性层包括纸,则使用在树脂浸渍后变得透明或半透明的纸,以便能够看到装饰性层中的有色图案。
也可在平衡层中使用以上纸。
为清楚起见,应明白,树脂涂覆的纸,所谓的RC(resin coated)纸,不是本发明的装饰性层压材料制造方法的热固性树脂浸渍纸。在家庭/办公水性喷墨印刷中使用的RC纸由不含树脂的多孔纸芯组成。RC纸只在其表面上具有树脂涂层,通常为聚乙烯或聚丙烯树脂涂层,且在其上具有一个或多个受墨层。这种RC纸具有对热固性树脂的低渗透性,导致不均树脂吸收和在压制后脱层的高风险。
热固性树脂
热固性树脂优选选自基于三聚氰胺-甲醛的树脂、基于脲-甲醛的树脂和基于苯酚-甲醛的树脂。用于浸渍纸的其他适合树脂在EP 2274485 A(HUELSTA)的[0028]中列出。
最优选的热固性树脂为基于三聚氰胺-甲醛的树脂,在本领域中常简称为“三聚氰胺(基)树脂”。
三聚氰胺甲醛树脂优选具有1.4至2的甲醛与三聚氰胺的比率。这种基于三聚氰胺的树脂为在暴露于在压制操作中的热时缩聚的树脂。所述缩聚反应产生作为副产物的水。本发明所关注的特别是这些种类的热固性树脂,即产生作为副产物的水的那些热固性树脂。所产生的水以及在压制之前在热固性树脂中的任何水残留在被截留并引起硬化层中的透明度损失之前必须在很大程度上离开硬化树脂层,然而本发明提供了限制这种障碍的手段。
所述纸优选提供有与所述纸的重量相比等于40-250%树脂干重的量的热固性树脂。实验表明该范围的施用树脂提供所述纸的充分浸渍,这在很大程度上避免了破裂并且使纸的尺寸非常稳定。
所述纸优选提供有如下量的热固性树脂,该量使得至少纸芯用所述树脂饱和。所述饱和可在提供相当于纸重量的至少1.5或至少2倍的量的树脂时实现。优选首先浸渍所述纸或使其饱和,且然后至少在其待印刷侧上部分地除去树脂。
优选在印刷时在所述纸上提供的树脂处于B-阶段。在热固性树脂未完全交联时存在这样的B-阶段。
优选提供在所述纸上的树脂在印刷时具有低于15重量%且更好是10重量%或更低的相对湿度。
优选为所述纸提供热固性树脂的步骤包括在纸上施用水和树脂的混合物。施用混合物可包括在混合物的浴中浸渍纸。优选所述树脂以定剂量方式例如通过使用一个或多个挤压辊和/或刮刀提供以设定加到纸层的树脂的量。
用树脂浸渍纸基材的方法在本领域中公知,如由WO 2012/126816 (VITS)和EP966641 A (VITS)举例说明。
用于浸渍的水和树脂的混合物的干树脂含量取决于树脂的类型。含有苯酚-甲醛树脂的水溶液优选具有约30重量%的干树脂含量,而含有三聚氰胺-甲醛树脂的水溶液优选具有约60重量%的干树脂含量。用所述溶液浸渍的方法由例如US 6773799 (DECORATIVESURFACES)公开。
所述纸优选用自US 4109043 (FORMICA CORP)和US 4112169 (FORMICA CORP)已知的混合物浸渍,由此优选(紧次于三聚氰胺甲醛树脂)还包含聚氨酯树脂和/或丙烯酸类树脂。
包含热固性树脂的混合物还可包括添加剂,例如着色剂、表面活性成分、杀生物剂、抗静电剂、耐磨的硬颗粒、弹性体、UV吸收剂、有机溶剂、酸、碱等。
将着色剂加到含有热固性树脂的混合物中的优势在于,可使用单一类型的白纸来生产装饰性层,由此减少装饰性层压材料生产商的纸库存。如上文已经描述,使用有色纸来减少印刷木材花纹所需要的油墨量在此通过用淡棕色热固性树脂浸渍使白纸着色来实现。后者允许较好地控制某些木材花纹所需要的棕色的量。
抗静电剂可用于热固性树脂中。然而,在所述树脂中优选不存在抗静电剂,如NaCl和KCl、碳颗粒和金属颗粒,因为它们常具有不期望的副作用,例如较低的耐水性或较低的透明度。其他合适的抗静电剂由EP 1567334 A (FLOORING IND)公开。
耐磨的硬颗粒优选包含在保护性层中。
油墨接受层
所述油墨接受层包含无机颜料和聚合物连结料,无机颜料P与聚合物连结料B的重量比P/B大于1.5、优选大于3.0。无机颜料可为单种类型的无机颜料或多种不同的无机颜料。所述聚合物连结料可为单种类型的聚合物连结料或多种不同的聚合物连结料。
在一个优选的实施方案中,油墨接受层具有2.0 g/m2-10.0 g/m2,更优选3.0-6.0g/m2的总干重。
在一个优选的实施方案中,油墨接受层包括选自以下的聚合物连结料:羟乙基纤维素;羟丙基纤维素;羟乙基甲基纤维素;羟丙基甲基纤维素、羟丁基甲基纤维素;甲基纤维素、羧甲基纤维素钠;羧甲基羟乙基纤维素钠;水溶性乙基羟乙基纤维素;硫酸纤维素;聚乙烯醇;乙烯基醇共聚物;聚乙酸乙烯酯;聚乙烯基乙缩醛;聚乙烯基吡咯烷酮;聚丙烯酰胺;丙烯酰胺/丙烯酸共聚物;聚苯乙烯;苯乙烯共聚物;丙烯酸类或甲基丙烯酸类聚合物;苯乙烯/丙烯酸类共聚物;乙烯-乙酸乙烯酯共聚物;乙烯基-甲基醚/马来酸共聚物;聚(2-丙烯酰氨基-2-甲基丙烷磺酸);聚(二亚乙基三胺-共-己二酸);聚乙烯基吡啶;聚乙烯基咪唑;表氯醇改性的聚乙烯亚胺;环氧乙烷改性的聚乙烯亚胺;含醚键的聚合物例如聚氧乙烯(PEO)、聚氧丙烯(PPO)、聚乙二醇(PEG)和聚乙烯基醚(PVE);聚氨酯;三聚氰胺树脂;明胶;角叉菜胶;葡聚糖;阿拉伯胶;酪蛋白;果胶;白蛋白;壳多糖;壳聚糖;淀粉;胶原衍生物;胶棉和琼脂。
在一个特别优选的实施方案中,油墨接受层包括聚合物连结料,优选水溶性聚合物连结料(> 1 g/L水),该水溶性聚合物连结料具有羟基作为亲水结构单元,例如聚乙烯醇。
用于油墨接受层的优选的聚合物为聚乙烯醇(PVA)、乙烯基醇共聚物或改性的聚乙烯基醇。所述改性的聚乙烯基醇可为阳离子型聚乙烯基醇,例如得自Nippon Goshei的Kuraray的各种系列的阳离子型聚乙烯醇,例如POVAL C506, POVAL C118。
油墨接受层中的颜料优选为无机颜料,其可选自中性、阴离子和阳离子颜料类型。有用的颜料包括例如二氧化硅、滑石、粘土、水滑石、高岭土、硅藻土、碳酸钙、碳酸镁、碱式碳酸镁、铝硅酸盐、三氢氧化铝、氧化铝、氧化钛、氧化锌、硫酸钡、硫酸钙、硫化锌、缎白(satin white)、氧化铝水合物例如勃母石、氧化锌或混合氧化物。
无机颜料优选选自氧化铝水合物、铝氧化物、铝氢氧化物、硅酸铝和二氧化硅。
