CN101432123A - 在固体表面材料的表面中形成装饰图案的方法 - Google Patents
在固体表面材料的表面中形成装饰图案的方法 Download PDFInfo
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- CN101432123A CN101432123A CNA2007800147593A CN200780014759A CN101432123A CN 101432123 A CN101432123 A CN 101432123A CN A2007800147593 A CNA2007800147593 A CN A2007800147593A CN 200780014759 A CN200780014759 A CN 200780014759A CN 101432123 A CN101432123 A CN 101432123A
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Abstract
使带有取向装饰性各向异性颗粒的聚合或可聚合材料经受使装饰性颗粒再取向的形变。结果产生美观的图案化外观。
Description
发明背景
发明领域
本发明涉及通过装饰性填料的选择性取向(selective orientation)制造装饰性饰面材料的方法。
相关技术描述
本发明方法的优选用途是制造装饰性固体表面材料。本文所用的固体表面材料以其普通含义理解并代表含有聚合物树脂和粒状填料的均匀的、非凝胶涂布的、非多孔的、三维固体材料，这类材料特别可在建筑业中用于厨房工作台面、水槽、墙面覆盖物和家具表面，其中功能性和有吸引力的外观都是必需的。固体表面材料的公知实例是E.I.DuPont de Nemours and Company生产的
。许多设计美学效果此前是固体表面材料，例如花岗岩和大理石中已知的，但它们具有主要二维的外观。
多数固体表面材料通过热固法制造，例如片材浇铸、模具浇铸(cell casting)、注射成型或本体模制(bulk molding)。为使复合材料类似天然石材而掺入颜料和有色颗粒极大影响这类产品的装饰品质。这些材料的制造中目前所用的中间体和方法限制了市售图案的范围。
固体表面材料在其各种应用中发挥功能性和装饰性用途。在固体表面材料中并入各种有吸引力的和/或独特的装饰图案提高了其效用。这类图案构成使产品彼此区别的本质上有用的性质。相同原理适用于天然形成的材料，例如木材、大理石和花岗岩，某些天然形成的图案，例如颗粒感、颜色变化、纹理、分层、夹杂物等会增强它们例如在家具构造中的效用。商业上制成的固体表面材料通常包含意在模仿或仿制花岗岩或大理石中天然形成的图案的装饰图案。但是，由于可行性和/或实用性的限制，某些装饰图案和/或装饰图案类型在之前尚未加入固体表面材料中。
之前在传统固体表面制造中已经实现的装饰图案通常使用三种方法之一：
(i)将现成固体表面产品的单色或多色碎块机械研磨以产生不规则形状的宏观颗粒，它们随后与未固化的固体表面浇铸组合物中的其它成分合并。工业中称作“crunchies”的常用宏观装饰性颗粒是各种填充和未填充的、颜料着色或染色的、不可溶或交联的聚合物碎料。在浇铸或模塑过程中使浇铸组合物固化产生固体表面材料，其中具有不规则形状和尺寸的有色夹杂物被不同颜色的连续基质包围并嵌在其中。
(ii)浇铸第一和第二可固化组合物，其中第二组合物与第一组合物的颜色不同，并以两者仅互混至有限程度的方式添加。在所得固体表面材料中，不同颜色的区域具有平整形状，并被具有连续颜色变化的区域隔开。
(iii)通过切割或机械加工成各种形状来制造不同颜色的固体表面产品，然后用粘合剂将它们接合产生多色镶嵌图案或设计。
使用这些传统方法，要求混合不同颜色或外观的材料以形成装饰图案。它们不能制造不依赖于不同颜色的组合的某些类型的装饰图案。
在授予Overholt等人的美国专利6,702,967中公开了固体表面材料的一种新型美学效果，该专利公开了通过制备含可取向的各向异性颗粒的可固化组合物、形成该组合物的许多片段、并将这些片段重组成粘结体(cohesive mass)(其中至少一些片段具有以不同方向取向的颗粒)来制造具有图案的装饰性饰面材料的方法。
发明概述
