WO2010133075A1 - 易剥离陶瓷贴花及其加工工艺 - Google Patents

易剥离陶瓷贴花及其加工工艺 Download PDF

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Publication number
WO2010133075A1
WO2010133075A1 PCT/CN2009/076134 CN2009076134W WO2010133075A1 WO 2010133075 A1 WO2010133075 A1 WO 2010133075A1 CN 2009076134 W CN2009076134 W CN 2009076134W WO 2010133075 A1 WO2010133075 A1 WO 2010133075A1
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Prior art keywords
coating
ceramic
ink
peelable
applique
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PCT/CN2009/076134
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English (en)
French (fr)
Inventor
刘权辉
西佛林·史蒂芬
刘权耀
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深圳市永丰源实业有限公司
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Publication of WO2010133075A1 publication Critical patent/WO2010133075A1/zh

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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B44DECORATIVE ARTS
    • B44CPRODUCING DECORATIVE EFFECTS; MOSAICS; TARSIA WORK; PAPERHANGING
    • 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

Definitions

  • the invention belongs to the technical field of surface decalization of silicate substrates, in particular to design an easily deductible ceramic decal and a processing technique thereof. Background technique
  • Silicate substrate products such as glass and ceramics can be decorated by appliques.
  • Such decals are typically constructed of a flexible substrate and a transferable thin coating or film layer.
  • the desired graphic decoration is printed on the supporting base paper, and then a cover layer is printed.
  • the decorative pattern will be transferred to the surface of the ceramic or glass product along with the transferable thin coating or film layer. It is then fired to obtain a permanent adherent pattern decorative finish.
  • the process of transferring a flower paper pattern to a glass or ceramic article includes: first peeling the pattern carrier layer (flexible substrate) from the transferable thin coating layer or film layer, and then placing the transferable thin coating layer or film layer In the desired location of glass or ceramic products.
  • a flower paper comprising a carrier paper, a resin printing ink and a binder is disclosed in U.S. Pat. No. 4,177,309.
  • this type of paper has limited wear resistance and a single font color.
  • the present invention adopts the following technical solutions:
  • An easily peelable ceramic applique comprising a peelable support substrate, a decal color layer fixed to the support substrate and separable from the support substrate, and a transfer film layer comprising a transparent gel
  • An organic copolymer binder in the form of an organic solvent system comprising
  • the decal color layer comprises a plurality of color printing ink layers, and the ink layers are copolymer materials.
  • the peelable support substrate comprises a base paper and a coating coated with a silicone, a fluorosilicate, a polyethylene or polypropylene film, a polyester or a mixture thereof;
  • the coating is 0.3-5 g/m 2 .
  • the ink system of the ink layer comprises 20-50% by weight of a binder, 45-65 ⁇ 1% solvent, 0-15 wt% of a plasticizer, 0.1 - 5 ⁇ 1% separating agent (wt is the weight fraction.
  • the binder is a monomeric homopolymer or a mixed copolymer of one or more low polarity resins.
  • the binder is (C3 - C12)-methyl methacrylate, or isooctyl acrylate, or acrylamide copolymer, or styrene-acrylate copolymer, or acrylic acid and Methacryloyl polymer.
  • the binder is 25-35 wt%.
  • the ink system further comprises 0.1 to 5% by weight of an additive, and the additive is one or more of a wetting agent, a dispersing agent, a defoaming aid or a rheological agent.
  • Another object of the present invention is to provide a new process for processing easily peelable ceramic decals, which adopts the following technical solutions:
  • a process for easily peeling ceramic decals comprising the following steps:
  • silicate products such as white porcelain, ceramics and glass is usually decorated by decaling and baking the above-mentioned "ceramic flower paper". After peeling off the picture carrier layer, it is directly attached to the surface of the ceramic body and then fired in the range of 480 to 1250 degrees Celsius. During the firing process, all organic compounds will be completely decomposed, leaving only inorganic pigments, which will aggregate with the body as heat builds up.
  • the ceramic decal paper using the dextrin-coated paper can be transferred to the surface of the ceramic body by a conventional method such as screen printing, and then fired.