特别优选的无机颜料为二氧化硅颗粒、胶体二氧化硅、氧化铝颗粒和假勃母石,原因是它们形成更多孔的结构。当在本文中使用时,颗粒可为原样直接使用的一级离子,或者它们可形成二级颗粒。优选所述颗粒具有2 µm或更小、优选200 nm或更小的平均一级颗粒直径。
一种优选类型的氧化铝水合物为结晶勃母石,即,γ-AlO(OH)。勃母石的有用类型包括得自Sasol的DISPERAL HP14、DISPERAL 40、DISPAL 23N4-20、DISPAL 14N-25和DISPERAL AL25;和得自Martinswerk GmbH的MARTOXIN VPP2000-2和GL-3。
有用的阳离子氧化铝类型包括α-Al2O3类型,例如NORTON E700,得自Saint-GobainCeramics & Plastics, Inc,和γ-Al2O3类型,例如得自Degussa的ALUMINUM OXID C。
其他有用的无机颜料包括三氢氧化铝例如三羟铝石,即,α-Al(OH)3,例如PLURALBT,得自Sasol;和水铝矿,即γ-Al(OH)3,例如得自Martinswerk GmbH的MARTINAL系列和MARTIFIN系列,得自JM Huber company的MICRAL系列;得自Showa Denka K.K.的HIGILITE系列。
另一优选类型的无机颜料为二氧化硅,其可原样使用、以其阴离子形式使用或在阴离子改性后使用。二氧化硅可选自不同的类型,例如结晶二氧化硅、无定形二氧化硅、沉淀二氧化硅、煅制二氧化硅、二氧化硅凝胶、球形和非球形二氧化硅。二氧化硅可包含少量的来自Al、Zr、Ti组的金属氧化物。有用的类型包括AEROSIL OX50 (BET表面积为50±15 m²/g,平均一级粒径为40 nm,SiO2含量> 99.8%, Al2O3含量< 0.08%)、AEROSIL MOX170 (BET表面积为170 g/m²,平均一级粒径为15 nm,SiO2含量> 98.3%,Al2O3含量为0.3-1.3%)、AEROSIL MOX80 (BET表面积为80 ±20 g/m²,平均一级粒径30 nm, SiO2含量> 98.3%,Al2O3含量为0.3-1.3%)或得自Degussa-Hüls AG的其他亲水性AEROSIL系列,其可获得小平均粒径(<500 nm)的水性分散体。
概括地讲,取决于其生产方法,二氧化硅颗粒分为两种类型:湿法颗粒和干法颗粒(气相法或煅烧法)颗粒。
在湿法工艺中,活性二氧化硅通过硅酸盐的酸解形成,且这被聚合到适合的程度并絮凝以获得含水二氧化硅。
气相法包括两种类型,一种包括卤化硅的高温气相水解以获得无水二氧化硅(火焰水解),另一种包括二氧化硅砂的热还原气化并在电炉中结焦,随后在空气中将其氧化也获得无水二氧化硅(电弧法)。“煅烧二氧化硅”是指在气相法中获得的无水二氧化硅颗粒。
对于用于本发明中的二氧化硅颗粒,特别优选煅烧二氧化硅颗粒。在表面硅醇基团的密度方面以及在其中是否存在孔方面,煅烧二氧化硅不同于含水二氧化硅,且这两种不同类型的二氧化硅具有不同的性质。煅烧二氧化硅适用于形成高孔隙率的三维结构。因为煅烧二氧化硅具有特别大的比表面积,其油墨吸收和保留高。优选地,气相二氧化硅具有30 nm或更小、更优选20 nm或更小、甚至更优选10 nm或更小、最优选3-10nm的平均一级粒径。煅烧二氧化硅颗粒容易地通过其中硅醇基团处的氢键聚结。因此,当其平均一级粒径不大于30nm时,二氧化硅颗粒可形成高孔隙率的结构。
在一个进一步优选的实施方案中,所述油墨接受层可进一步被交联。可使用本领域公知的任何适合的交联剂。特别优选硼酸作为交联剂用于根据本发明的油墨接受层。
油墨接受层可包括其他添加剂,例如着色剂、表面活性剂、杀生物剂、抗静电剂、耐磨硬颗粒、弹性体、UV吸收剂、有机溶剂、增塑剂、光稳定剂、pH调节剂、抗静电剂、增白剂、消光剂等。
油墨接受层可由单层组成,或可由两个、三个或更多个甚至具有不同组成的层组成。
可通过任何常规涂布技术将油墨接受层涂布在载体上,涂布技术例如浸涂、刮涂、挤出涂布、旋涂、滑斗涂布和帘涂。
或者,可通过印刷技术施用油墨接受层,例如柔版印刷、丝网印刷和喷墨印刷。喷墨印刷机优选采用阀式喷墨印刷头。
有色图案
有色图案通过在存在于热固性树脂浸渍的纸基材的表面上的油墨接受层上喷射加有颜料的喷墨油墨来获得。
对于有色图案的内容没有实际局限。有色图案还可含有例如文字、箭头、标识(logo)等信息。喷墨印刷的优势在于,与凹版印刷相反,所述信息可以少量印刷而不需要额外费用。
在一个优选的实施方案中,有色图案为木材复制或石头复制,但其也可为幻想或创意图案,例如古代世界地图或几何图案,或甚至用于制造例如由黑色和红色块组成的地板的单一颜色或单色家具门。
印刷木色图案的一个优势在于,除了橡木、松木和榉木之外,还可以模仿非常昂贵的木材如黑胡桃来生产地板,而这些非常昂贵的木材总是不常用于室内装饰。
印刷石头色图案的一个优势在于,可生产真切地模仿石头地板、但在其上光脚行走时不会有寒冷感觉且根据时尚随时间容易替换的地板。
保护性层
优选保护性层在喷墨印刷之后例如当作覆盖层(即提供有树脂的载体或液体涂料)施用在有色图案上,优选同时装饰层铺展在基材上,该基材松散地或已经连接或附着到装饰层上。
在一个优选的实施方案中,覆盖层的载体为用热固性树脂浸渍的纸,其在DPL方法中热压之后变成透明或半透明。
制造这种覆盖层的优选方法描述在US 2009208646 (DEKOR-KUNSTSTOFFE)中。
所述液体涂料优选包含热固性树脂,但还可为另一类型的液体,例如UV可固化或EB可固化的清漆。
在一个特别优选的实施方案中,所述液体涂料包含三聚氰胺树脂和硬颗粒如金刚砂。
所述保护性层优选为最外层,但在另一实施方案中,热塑性或弹性体表面层可涂覆在优选为纯热塑性或弹性体材料的保护性层上。在后一情况下,优选基于热塑性或弹性体材料的层也施用在芯层的另一侧上。
液体三聚氰胺涂料在DE 19725829 C (LS INDUSTRIELACKE)和US 3173804(RENKL PAIDIWERK)中举例说明。
液体涂料可含有硬颗粒,优选透明硬颗粒。含有硬颗粒的用于防磨损的合适液体涂料和这样的保护性层的方法由US 2011300372 (CT FOR ABRASIVES AND REFRACTORIES)和US 8410209 (CT FOR ABRASIVES AND REFRACTORIES)公开。