本发明是在含有各向异性颗粒的固体表面材料的表面中形成装饰图案的方法，包括下列步骤，使可流动固体表面材料中的至少大部分各向异性颗粒取向，压印(indenting)可流动固体表面材料中的多个表面区域以破坏已压印表面区域中各向异性颗粒的取向，使具有已压印表面区域的可流动固体表面材料的表面平整化，并使可流动固体表面材料固化。
附图
参照下列描述、所附权利要求和附图，更好地理解本发明的这些和其它特征、方面和优点。
图1是带有取向的各向异性粒状填料的材料片的横截面。
图2是具有再取向的各向异性粒状填料区域的材料片的横截面。
图3是具有含表面压痕的再取向的各向异性粒状填料区域的材料片的横截面。
图4是平整化的表面压痕的任选实施方案的示意图。
优选实施方案详述
本发明是通过使各向异性的粒状填料取向来在带有各向异性颗粒的固体表面材料中形成装饰图案的方法。未固化的固体表面组合物中的各向异性粒状填料可以通过各种方式取向，其中至少一些可取向颗粒处于共同取向，并随后通过各种方式使特定区域中的至少一些取向的各向异性颗粒(即薄片)再取向以在固体表面材料中形成装饰图案。本发明的另一实施方案在未固化固体表面组合物中包含大致未取向的填料并随后通过各种方式使特定区域中的至少一些取向的各向异性颗粒(即薄片)取向形成装饰图案。通过固体表面材料内相邻区域之间的各向异性颗粒取向的差异来产生图案。由于颗粒取向，环境光与相邻区域不同地相互作用，由此该方法在固体表面材料中产生美观的三维外观。
本发明中可用的固体表面组合物不受具体限制，只要它们在工艺条件下可流动，并可以形成固体表面材料。可聚合组合物可以是如Bosworth的美国专利3,474,081中所公开的浇铸浆料(sirup)，并如Duggins的美国专利3,528,131中所公开在传送带上浇铸。在本发明的另一实施方案中，可以通过下述方法制造可聚合组合物，其中如Weberg等人在美国专利6,203,911中所述制造和加工模制的可热固化制剂并使该模制化合物经过挤出工艺步骤。固体表面制剂也可以包括能压模的各种热塑性树脂。在本发明的另一实施方案中，可以根据Beauchemin等人在美国专利6,476,111中的公开制造和挤出可聚合组合物。在所有实施方案中，如下所述在可聚合组合物中包含可取向的各向异性的增强美观的颗粒。可以使用各向异性颜料、反射性颗粒、纤维、薄膜和细碎固体(或染料)作为增强美观的颗粒以突出取向效果。通过控制增强颗粒的量和再取向区域的形状和尺寸，可以控制所得固体表面材料的半透明性以产生所需美学效果。可以通过合并不同量的增强颗粒、填料和着色剂并通过各向异性填料颗粒的再取向程度来实现不同的颜色、反射性和半透明性。
本发明中可用的各向异性粒状填料不受具体限制，只要它们的纵横比高到足以促进材料加工过程中的颗粒取向并具有随着与材料和观察者的取向改变的外观。优选的各向异性粒状填料包括纵横比高到足以促进材料加工过程中的颗粒取向且外观随着与材料和观察者的取向改变的材料。合适的增强颗粒的纵横比覆盖宽的范围，例如金属薄片(20-100)、云母(10-70)、磨碎的玻璃纤维(3-25)、芳族聚酰胺纤维(100-500)、切碎的碳纤维(800)、切碎的玻璃纤维(250-800)和磨碎的涂布碳纤维(200-1600)。这些视觉效果可以归因于角依赖性反射率、角依赖性色吸收/反射或可见形状。这些颗粒可以是片状、纤维、或条带。纵横比是颗粒的最大长度与其厚度的比率。通常，纵横比为至少3，更通常至少20。片状材料的两个维度明显大于第三个维度。片状材料的实例包括但不限于：云母、合成云母、玻璃薄片、金属薄片、氧化铝和二氧化硅基底、聚合物薄膜片以及合成材料，如超薄多层干涉薄片(例如来自Flex Products的
)和螺旋状超结构、雪茄形液晶分子(例如来自Wacker的
HC)。在许多情况下，片状基底的表面被各种金属氧化物或颜料涂布以控制颜色和光干涉效应。一些材料在不同角度下呈现不同颜色。
纤维的一个维度明显大于另两个维度。纤维的实例包括金属、聚合物、碳、玻璃、陶瓷和各种天然纤维。条带的一个维度明显大于另两个维度，但第二维度明显大于第三维度。条带的实例包括金属和聚合物薄膜。