  • the peelable paper consists of a base paper having a puree of 60 to 300 g/m 2 and a coating of 0.3 to 5 g/m 2 .
  • the coating material may be silicone, fluorosilicate, polyethylene and polypropylene film or polyester (PET).
  • PET polyester
  • cover oil and printing varnish systems for glass, porcelain and ceramic surface decorative decals including binders in the range of 20%-50% by weight, dissolved in a weight fraction of 45-65 wt % solvent system, aromatic hydrocarbons ranging from 100 degrees Celsius to 200 degrees Celsius, 0-15 wt% plasticizer, 0.1-5 wt% special reagents for separation (usually 0.1% by weight) Between 1%, the following will be mentioned).
  • the gel can be obtained by adding a rheological agent (thickener) such as a dehydrogenated castor oil derivative to the formulation (see Example 1--toner oil).
  • the reagents that can be selected for separation are microcrystalline wax, siloxane, adipic acid, adipic acid ester, aliphatic Amide and glycol compounds.
  • a silicon compound as a separating agent in the cover oil.
  • the characteristics of the cover oil binder are high molecular weight, but the molecular weight of the varnish is relatively low.
  • the polymeric binder of the printing ink can be composed of one or more resins which are of low polarity. They should be dissolved in the solvent system described above. The content of the binder is between 20% and 50% by weight, and most is between 32% and 42%.
  • the binder is a homopolymer or a mixed copolymer of a low polar monomer such as (C3 - C12)-methyl methacrylate, such as 2-Ethylhexylacrylate isooctyl acrylate, Acylamid copolymer acrylamide copolymer, Styreneacrylate copolymer benzene Ethylene-acrylate copolymer, acrylic acid, methacryl polymer, and the like.
  • the adhesive for the cover oil is DEGALAN LP 62-05 from Evonik
  • the adhesive for varnish is ELVACITE 4048 from Lucite.
  • additives In order to improve the specific quality of the cover oil and the varnish, an appropriate amount of additives is usually added; in general, the use ratio of these additives is 0.1 to 5% by weight; the total weight ratio of these materials cannot exceed the cover oil, 10% of the total composition of the varnish.
  • Commonly used additives are wetting agents and dispersing agents, such as castor oil derivatives; defoaming aids and flow aids such as silicon compounds; rheology aids such as deoxidized castor oil compounds.
  • the colorant includes a ratio of oil to 6-9 to 10, that is, the weight fraction of the ceramic pigment (including the colored pigment and its suitable glassy auxiliary volume) is 100, and the weight fraction of the printing varnish is 60-90. .
  • Both the film forming solution and the printing varnish are produced by dissolving the polymer binder in a solvent system and then adding the additive to the hot resin solution in the solvent. Generally, this process is carried out at high temperatures. After cooling to room temperature, the cover oil can be printed on a special paper with a coarse screen through a suitable screen printing paste.
  • the decorative paper-bearing layer of the new flower paper system of the invention can be easily peeled off, and the paper can be reused, the process is simple, and the use is convenient.
  • FIG. 1 is a schematic view of the structure of the present invention. detailed description The present invention will be further described in detail below with reference to the accompanying drawings and specific embodiments:
  • the easily peelable ceramic applique of the present invention comprises a peelable support substrate 1, an ink coating 2 and a peelable adhesive coating 3.
  • Aromatic hydrocarbon mixed solvent (Shellsol AB 1 ) 56.3% (weight fraction)
  • ELVACITE 4048/LUCITE the basic component acrylic resin
  • An ink layer of different colors is printed on the above-mentioned carrier paper by a screen printing method to form a desired pattern decoration screen. See Example 1 for the composition of the varnish in the ink.
  • cover oil is printed on the carrier layer.
  • the print area of the cover oil is slightly larger than the area of the carrier pattern layer.
  • the cover oil contains the following ingredients:
  • Aromatic hydrocarbon mixed solvent (Shellsol A 1 ) 60.8 %
  • Acrylic copolymer (DEGALAN LP 62-05 3 ) 34.0 %
  • Ceramic pigment (121235 type, FERRO), blue, containing cobalt oxide and lead borosilicate toner. When it was mixed with the varnish in Example 1, a color paste was formed.
  • the varnish is 24.75%.