保护性层的透明度以及颜色可通过硬颗粒控制,此时它们含有来自元素Li、Na、K、Ca、Mg、Ba、Sr、Zn、Al、Si、Ti、Nb、La、Y、Ce或B的氧化物、氮氧化物或混合氧化物中的一种或多种。
硬颗粒和透明固体材料颗粒的总量基于液体涂料的总体积通常为5体积%-70体积%。硬颗粒的总量为1 g/m2-100 g/m2,优选为2 g/m2-50 g/m2。
如果所述保护性层包括纸作为用于热固性树脂的载体片材,则优选将例如氧化铝颗粒的硬颗粒结合在纸中或结合在纸上。优选的硬颗粒为选自氧化铝、碳化硅、氧化硅、氮化硅、碳化钨、碳化硼和二氧化钛或选自任何其他金属氧化物、金属碳化物、金属氮化物或金属碳氮化物的陶瓷或矿物颗粒。最优选的硬颗粒为金刚砂和所谓的赛隆陶瓷。原则上,可使用多种颗粒。当然,还可施用上文提到的硬颗粒的任何混合物。
在包括纸作为用于热固性树脂的载体片材的保护性层的一个备选的实施方案中,喷墨印刷在保护性层的热固性树脂浸渍的纸上进行。包含例如二氧化钛的增白剂的其他纸基材则仅可用于掩蔽芯层的表面缺陷。
可根据所需的耐磨性决定保护性层中硬颗粒的量,优选通过如在EN 13329中限定并且公开在WO 2013/050910 A (UNILIN)和US 8410209 (CT FOR ABRASIVES ANDREFRACTOR)中的所谓翼片试验(Taber test)测定。
优选具有1-200µm的平均粒度的硬颗粒。优选在印刷图案上施用1-40 g/m2的量的这类颗粒。低于20 g/m2的量对于较低的品质而言可足够。
如果保护性层包括纸,则其优选具有10-50 g/m2的纸重。这类纸常常也被称作通常用于层压板中的所谓的覆盖层。制造这类覆盖层的优选方法由WO 2007/144718(FLOORING IND)公开。
优选在印刷图案之上提供热固性树脂的保护性层的步骤包括压制处理。优选在压制处理中施用高于150℃的温度,更优选施用180℃-220℃的温度和大于20巴、更优选35-40巴的压力。
在另一个优选的实施方案中,所述装饰性层压材料使用两次压制处理制造,因为这产生极高的耐磨性。实际上,在第一压制处理期间,优选直接在耐磨保护性层之下的层基本或完全固化。籍此,包含在耐磨保护性层中的硬颗粒被防止向下推出地板的顶部区域而进入有色图案中或有色图案以下,且呆在它们最有效的区域中,即基本上在有色图案之上。这可以实现超过10000轮的根据EN 13329中限定的翼片试验的初始磨损点,而在具有相同组成的层的一次压制处理中,仅实现超过4000轮。显然使用如上限定的两次压制处理导致更有效地使用可得的硬颗粒。使用至少两次压制处理的一个备选优势在于,如果产品被压制两次,则可在用较少硬颗粒的情况下得到与使用单一压制处理的情况类似的磨损率。降低硬颗粒的量是令人关注的,因为硬颗粒趋于降低耐磨保护性层的透明度,这是不合需要的。这还可以用较小直径的硬颗粒,例如具有15µm或更小或甚至5µm或更小的平均粒径的颗粒工作。
平衡层
所述一个或多个平衡层的主要目的是补偿在芯层的相对侧上的各层的拉伸力,从而得到基本平坦的装饰性板。这样的平衡层优选为热固性树脂层,其可包括一个或多个载体层,例如纸张。
如上文对于家具板已经解释,所述一个或多个平衡层可为任选保护性层互补的装饰性层。
代替一个或多个透明平衡层,还可使用不透明的平衡层,这通过掩蔽表面不规则而给予装饰性板更吸引人的外观。此外,其可包含文字或图形信息,例如公司标识或文字信息。
加有颜料的喷墨油墨
有色图案使用一种或多种包含有色颜料的水性加有颜料的喷墨油墨和/或基于有机溶剂的加有颜料的喷墨油墨来印刷。
水性加有颜料的喷墨油墨的液相可为纯水,但优选存在一些有机溶剂,例如润湿剂。
基于有机溶剂的加有颜料的喷墨油墨不含故意加入的水,但是可包含非常少量的水,通常小于5%重量的水,基于油墨总重量计算。该水并非故意加入,而是作为污染物通过其他组分进入配方中,例如来自极性有机溶剂。基于油墨总重量计算高于5%重量的水会使得喷墨油墨不稳定,优选水含量小于1%重量,基于油墨总重量计算,最优选完全不存在水。
加有颜料的水性喷墨油墨优选包括至少一种或多种有色颜料和水,如果有色颜料不是自分散型有色颜料的话,则最后加有一种或多种分散剂。基于有机溶剂的加有颜料的喷墨油墨优选包括至少一种或多种有色颜料、一种或多种分散剂和一种或多种有机溶剂。
将喷墨油墨组成具有不同颜色的喷墨油墨的喷墨油墨套装。喷墨油墨套装可为标准CMYK油墨套装,但是优选为CRYK油墨套装,其中品红色(M)油墨用红色(R)喷墨油墨替换。使用红色喷墨油墨增强了基于木头的有色图案的色域,而这种图案代表了地板用层压材料中的大多数装饰性层压材料。
喷墨油墨套装可用额外的油墨来拓展,例如白色、棕色、红色、绿色、蓝色和/或橙色以进一步扩大图像的色域。喷墨油墨套装还可通过将全密度喷墨油墨与浅密度喷墨油墨结合来拓展。深色油墨与浅色油墨和/黑色和灰色油墨的组合通过降低的颗粒度改善了图像品质。然而,优选喷墨油墨套装由不超过3种或4种喷墨油墨组成,使得以可接受的成本设计高产出的多程喷墨印刷机。
有色颜料
喷墨油墨的着色剂优选由一种或多种有色颜料组成。有色颜料具有比染料高得多的光稳定性。加有颜料的喷墨油墨优选含有用于分散颜料的分散剂,更优选为聚合物分散剂。除了聚合物分散剂之外,所述加有颜料的喷墨油墨还可含有分散增效剂,以进一步改进油墨的分散品质和稳定性。
在加有颜料的水性喷墨油墨中,所述水性喷墨油墨可含有所谓的“可自分散的”有色颜料。可自分散的有色颜料不需要分散剂,因为颜料表面具有实现颜料分散体的静电稳定化的离子基团。在可自分散的有色颜料的情况下,通过使用聚合物分散剂得到的立体稳定化变成可选的。可自分散的有色颜料的制备在本领域中公知且可由EP 904327 A(CABOT)举例说明。
有色颜料可为黑色、白色、青色、品红色、黄色、红色、橙色、紫色、蓝色、绿色、棕色、其混合色等。有色颜料可选自HERBST,Willy等,Industrial Organic Pigments,Production, Properties, Applications(工业有机颜料、生产、性能、应用),第三版,Wiley-VCH, 2004. ISBN 3527305769中公开的那些颜料。
用于青色水性喷墨油墨的特别优选的颜料为铜酞菁颜料,更优选为C. I. 颜料蓝15:3或C. I. 颜料蓝15:4。