任选地，聚合组合物可以包括非各向同性或不美观的粒状或纤维填料。一般而言，与纯聚合物或纯聚合物的组合相比，填料提高最终制品的硬度、劲度或强度。要理解的是，此外，填料可以为最终制品提供其它属性。例如其可以提供其它功能性质，例如阻燃性，或其可以发挥装饰性用途和改变美学效果。一些代表性填料包括氧化铝、三水合氧化铝(ATH)、一水合氧化铝、氢氧化铝、氧化铝、硫酸铝、磷酸铝、硅酸铝、Bayer水合物、硼硅酸盐、硫酸钙、硅酸钙、磷酸钙、碳酸钙、氢氧化钙、氧化钙、磷灰石、玻璃泡、玻璃微球、玻璃纤维、玻璃珠、玻璃薄片、玻璃粉、玻璃球、碳酸钡、氢氧化钡、氧化钡、硫酸钡、磷酸钡、硅酸钡、硫酸镁、硅酸镁、磷酸镁、氢氧化镁、氧化镁、高岭土、蒙脱土、膨润土、叶蜡石、云母、石膏、二氧化硅(包括砂石)、陶瓷微球、陶瓷颗粒、陶瓷晶须、粉末滑石、二氧化钛、硅藻土、木粉、硼砂或其组合。
此外，填料可以任选用施胶剂，例如可作为Silane 8 MethacrylateA-174购自OSI Specialties(Friendly，WV)的硅烷(甲基)丙烯酸酯涂布。填料以平均粒度为大约5-500微米的小颗粒形式存在，并且可以以可聚合组合物的最多65重量％的量存在。
填料颗粒的性质，特别是折光指数，对最终制品的美观性具有显著影响。当填料的折光指数与可聚合组分的折光指数密切匹配时，所得最终制品具有半透明外观。随着该折光指数偏离可聚合组分的折光指数，所得外观更不透明。ATH通常是用于聚(甲基丙烯酸甲酯)(PMMA)体系的优选填料，因为ATH的折光指数接近PMMA。特别有用的是粒度为10微米至100微米的填料。氧化铝(Al2O3)改进了抗污损性(resistance to marring)。纤维(例如玻璃、尼龙、芳族聚酰胺和碳纤维)改进了机械性质。一些功能填料的实例是抗氧化剂(如叔胺或芳胺、由Ciba Specialty Chemicals Corp.供应的
(3，5-二-(叔)丁基-4-羟基氢化肉桂酸十八烷基酯)、和次磷酸钠、阻燃剂(例如卤化烃、矿物碳酸盐、水合矿物和氧化锑)、UV稳定剂(例如Ciba Geigy供应的)、防污剂(例如硬脂酸和硬脂酸锌)，或其组合。
在进行本发明的方法时，可以如图1中示意性所示利用在可聚合基质的层流过程中颗粒自排列(align themselves)的趋势，实现各向异性粒状填料的取向，其中取向的各向异性颗粒(200)被显示为大致平行于片材(100)表面。可以根据可聚合组合物的流变性质通过许多方法产生层流。可流动的组合物可以具有通过在传送带上浇铸而取向的各向异性粒状填料，任选使用刮刀。可挤出的未固化固体表面模塑组合物可以通过模板挤出，对模头几何形状没有限制。可以使用压延辊作为各向异性粒状填料取向的主要工具，或作为附加手段。附加的压延步骤可用于使各向异性粒状填料取向或可用于任何其它用途，例如测量该材料的厚度或在表面上添加纹理。一般而言，至少70％的各向异性颗粒，更通常至少90％具有相同取向。
通过各向异性颗粒的选择性再取向，在未固化的固体表面组合物中产生美学效果。在选择性再取向后，再取向颗粒与材料主体具有不同取向，这如图2中所示产生视觉上不同的再取向区域(400)。所选再取向的实际方法可以随未固化的固体表面组合物的性质和所需美学效果而变。在本发明的一个实施方案中，通过材料的物理形变引起再取向。使材料形变以使颗粒再取向的方法包括用实体物，如螺丝刀、贝壳、刀、辊、硬币等手工压印。自动化加工法可以包括图案化辊、压机等。根据要形变的材料的性质，形变方法不一定是实体物，也可以使用空气或流体射流。在低粘体系中，可以使用更稠密的流体来创造图案。随着更稠密的流体在基质中下沉，材料流动使各向异性装饰性粒状填料再取向，从而产生所需美学效果。
如图3中所示，使各向异性颗粒再取向的一些实施方案会在可聚合组合物的表面中形成压痕(300)。这些压痕在一些美学设计中可能有用，但一般而言，据发现，平坦表面是优选的。这可以通过在可聚合组合物固化成片材后将材料去除(即，打磨)至最深压痕以下的水平面(400)来实现。在固化前在不去除材料的情况下弄平片材的任选加工步骤是合意的。这通常导致一部分再取向区域在主体组合物的方向上再取向，但它们往往不会完全恢复至其原始取向。在低粘体系中，该材料可以通过重力引发的材料流动自匀平。在更高粘度体系中，平整化的一个优选实施方案显示在图4中，其中使用压延辊(500)将该表面压平。压延辊可任选用于在表面上形成纹理。
在任何表面平整化或纹理化后，使未固化的组合物固化。在各向异性颗粒再取向后的可聚合组合物的固化取决于使用哪种聚合物体系而进行。通过热固过程，如片材浇铸、模具浇铸(cell casting)、注射成型或本体模制(bulk molding)制成的多数固体表面材料使用在热活化时会产生自由基的固化剂，其随后引发所需聚合反应。在此可以使用化学活化的热引发或纯温度驱动的热引发来固化丙烯酸系可聚合部分。这两种固化体系都是本领域中公知的。本发明的热塑性实施方案，例如挤出的热塑性塑料的固化通过使该组合物冷却至玻璃化转变温度以下来实现。