Landscapes

  • Decoration By Transfer Pictures (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)

Description

易剥离陶瓷贴花及其加工工艺
技术领域
本发明属于硅酸盐基材表面贴花技术领域, 尤其是设计一种易剥离的陶瓷 贴花及其加工工艺。 背景技术
玻璃和陶瓷等硅酸盐基材制品可以通过贴花进行装饰。 这种贴花的花纸通 常由柔性衬底和可转移薄涂层或薄膜层构成。 首先将期望的图文装饰饰样印于 支承的底纸后, 接着印刷一层覆盖层, 图紋装饰饰样会随可转移薄涂层或薄膜 层一起转移印制到陶瓷或玻璃制品表面, 然后进行烧制获得永久的粘附图紋装 饰饰样涂层。
实现把花纸图案移印到玻璃或陶瓷制品的过程, 包括: 首先要把图案承载 层 (柔性衬底) 与可转移薄涂层或薄膜层剥离, 接着把可转移薄涂层或薄膜层 置于玻璃或陶瓷制品期望的位置。
一些专利对其它类型的可剥离花纸进行了详细描述, 例如 Reed 的 U.S. 3,987,225 或 Mackenzie的 U.S. 3,212,913。尽管所述专利描述得十分详细,但这 类型的花纸是印在透明塑料基体上的, 其设计是为了完成原始设计图稿, 并不 是用于最终的装饰。 Reed 等公开了如何使用 低漆膜厚度 (通常为 0.003 到 0.0005 英寸) 和低粘性胶粘剂的硝酸纤维油墨。 然而, 这些花纸的拉伸强度仍 达不到本发明所公开的花纸的拉伸强度。
Keough等在专利 U.S. 4,022,926中公开了一种压印标签, 它是通过在表面 个别区域覆盖粘合剂的承载或支承纸张上印刷放射聚合性液体来实现的。 放射 处理对于整个花纸生产过程来说是一个附加过程, 并不是实用。
Shadbolt等在专利 U.S. Pat. No. 4,177,309公开了一种花纸, 它包括承载纸 张, 树脂印刷油墨和粘合剂。 然而, 这种花纸的抗磨损性能有限而且字体颜色 单一。
传统的方式制造这种花纸的方法成本高, 耗时长。 由于在油墨及支承纸张 上不停地进行层印, 因此花纸在最终使用前必须从后面连接的纸张剪切下来。 对切割设备的需求也导致了成本的增加, 特别是花纸形状很复杂时, 额外的成 本会更多。 发明内容
本发明的目的在于提供一种新的易剥离陶瓷贴花, 解决现有技术存在的缺 陷。
为实现上述目的, 本发明采用如下技术方案:
一种易剥离陶瓷贴花, 包括可剥离支承底材, 固定于支撑底材且可与支持 底材分离的贴花色彩层, 和转印膜层, 所述的转印膜层包括以透明凝胶的形式 溶解于有机溶剂系统中的有机共聚物粘合剂。
优选的方案是: 所述的贴花色彩层包括多层彩色印刷油墨层, 所述的油墨 层之间为共聚物材料。
更为优选的方案是: 所述的可剥离支承底材包括原纸和涂有硅酮、 氟代硅 酸盐、 聚乙烯类或聚丙烯薄膜、 聚酯或其混合物的涂层; 所述的原纸浆料为
60-300g/m2, 所述涂层为 0.3-5 g/m2
更为优选的方案是: 所述的油墨层的油墨体系包括 20-50wt%的粘合剂, 45-65 \¥1%的溶剂, 0-15 wt%的增塑剂, 0.1 - 5 \¥1%的分离剂 (wt为重量分数。
更为优选的方案是: 所述的粘合剂为一种或多种低极性树脂的单体均聚物 或混合共聚物。
更为优选的方案是:所述的粘合剂为 (C3 - C12)-垸基丙烯酸甲酯, 或丙烯酸 异辛酯, 或丙烯酰胺共聚物, 或苯乙烯 -丙烯酸酯共聚物, 或丙烯酸和甲基丙烯 酰聚合物。
更为优选的方案是: 所述的粘合剂为 25-35wt%。
更为优选的方案是: 所述的油墨体系还包括 0.1-5 wt%的添加剂, 所述的添 加剂为润湿剂、 分散剂、 消泡助剂或流变剂中的一种或几种。
本发明的另一目的在于提供一种新的易剥离陶瓷贴花的加工工艺, 采用如 下技术方案: 一种易剥离陶瓷贴花的加工工艺, 包括如下步骤:
1 ) 预制好前一发明目的所述的涂层, 油墨体系, 和粘合剂;
2)将印刷有期望装饰饰样的花纸布置于可剥离支撑底材上, 涂布步骤 1预 制好的涂层;
3 ) 在涂层上涂布步骤 1预制好的油墨体系的油墨涂层;
4) 在油墨涂层上涂布步骤 1预制好的可剥离粘性涂层;
5 ) 转印于陶瓷、 玻璃、 瓷器类硅酸盐基材表面烧制成型。
我们研究发现, 使用压敏胶粘剂可以使图案转印层从花纸转印到被装饰物 件上的过程变得容易些; 这一新工艺不需要可熔性油墨层并能在室温下进行。 在使用压敏胶粘剂进行转印的过程中, 直接把装饰图案转印层转印到被装饰物 件上效果更好。