用于红色水性喷墨油墨的特别优选的颜料为C. I. 颜料红254、C. I. 颜料红176和C. I. 颜料红122及其混晶。
用于黄色水性喷墨油墨的特别优选的颜料为C. I. 颜料黄151、C. I. 颜料黄180、C. I. 颜料黄74及其混晶。
对于黑色油墨,合适的颜料材料包括碳黑,例如得自Cabot Co.的RegalTM 400R、MogulTM L、ElftexTM 320;或得自DEGUSSA Co.的Carbon Black FW18、Special BlackTM250、Special BlackTM 350、Special BlackTM 550、PrintexTM 25、PrintexTM 35、PrintexTM55、PrintexTM 90、PrintexTM 150T;得自MITSUBISHI CHEMICAL Co.的MA8;和C. I. 颜料黑7和C. I. 颜料黑11。
还可使用混晶。混晶也称作固溶体。例如,在一定条件下,不同的喹吖啶酮彼此混合以形成固溶体,其与这些化合物的物理混合物和化合物本身完全不同。在固溶体中,组分的分子通常(但并不总是)与所述组分之一进入相同的晶格中。所得结晶固体的x-射线衍射图为该固体所特有的并且可明确地区分于相同组分以相同比例的物理混合物的图案。在这样的物理混合物中,所述组分中的每一种的x-射线图均可区分,并且这些线中许多线的消失为固溶体形成的标准之一。市售的实例为得自Ciba Specialty Chemicals的CinquasiaTMMagenta RT-355-D。
并且可使用颜料的混合物。例如,黑色喷墨油墨可包含碳黑颜料和至少一种选自蓝色颜料、青色颜料、品红色颜料和红色颜料的颜料。发现这类黑色喷墨油墨允许对于木色更容易且更好地颜色管理。
在一个特别优选的实施方案中,喷射的加有颜料的油墨包括至少三种水性加有颜料的喷墨油墨和/或基于有机溶剂的加有颜料的喷墨油墨包括选自以下的颜料:碳黑、C.I. 颜料蓝15:3、C. I. 颜料蓝15:4、C.I颜料黄151、C. I. 颜料黄180、C. I. 颜料黄74、C.I. 颜料红254、C. I. 颜料红176、C. I. 颜料红122及其混晶。发现在这种情况下,可获得非常光稳定的有色图案。
在加有颜料的喷墨油墨中的颜料颗粒应足够小以允许墨水经由喷墨印刷装置,特别是在喷嘴处自由流动。为了最大色强度且为了减慢沉降,使用小颗粒也是合乎需要的。
在加有颜料的喷墨油墨中颜料的平均粒度应该为0.005µm-15µm。优选平均颜料粒径为0.005-5µm,更优选为0.005-1µm,特别优选为0.005-0.3µm且最优选为0.040-0.150µm。
颜料在加有颜料的喷墨油墨中以基于加有颜料的喷墨油墨的总重量计算0.1-20重量%、优选1-10重量%且最优选2-5重量%的量使用。优选至少2重量%的颜料浓度以降低产生有色图案所需的喷墨油墨的量,而高于5重量%的颜料浓度降低用具有20-50μm的喷嘴直径的印刷头印刷有色图案的色域。
分散剂
加有颜料的喷墨油墨可包含用于分散颜料的分散剂,更优选为聚合物分散剂。
合适的聚合物分散剂为两种单体的共聚物,但它们可含有三种、四种、五种或甚至更多种单体。聚合物分散剂的性质取决于单体的性质和其在聚合物中的分布二者。共聚分散剂优选具有以下聚合物组分:
• 统计学聚合的单体(例如,聚合成ABBAABAB的单体A和B);
• 交替聚合的单体(例如,聚合成ABABABAB的单体A和B);
• 梯度(梯状)聚合的单体(例如,聚合成AAABAABBABBB的单体A和B);
• 嵌段共聚物(例如,聚合成AAAAABBBBBB的单体A和B),其中各嵌段(2、3、4、5或甚至更大)的嵌段长度对聚合物分散剂的分散能力是重要的;
• 接枝共聚物(接枝共聚物由聚合物主链和与主链连接的聚合物侧链组成);和
• 这些聚合物的混合形式,例如嵌段梯度共聚物。
合适的分散剂为自BYK CHEMIE购得的DISPERBYKTM分散剂、自JOHNSON POLYMERS购得的JONCRYLTM分散剂和自ZENECA购得的SOLSPERSETM分散剂。非聚合物分散剂以及一些聚合物分散剂的详细列表由MC CUTCHEON. Functional Materials, North AmericanEdition. Glen Rock, N.J.: Manufacturing Confectioner Publishing Co., 1990.110-129页公开。
所述聚合物分散剂优选具有500-30000、更优选1500-10000的数均分子量Mn。
所述聚合物分散剂优选具有小于100,000、更优选小于50,000且最优选小于30,000的重均分子量Mw。
所述聚合物分散剂优选具有小于2、更优选小于1.75且最优选小于1.5的多分散性PD。
聚合物分散剂的市售实例有下述物质:
DISPERBYKTM 分散剂,得自BYK CHEMIE GMBH;
SOLSPERSETM 分散剂,得自NOVEON;
TEGOTM DISPERSTM分散剂,得自DEGUSSA;
EDAPLANTM分散剂,得自MÜNZING CHEMIE;
ETHACRYLTM分散剂,得自LYONDELL;
GANEXTM分散剂,得自ISP;
DISPEXTM和 EFKATM分散剂,得自CIBA SPECIALTY CHEMICALS INC;
DISPONERTM分散剂,得自DEUCHEM;和
JONCRYLTM分散剂,得自JOHNSON POLYMER。
对于非水性喷墨油墨特别优选的包括得自NOVEON的SolsperseTM分散剂、得自CIBASPECIALTY CHEMICALS INC的EfkaTM分散剂、得自BYK CHEMIE GMBH的DisperbykTM分散剂。
对于基于溶剂的颜料分散体特别优选的分散剂为得自NOVEON的SolsperseTM32000和39000。
聚合物分散剂优选以2-600%重量、更优选5-200%重量的量用于颜料分散体中,基于颜料的重量计算。
在一个特别优选的实施方案中,在水性加有颜料的喷墨油墨中使用的聚合物分散剂为包含3-11摩尔%的长脂族链(甲基)丙烯酸酯的共聚物,其中所述长脂族链含有至少10个碳原子。