包括下列实施例作为本发明的实施方案的代表。除非另行指明，百分比按重量计，且温度按℃计。
实施例
实施例1
称重下列成分：
1120克三水合氧化铝(ATH)
401克 Latex K120ND聚(甲基丙烯酸甲酯/丙烯酸乙酯)聚合物颗粒硬化剂(来自Rohm & Haas)
6克硬脂酸锌
40克
500金云母(Bronze Mica)
361克甲基丙烯酸甲酯(MMA)
57.8克二甲基丙烯酸乙二醇酯(EGDMA)
6.92克
575(叔戊基过氧基-2-乙基己酸酯)热引发剂(来自Atofina)
1.13克
67，2，2＇-偶氮双(甲基丁腈)热引发剂(来自Du Pont)
1.68克
MO偶联剂(来自DuPont)
4克颜料分散体
液体预混物
通过在小容器中合并MMA、EGDMA和
MO并用叶片将它们混合2分钟以将它们均匀混合，制备液体预混物。然后加入
575和 67并混合10分钟以充分混合和确保
67完全溶解。
干掺合
然后通过在配有高粘度混合叶片的双行星式混合机中干掺合ATH、
和硬脂酸锌来制备固体混合物。将这些成分掺合5分钟，此后向混合的固体中加入40克
500金云母。
混合
将4克红氧化铁颜料分散体添加到双行星式混合机(DPM)的成分中。然后将来自液体预混物的液体添加到混合物中并掺合6分钟，超出成分聚结成粘结制剂的点。然后从混合物中取出粘结体并密封在对MMA不可透的容器中，并使其静置最少1小时以使MMA额外吸附到
胶乳颗粒中。
使颗粒取向和再取向
将静置后的混合物添加到挤出机中。将模塑化合物通过压片模头挤出，使云母颗粒以大致相同的方向取向。在离开模头后立即通过各种方法，包括切割、压印、图案化模具或辊来使材料形变，从而实现各向异性颗粒的选择性重排。通过用一种或多种不同物体，包括刀、螺丝刀、锤子、棍棒、贝壳和辊冲击该表面来实现形变，从而进行压印。具有再取向的各向异性颗粒的形变片材可以随后穿过压延辊以压平片材。最终步骤是将模塑化合物固化。
实施例2
称重下列成分：
2.331千克 尼龙
4.604千克 聚(甲基丙烯酸甲酯)
0.163千克 乙烯正丁基丙烯酸酯缩水甘油基甲基丙烯酸酯(EBAGMA)
1.040千克 环氧树脂
0.074千克 尼龙稳定剂
0.490千克 聚(四氟乙烯)(PTFE)
3.638千克 玻璃纤维
2.510千克 BaSO4
0.150千克 金色云母
将这些成分在挤出机中配混并通过狭缝模头。用各种物体，包括螺丝刀、贝壳等使挤出的条带形变。然后使条带通过压延辊，这使条带恢复成平片。
在压痕点可以看见美观图案。在与该片材垂直观看时，之前压印的区域较暗，但在其它角度下反射光，表明云母与未受干扰的区域相比不再在片材平面上取向。
Claims (4)
1.在含有各向异性颗粒的固体表面材料的表面中形成装饰图案的方法，包括下列步骤：
(a)使可流动固体表面材料中的至少大部分各向异性颗粒取向，
(b)压印可流动固体表面材料中的多个表面区域以破坏压印表面区域处各向异性颗粒的取向，
(c)使具有压印表面区域的可流动固体表面材料的表面平整化，并
(d)使可流动固体表面材料固化。
2.权利要求1的方法，其中固体表面材料包括丙烯酸系树脂。
3.权利要求1的方法，其中固体表面材料包括聚酯树脂。
4.权利要求1的方法，其中各向异性颗粒的纵横比具有至少3的纵横比。
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| US11/412,021 | 2006-04-26 | ||
| US11/412,021 US20070252300A1 (en) | 2006-04-26 | 2006-04-26 | Novel aesthetics in surfaces |
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| EP (1) | EP2013000A1 (zh) |
| JP (1) | JP2009535238A (zh) |
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| CN (1) | CN101432123A (zh) |