所述长脂族链(甲基)丙烯酸酯优选含有10-18个碳原子。所述长脂族链(甲基)丙烯酸酯优选为(甲基)丙烯酸癸酯。所述聚合物分散剂可用包含3-11摩尔%的长脂族链(甲基)丙烯酸酯的单体和/或低聚物的混合物的简单受控聚合制备,其中所述长脂族链含有至少10个碳原子。
为包含3-11摩尔%的长脂族链(甲基)丙烯酸酯的共聚物的市售聚合物分散剂为EdaplanTM 482,一种得自MUNZING的聚合物分散剂。
有机溶剂
所述一种或多种基于有机溶剂的加有颜料的喷墨油墨优选包括至少一种具有至少为250的分子量的聚亚烷基二醇二烷基醚。
所述聚亚烷基二醇二烷基醚优选由式(I)表示:
式(I)
其中,R1和R2各自独立地选自具有1-4个碳原子的烷基;Y表示亚乙基或亚丙基;n为选自5-20的整数。根据式(I)的聚亚烷基二醇二烷基醚的烷基R1和R2优选表示甲基和/或乙基。最优选,烷基R1和R2均为甲基。在一个优选的实施方案中,根据式(I)的聚亚烷基二醇二烷基醚为聚亚乙基二醇二烷基醚。
所述一种或多种基于有机溶剂的加有颜料的喷墨油墨优选包括根据式(I)的第二聚亚烷基二醇二烷基醚,其中整数n选自4-20,更优选整数n选自6-17。
在一个优选的实施方案中,所述基于有机溶剂的加有颜料的喷墨油墨包括至少两种具有四个或更多个亚烷基二醇基团的聚亚烷基二醇二烷基醚的混合物,但是其中在所述两个聚亚烷基二醇二烷基醚中的亚烷基二醇基团的数目不相同。
用于根据本发明的颜料分散体的聚亚烷基二醇二烷基醚的适合的混合物包括分子量至少为200的聚亚乙基二醇二甲基醚的混合物,例如得自CLARIANT的Polyglycol DME200TM、Polyglycol DME 250TM和Polyglycol DME 500TM。用于非水性喷墨油墨的聚亚烷基二醇二烷基醚优选具有200-800的平均分子量,更优选不存在分子量大于800的聚亚烷基二醇二烷基醚。聚亚烷基二醇二烷基醚的混合物优选在室温下为均匀的液体混合物。
所述基于有机溶剂的加有颜料的喷墨油墨可包括选自聚亚烷基二醇单烷基醚乙酸酯和聚亚烷基二醇单烷基醚的聚亚烷基二醇衍生物。在一个优选的实施方案中,聚亚烷基二醇衍生物选自二亚丙基二醇单甲基醚乙酸酯、二亚乙基二醇单丁基醚乙酸酯、三亚乙基二醇单丁基醚和三亚丙基二醇单甲基醚。
在一个非常优选的实施方案中,聚亚烷基二醇单烷基醚乙酸酯选自二亚丙基二醇单甲基醚乙酸酯和二亚乙基二醇单丁基醚乙酸酯。
在另一个非常优选的实施方案中,聚亚烷基二醇单烷基醚选自三亚乙基二醇单丁基醚和三亚丙基二醇单甲基醚。
在另一个非常优选的实施方案中,基于有机溶剂的加有颜料的喷墨油墨具有由一种或多种聚亚烷基二醇衍生物以及聚亚烷基二醇二烷基醚的混合物组成的液相。
基于有机溶剂的加有颜料的喷墨油墨可包括少量选自以下的有机溶剂:醇、酮、酯、醚、二醇和聚二醇及其衍生物、内酯、含氮溶剂例如酰胺。
适合的亚烷基二醇单烷基醚的实例包括亚乙基二醇单甲基醚、亚乙基二醇单乙基醚、亚乙基二醇单丙基醚、亚乙基二醇单丁基醚、亚乙基二醇单己基醚、亚乙基二醇单2-乙基-己基醚、亚乙基二醇单苯基醚、亚丙基二醇单甲基醚、亚丙基二醇单乙基醚、亚丙基二醇单正丙基醚、亚丙基二醇单正丁基醚、亚丙基二醇单异丁基醚、亚丙基二醇单叔丁基醚和亚丙基二醇单苯基醚。
适合的亚烷基二醇二烷基醚的实例包括亚乙基二醇二甲基醚、亚乙基二醇二乙基醚、亚乙基二醇甲基乙基醚、亚乙基二醇二丁基醚、亚丙基二醇二甲基醚、亚丙基二醇二乙基醚和亚丙基二醇二丁基醚。
适合的聚亚烷基二醇单烷基醚的实例包括二亚乙基二醇单甲基醚、二亚乙基二醇单乙基醚、二亚乙基二醇单正丙基醚、二亚乙基二醇单正丁基醚、二亚乙基二醇单己基醚、三亚乙基二醇单甲基醚、三亚乙基单乙基醚、三亚乙基二醇单丁基醚、二亚丙基单甲基醚、二亚丙基二醇单乙基醚、二亚丙基二醇正丙基醚、二亚丙基二醇单正丁基醚、二亚丙基单叔丁基醚、三亚丙基二醇单甲基醚、三亚丙基二醇单乙基醚、三亚丙基二醇单正丙基醚和三亚丙基二醇单正丁基醚。
适合的聚亚烷基二醇二烷基醚的实例包括二亚乙基二醇二甲基醚、三亚乙基二醇二甲基醚、二亚乙基二醇二乙基醚、三亚乙基二醇二乙基醚、二亚乙基二醇甲基乙基醚、三亚乙基二醇甲基乙基醚、二亚丙基二醇二甲基醚、二亚丙基二醇二乙基醚、二亚丙基二醇二正丙基醚(dipropylene di n-propyl ether)、二亚丙基二醇二叔丁基醚(dipropylene dit-butyl ether)、三亚丙基二醇二甲基醚和三亚丙基二醇二乙基醚。
适合的二醇酯的实例包括亚乙基二醇单甲基醚乙酸酯、亚乙基二醇单乙基醚乙酸酯、亚乙基二醇单丙基醚乙酸酯、亚乙基二醇单丁基醚乙酸酯、二亚乙基二醇单乙基醚乙酸酯、二亚乙基二醇单丁基醚乙酸酯、亚丙基二醇单甲基醚乙酸酯、亚丙基二醇单乙基醚乙酸酯、二亚丙基二醇单甲基醚乙酸酯和亚丙基二醇单甲基醚丙酸酯。
适合的市售二醇醚溶剂包括得自UNION CARBIDE的CellosolveTM溶剂和CarbitolTM溶剂、得自EASTMAN的EktasolveTM溶剂、得自DOW的DowanolTM溶剂、得自SHELLCHEMICAL的OxitollTM溶剂、DioxitollTM溶剂、ProxitollTM溶剂和DiproxitollTM溶剂、得自LYONDELL的ArcosolvTM溶剂。
内酯为具有由酯键形成的环结构的化合物,且可为γ-内酯(5-元环结构)、δ-内酯(6-元环结构)或ε-内酯(7-元环结构)类型。内酯的适合实例包括γ-丁内酯、γ-戊内酯、γ-己内酯、γ-庚内酯、γ-辛内酯、γ-壬内酯、γ-癸内酯、γ-十一烷酸内酯、δ-戊内酯、δ-己内酯、δ-庚内酯、δ-辛内酯、δ-壬内酯、δ-十二烷酸内酯、δ-十一烷酸内酯和ε-己内酯。
含氮有机溶剂的适合实例包括2-吡咯烷酮、N-甲基吡咯烷酮、N,N-二甲基乙酰胺、N,N-二甲基甲酰胺、乙腈和N-二甲基十二烷酰胺。
聚合物胶乳连结料
所述水性加有颜料的喷墨油墨可包含聚合物胶乳连结料。
聚合物胶乳没有特别限制,只要其在油墨组合物中具有稳定的可分散性。对水不溶性聚合物的主链骨架没有限制。聚合物的实例包括乙烯基聚合物和缩合聚合物(例如环氧树脂、聚酯、聚氨酯、聚酰胺、纤维素、聚醚、聚脲、聚酰亚胺和聚碳酸酯)。在上述物质当中,特别优选乙烯基聚合物,原因是容易控制的合成。