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| US10157555B2 (en) * | 2016-05-26 | 2018-12-18 | Optic Clear Solutions, Llc | Ruggedized placard |
| CN114206597A (zh) * | 2019-08-05 | 2022-03-18 | 新加坡国立大学 | 图案化的包含各向异性的复合材料的制备 |
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| US3474081A (en) * | 1966-03-14 | 1969-10-21 | Du Pont | Methyl methacrylate polymer and process for making same |
| US3528131A (en) * | 1968-12-19 | 1970-09-15 | Du Pont | Cast simulated marble building product and its manufacture |
| US4089922A (en) * | 1975-02-07 | 1978-05-16 | Yoshino Kogyosho Co., Ltd. | Molded article having stereoscopic decorative pattern and fabrication process therefor |
| JPS57167213A (en) * | 1981-04-09 | 1982-10-15 | Taihei Kagaku Seihin Kk | Plastic card having solid pattern and its manufacture |
| US4756951A (en) * | 1986-06-12 | 1988-07-12 | Mannington Mills Inc. | Decorative surface coverings having platey material |
| JPH0818377B2 (ja) * | 1991-09-13 | 1996-02-28 | 株式会社ホリカワ | 眼鏡フレームの合成樹脂化粧部品、およびその製造方法 |
| US6203911B1 (en) * | 1998-06-17 | 2001-03-20 | E. I. Du Pont De Nemours And Company | Thermoset volatile monomer molding compositions |
| US6702967B2 (en) * | 2001-07-27 | 2004-03-09 | E. I. Du Pont De Nemours And Company | Process for preparing decorative surface materials having a decorative pattern |
| US6476111B1 (en) * | 2001-08-01 | 2002-11-05 | E. I Du Pont De Nemours And Company | Extrudable highly filled thermoplastic sheet composition |
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2006
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| JP2009535238A (ja) | 2009-10-01 |
| CA2646072A1 (en) | 2007-11-08 |
| KR20090018064A (ko) | 2009-02-19 |
| US20070252300A1 (en) | 2007-11-01 |
| AU2007243379A1 (en) | 2007-11-08 |
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