在一个特别优选的实施方案中,聚合物胶乳为聚氨酯胶乳,更优选为自分散聚氨酯胶乳。在所述一种或多种水性喷墨油墨中的聚合物胶乳连结料优选为基于聚氨酯的胶乳连结料,原因是与热固性树脂相容。
从使用有色颜料时的喷射稳定性和液体稳定性(特别是分散稳定性)的角度来看,在本发明中的聚合物胶乳优选为自分散的聚合物胶乳,更优选为具有羧基的自分散聚合物胶乳。自分散聚合物胶乳是指水不可溶的聚合物的胶乳,其不含游离的乳化剂且能够由于该聚合物自身所具有的官能团(特别是酸性基团或其盐)甚至在不存在其他表面活性剂的情况下在水性介质中进入分散状态。
在制备自分散聚合物胶乳中,优选所用单体选自不饱和羧酸单体、不饱和磺酸单体和不饱和磷酸单体。
不饱和羧酸单体的具体实例包括丙烯酸、甲基丙烯酸、巴豆酸、衣康酸、马来酸、富马酸、柠康酸和2-甲基丙烯酰基氧基甲基琥珀酸。不饱和磺酸单体的具体实例包括苯乙烯磺酸、2-丙烯酰氨基-2-甲基丙烷磺酸、(甲基)丙烯酸3-磺基丙基酯和衣康酸双(3-磺基丙基酯)。不饱和磷酸单体的具体实例包括乙烯基磷酸、磷酸乙烯基酯、磷酸双(甲基丙烯酰氧基乙酯)、磷酸二苯基酯2-丙烯酰氧基乙基酯、磷酸二苯基酯2-甲基丙烯酰氧基乙基酯和磷酸二丁基酯2-丙烯酰氧基乙基酯。
胶乳连结料聚合物颗粒优选具有30℃或更高的玻璃化转变温度(Tg)。
聚合物胶乳的最小成膜温度(MFT)优选为-25至150℃,更优选为35-130℃。
杀生物剂
用于水性喷墨油墨的合适杀生物剂包括脱水乙酸钠、2-苯氧基乙醇、苯甲酸钠、吡啶硫酮钠-1-氧化物(sodium pyridinethion-1-oxide)、对羟基苯甲酸乙酯和1,2-苯并异噻唑啉-3-酮及其盐。
优选的杀生物剂为自ARCH UK BIOCIDES得到的ProxelTM GXL和ProxelTM Ultra 5及自COGNIS得到的BronidoxTM。
杀生物剂的加入量优选为0.001-3.0重量%,更优选为0.01-1.0重量%,各自基于加有颜料的喷墨油墨的总重量计算。
表面活性剂
所述一种或多种加有颜料的喷墨油墨可含有至少一种表面活性剂。所述一种或多种表面活性剂可为阴离子型、阳离子型、非离子型或两性离子型,且基于喷墨油墨的总重量计算,优选加入总量小于5%重量,并且特别地基于喷墨油墨的总重量计算,总量小于2重量%。
所述一种或多种加有颜料的喷墨油墨优选具有在25℃下18.0-45.0mN/m的表面张力,更优选在25℃下21.0-39.0mN/m的表面张力。
用于所述加有颜料的喷墨油墨的适合的表面活性剂包括脂肪酸盐、高级醇的酯盐、烷基苯磺酸盐、磺基丁二酸酯盐和高级醇的磷酸酯盐(例如,十二烷基苯磺酸钠和二辛基磺基丁二酸钠)、高级醇的环氧乙烷加合物、烷基酚的环氧乙烷加合物、多元醇脂肪酸酯的环氧乙烷加合物、乙炔二醇及其环氧乙烷加合物(例如,聚氧乙烯壬基苯基醚和得自AIRPRODUCTS & CHEMICALS INC.的SURFYNOLTM 104、104H、440、465和TG)。
优选的表面活性剂选自含氟表面活性剂(例如,氟代烃)和/或聚硅氧烷表面活性剂。
聚硅氧烷表面活性剂优选为硅氧烷类,并且可为烷氧基化、聚酯改性、聚醚改性、聚醚改性羟基官能、胺改性、环氧改性和其他改性或其组合。优选的硅氧烷为聚合的,例如聚二甲基硅氧烷。优选的市售聚硅氧烷表面活性剂包括购自BYK Chemie的BYKTM 333和BYKTM UV3510。
一种特别优选的市售含氟表面化学剂为得自DU PONT的CapstoneTM FS3100。
润湿剂
合适的润湿剂包括三醋酸甘油酯、N-甲基-2-吡咯烷酮、2-吡咯烷酮、甘油、脲、硫脲、亚乙基脲、烷基脲、烷基硫脲、二烷基脲和二烷基硫脲;二元醇类,包括乙二醇、丙二醇、丙三醇、丁二醇、戊二醇和己二醇;二醇类,包括丙二醇、聚丙二醇、乙二醇、聚乙二醇、二乙二醇、四乙二醇及其混合物和衍生物。优选的润湿剂为2-吡咯烷酮、甘油和1,2-己二醇,因为发现后者对于改进在工业环境中的喷墨印刷可靠性最有效。
润湿剂优选以制剂的0.1-35重量%、更优选占制剂的1-30重量%且最优选占制剂的3-25重量%的量加到喷墨油墨制剂中。
pH调节剂
所述水性喷墨油墨可含有至少一种pH调节剂。合适的pH调节剂包括NaOH、KOH、NEt3、NH3、HCl、HNO3、H2SO4和(聚)烷醇胺,例如三乙醇胺和2-氨基-2-甲基-1-丙醇。优选的pH调节剂为三乙醇胺、NaOH和H2SO4。
喷墨油墨的制备
所述一种或多种加有颜料的喷墨油墨可通过在聚合物分散剂存在下在分散介质中沉淀或研磨有色颜料或简单地通过在油墨中混合可自分散的有色颜料来制备。
混合设备可包括加压捏合机、敞开式捏合机、行星式混合机、溶解器和道尔顿通用混合机(Dalton Universal Mixer)。合适的研磨和分散设备有球磨机、珠磨机(pearlmill)、胶体磨、高速分散器、双辊机、珠粒研磨机(bead mill)、调漆器和三辊机。分散体还可使用超声波能量制备。
如果喷墨油墨含有多于一种颜料,则所述有色油墨可使用各颜料的单独分散体来制备,或者在制备分散体的过程中可将多种颜料混合且共研磨。
分散过程可以连续、间歇或半间歇模式进行。
研磨物(mill grind)的各成分的优选量和比率将根据具体材料和预期应用而广泛变化。研磨混合物的内含物包括研磨物和研磨介质。研磨物包括颜料、分散剂和例如水的液体载体。颜料在研磨物(除了研磨介质之外)中的量通常为1-50重量%。颜料与分散剂的重量比为20:1至1:2。
研磨时间可广泛变化且取决于所选择的颜料、机械工具和驻留条件、初始粒度和所需最终粒度等。在本发明中,可制备具有小于100nm的平均粒度的颜料分散体。
在研磨完成之后,使用常规分离技术(例如,通过过滤、经筛网筛分等)将研磨介质从已研磨的微粒产物(呈干燥形式或液体分散体形式)中分离。常将筛网构造在研磨机中,例如珠粒研磨机。研磨的颜料浓缩物优选通过过滤从研磨介质中分离。
一般而言,期望制造呈浓缩研磨物形式的有色油墨,随后将其稀释到适当浓度以供喷墨印刷系统使用。这种技术允许由所述设备制备更大量的加有颜料的油墨。如果研磨物在溶剂中制造,则将其用水和任选的其他溶剂稀释到适当浓度。如果研磨物在水中制造,则用额外的水或水混溶性溶剂将其稀释以制造期望浓度的研磨物。通过稀释,将油墨调节到对于特定应用所期望的粘度、颜色、色调、饱和密度和印刷区域覆盖度。
实施例
原料
除非另外说明,否则用于以下实施例的所有原料均容易地得自标准来源,例如AldrichChemical Co.(Belgium)和Acros(Belgium)。
PR254为C. I. 颜料红254的缩写,对此使用IrgazinTM DPP Red BTR,购自CibaSpecialty Chemicals。
Edaplan为EdaplanTM 482的缩写,得自MUNZING的聚合物分散剂。
Proxel为杀生物剂ProxelTM Ultra 5的缩写,得自AVECIA。
PEG 200为平均分子量为200的聚乙二醇,得自CLARIANT。
TEA为三乙醇胺。
SyloidTM 72为合成的无定形二氧化硅,表现为白色自由流动的粉末,得自GRACE。
PVA-sol为7.5%重量的聚乙烯醇聚合物ErkolTM W48/20的溶液,得自ERKOL。
测定方法
1. 表面张力
水性喷墨油墨的静态表面张力用购自KRÜSS GmbH, Germany的KRÜS张力计K9在25℃在60秒后测定。
2. 粘度
喷墨油墨的粘度用Brookfield DV-II+粘度计在32℃以1000s-1剪切速率测定。
3. 平均粒径
油墨样品用乙酸乙酯稀释至0.002%重量颜料浓度。颜料颗粒的平均粒径基于动态光散射原理用NicompTM 30 Submicron Particle Analyzer亚微米颗粒分析仪测定。
为了得到良好的喷墨特性(喷墨和印刷品质),优选分散颗粒的平均粒径小于250nm。
4. 清晰度(Sharpness,S)
在DPL工艺后印刷图像的清晰度根据在表1中所描述的0-6的评级标准进行评估。
表1
5. 渗色(Ink Bleeding,IB)
由于在DPL过程期间产生的水蒸气使有色颜料移位(deplace),发生油墨渗色。根据表2中所述的0-6的评级标准进行评价。
表2
6. 均匀性(Homogeneity,H)
均匀性使用二进制标度(好/不好)在存在于技术性有色图案中的9 cm x 2.5 cm的长方形中评估。
7. 粘着(Adhesion,A)
根据ISO2409:1992(E). Paints. International standard(油漆 国际标准)1992-08-15,使用购自BRAIVE INSTRUMENTS的Braive No.1536十字切割试验仪,以1mm切口间距并用600g重量与TesatapeTM 4104 PVC带组合评价来评价粘着。根据表3中所述标准进行评价。
表3
实施例1
制备水性加有颜料的喷墨油墨
制备浓缩的水性颜料分散体,做法是使用DisperluxTM Yellow混合器混合根据表4的组合物30分钟。
表4
随后使用DynomillTM KDL用0.04 mm钇稳定的锆珠粒YTZTM研磨介质(得自TOSOHCorp.)研磨浓缩的水性颜料分散体。用研磨珠粒填充磨机至其一半体积且分散体在200mL/min的流速和15 m/s的旋转速率下研磨3小时。在研磨后,将分散体与珠粒分开。浓缩的水性颜料分散体用作制备喷墨油墨的基础物质。
制备红色加有颜料的喷墨油墨“油墨R”,做法是根据表7用另外的油墨组分稀释浓缩的颜料分散体,其中%重量基于油墨的总重量计算。组分TEA用于将pH设定为8.2。加入水以使油墨完成所需的颜料浓度。
表5
制备用于油墨接受层的涂料溶液
涂料溶液DIS-1至DIS-4都以相同的方式使用在表6中所列出的量来制备。使用DisperluxTM混合器将无机颜料SyloidTM 72在PVA-sol中分散30分钟。往分散体中加入氨以将pH提高到高于8.0。各涂料溶液的pH在25℃下测定。
表6
涂料溶液DIS-5通过用968g水稀释83 g PVA-sol来制备。DIS-5中不包含无机颜料。
油墨接受层的制备
用于装饰印刷的80 g/m2的多孔纸用含有60%重量的基于三聚氰胺-甲醛的树脂的水溶液浸渍,甲醛与三聚氰胺的比率为1.7,然后干燥至残留湿度为约8 g/m2。
根据表7通过棒式涂布器将油墨接受层涂布在浸渍的纸上,提供厚度为20 µm或40µm的湿层。涂布样品在125℃的烘箱中干燥1分钟。
表7
结果和评价
根据表8通过使用表5的油墨R和KJ4B Kyocera印刷头(以32℃的印刷头温度和600dpi)在基于三聚氰胺-甲醛的树脂浸渍的纸上印刷技术性有色图案(参见图5和图6)获得装饰性层。将印刷样品在50℃下干燥30分钟。喷射的有色颜料C (=PR254)的量列于表8,以gC/m2表示。P/B比为无机颜料P(=SyloidTM 72)与聚合物连结料的重量比。P/C为无机颜料P(=SyloidTM 72)与喷射的有色颜料C(=PR254)的重量比。
如图3所述制备组件,其中将制好的装饰性层夹在HDF芯层与为了耐久包含氧化铝的未印刷的三聚氰胺-甲醛树脂浸渍的纸的保护性层之间。随后通过DPL工艺将该组件在195℃下热压20秒,使用138巴和50 kg/cm2作为设定值。
检查所得到的地板层压材料的清晰度(S)、油墨渗出(IB)、均匀性(H)和粘着(A)。结果示于表8中。
表8
从表8应当清楚看出,如果P/B比率大于1.5且P/C比率大于4.0,则清晰度、油墨渗色、均匀性和粘着有良好的结果。
参考标记列表
表9
Claims (15)
1.一种用于制造装饰性层压材料的方法,其包括以下步骤:
a) 通过将纸基材浸没在热固性树脂浴中用热固性树脂浸渍纸基材;
b) 在热固性树脂浸渍的纸基材上施用油墨接受层,所述油墨接受层包含无机颜料P和聚合物连结料B,无机颜料与聚合物连结料的重量比P/B大于1.5;
c) 用一种或多种含有有色颜料C的水性加有颜料的喷墨油墨和/或基于有机溶剂的加有颜料的喷墨油墨在所述油墨接受层上喷射有色图案;和
d) 将热固性纸热压成装饰性层压材料,
其中油墨接受层的无机颜料与有色图案中的喷射有色颜料的重量比P/C大于4.0。
2.根据权利要求1的方法,其中步骤d)包括将凸纹压印在装饰性层压材料中。
3. 根据权利要求1或2的方法,其中由所述一种或多种水性加有颜料的喷墨油墨和/或基于有机溶剂的加有颜料的喷墨油墨喷射的有色颜料的干重为至少0.30 g/m2。
4. 根据权利要求1-3中任一项的方法,其中所述油墨接受层具有不超过10 g/m2的总干重。
5.根据权利要求1-4中任一项的方法,其中所述热固性树脂选自基于三聚氰胺-甲醛的树脂、基于脲-甲醛的树脂和基于苯酚-甲醛的树脂。
6.根据权利要求1-5中任一项的方法,其中所述无机颜料选自氧化铝水合物、铝氧化物、铝氢氧化物、硅酸铝和二氧化硅。
7. 根据权利要求1-6中任一项的方法,其中所述聚合物连结料为包含羟基作为亲水结构单元且具有大于1 g/L水的水溶性的水溶性聚合物连结料。
8.根据权利要求1-7中任一项的方法,其中所述油墨的喷射以单程喷墨印刷模式进行。
9.根据权利要求1-8中任一项的方法,其中一种或多种基于有机溶剂的加有颜料的喷墨油墨包括具有至少250的分子量的至少一种聚亚烷基二醇二烷基醚。
10.根据权利要求1-9中任一项的方法,其中所述纸基材为形成一定厚度的有色纸。
11.根据权利要求1-10中任一项的方法,其中所述水性加有颜料的喷墨油墨包括至少一种聚合物胶乳。
12. 根据权利要求1-11中任一项的方法,其中至少三种水性加有颜料的喷墨油墨和/或基于有机溶剂的加有颜料的喷墨油墨包括选自以下的颜料:碳黑、C. I. 颜料蓝15:3、C.I. 颜料蓝15:4、C. I颜料黄151、C. I. 颜料黄180、C. I. 颜料黄74、C. I颜料红254、C.I. 颜料红176、C. I. 颜料红122及其混晶。
13.一种喷墨印刷的热固性树脂浸渍的纸,其包括:在油墨接受层中的有色图案,所述油墨接受层包含无机颜料和聚合物连结料,无机颜料P与聚合物连结料B的重量比P/B大于1.5,其中油墨接受层的无机颜料P与有色图案中的喷射有色颜料C的重量比P/C大于4.0;且其中所述油墨接受层基本不含热固性树脂。
14.一种包含热压有芯层和保护性层的根据权利要求13的喷墨印刷的热固性树脂浸渍的纸的装饰性层压材料,其中所述装饰性层压材料选自地板、厨房板、家具板和墙板。
15.根据权利要求14的装饰性层压材料,其中所述装饰性层压材料包括能够实现少胶水机械连接的榫和槽。
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CN111674173A (zh) * | 2020-06-12 | 2020-09-18 | 贾松 | 一种应用于木门面板的拼色打印方法 |
CN111699093A (zh) * | 2018-01-31 | 2020-09-22 | 爱克发有限公司 | 用于装饰层合镶板的喷墨印刷方法 |
CN115443359A (zh) * | 2020-04-20 | 2022-12-06 | 地板工业有限公司 | 用于制造层压板的装饰纸层和方法 |
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Cited By (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN110234809A (zh) * | 2017-02-03 | 2019-09-13 | 奥斯龙-明士克公司 | 用于层压材料的装饰纸 |
CN110234809B (zh) * | 2017-02-03 | 2021-12-03 | 奥斯龙-明士克公司 | 用于层压材料的装饰纸 |
CN110997342A (zh) * | 2017-06-14 | 2020-04-10 | 尤尼林有限公司 | 制造用作装饰纸或箔的可喷墨打印的纸或箔的方法 |
CN111032798A (zh) * | 2017-08-22 | 2020-04-17 | 爱克发有限公司 | 水性喷墨油墨组和喷墨印刷方法 |
CN111433024A (zh) * | 2017-11-15 | 2020-07-17 | 株式会社理光 | 叠层体,制造叠层体的方法,以及制造叠层体的装置 |
CN111699093A (zh) * | 2018-01-31 | 2020-09-22 | 爱克发有限公司 | 用于装饰层合镶板的喷墨印刷方法 |
CN111699093B (zh) * | 2018-01-31 | 2022-05-03 | 爱克发有限公司 | 用于装饰层合镶板的喷墨印刷方法、制造装饰层合镶板的方法、装饰层合镶板组 |
CN115443359A (zh) * | 2020-04-20 | 2022-12-06 | 地板工业有限公司 | 用于制造层压板的装饰纸层和方法 |
CN115443359B (zh) * | 2020-04-20 | 2023-11-10 | 地板工业有限公司 | 用于制造层压板的装饰纸层和方法 |
CN111674173A (zh) * | 2020-06-12 | 2020-09-18 | 贾松 | 一种应用于木门面板的拼色打印方法 |
Also Published As
Publication number | Publication date |
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RU2016135785A3 (zh) | 2018-07-24 |
EP2905376B1 (en) | 2018-09-19 |
EP2905376A1 (en) | 2015-08-12 |
CA2935663C (en) | 2022-05-03 |
BR112016017950B1 (pt) | 2022-02-01 |
CA2935663A1 (en) | 2015-08-13 |
US20170058456A1 (en) | 2017-03-02 |
AU2015215145B2 (en) | 2018-07-05 |
RU2675142C2 (ru) | 2018-12-17 |
BR112016017950A2 (zh) | 2017-08-08 |
WO2015117910A1 (en) | 2015-08-13 |
PL2905376T3 (pl) | 2019-02-28 |
ES2701499T3 (es) | 2019-02-22 |
CN106068349B (zh) | 2018-10-19 |
AU2015215145A1 (en) | 2016-07-07 |
RU2016135785A (ru) | 2018-03-15 |
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