白瓷、 陶瓷和玻璃等硅酸盐制品的表面通常是通过贴花和烘烤上述 "陶瓷 花纸"来进行装饰的。 剥离画面承载层后, 直接贴于陶瓷坯体表面, 然后在摄氏 480度到 1250度范围内进行烧制。 烧制过程中, 所有的有机化合物会全部会分 解, 只剩下无机色料, 无机色料会随热量的不断聚集与坯体熔合。 可以通过传 统方法如丝网印刷将使用糊精涂层纸张的陶瓷贴花纸转印到陶瓷坯体表面贴花 后进行烧制。
可剥离纸张由原浆为 60-300g/m2的原纸和 0.3-5g/m2的涂层组成。 涂层材料 可以是硅酮、 氟代硅酸盐、 聚乙烯类和聚丙烯薄膜或聚酯 (PET) 。 在套印后和 按下文方法涂清漆层后, 这类纸张的脱离性能能够得到充分发挥并有所提升。
我们已经发现了适用于玻璃 、 瓷器和陶瓷表面装饰性贴花纸的封面油和印 刷调墨油体系,包括含量为 20%-50 wt%的粘合剂,溶解于含有重量比重为 45-65 wt%的溶剂系统, 蒸馏范围在摄氏 100度到摄氏 200度之间的芳香烃, 0-15 wt% 的增塑剂, 0.1-5 wt%用于分离的特殊试剂 (通常重量比重为 0.1%到 1%之间, 下面的内容会提到)。 凝胶可以通过在配方里填加类似脱氢蓖麻油衍生物这样的 流变剂 (增稠剂) 来实现 (见实施例 1--调墨油)。
为了改进上述丙烯酸树脂的剥离性能, 待成膜溶液完全干燥后需要添加添 加剂。 可选择用于分离的试剂有微晶蜡、 硅氧垸、 己二酸、 葵二酸酯、 脂肪族 酰胺和二醇类化合物。 在我们的实施例中, 封面油中我们选用了硅的化合物作 为分离剂。 封面油粘合剂的特性是具有高分子量, 但调墨油的分子量却比较低。 印刷油墨的聚合物粘合剂可由一种或多种树脂组成, 其性质是极性低。 他们应 溶解于上述的溶剂系统中。 按重量比计算, 粘合剂这部分的含量在 20%-50%之 间, 大部分在 32%至 42%之间。
粘合剂是低极性单体的均聚物或混合共聚物, 例如 (C3 - C12)- 垸基丙烯酸 甲酯、 例如 2 -Ethylhexylacrylate丙烯酸异辛酯、 Acylamid copolymers丙烯酰胺 共聚物、 Styreneacrylate copolymers苯乙烯 -丙烯酸酯共聚物、 丙烯酸和甲基丙烯 酰聚合物等。 适用于封面油的粘合剂是 Evonik生产的 DEGALAN LP 62-05, 适 用于调墨油的粘合剂是 Lucite生产的 ELVACITE 4048。
为了提高封面油和调墨油的特定质量, 通常会添加适量添加剂; 总体来说, 按重量比计算, 这些添加剂的使用范围是 0.1到 5%; 这些物质的总合重量比不 能超过封面油、 调墨油总构成成分的 10%。 常使用的添加剂是润湿剂和分散剂, 例如蓖麻油衍生物; 消泡助剂和流动助剂如硅化合物; 流变助剂如脱氧蓖麻油 化合物。
色浆包括的油料比例为 6-9比 10, 也就是说陶瓷颜料 (包括着色色料及其 合适的玻璃状助容积) 的重量份数为 100, 印刷调墨油的重量份数为 60-90。
成膜溶液及印刷调墨油的生产都是通过在溶剂系统中溶解聚合物粘合剂, 然后在溶剂里的热树脂溶液中加入添加剂。 一般来讲, 这个过程是在高温下进 行的。 冷却到室温后, 就可以通过合适的丝网印色浆, 用粗筛在特殊纸张上印 封面油。
本发明所述新的花纸体系装饰承载层能十分轻松的被剥离后, 而且纸张可 再次使用, 工艺简单, 使用方便。 附图说明
图 1为本发明的结构示意图。 具体实施方式 下面结合附图和具体实施例对本发明做进一步详细说明:
如图 1所示, 本发明的易剥离陶瓷贴花包括可剥离支撑底材 1, 油墨涂层 2 和可剥离粘性涂层 3。
实施例 1 调墨油 (Medium)
芳香烃混合溶剂 (Shellsol AB1 ) 56.3% (重量分数)
邻苯二甲酸二辛
Elvacite 40483
BYK 0884
Butyllactat5
Thixatrol super6
1, AB型, 沸点范围 摄氏 186度到 216度;
2, DOP, 邻苯二甲酸二辛酯;
3, ELVACITE 4048/LUCITE, 基本成份丙烯酸树脂;
4, BYK 088, 分散剂, ALTANA CHEMIE ;
5, Butyllactat, 溶剂, 沸点摄氏 188度;
6, THIXATROL SUPER, 增稠剂。
生产如实施例 1和 2种这些物质, 需要用溶解器混合并溶解搅拌 30分钟, 这个过程中不能进行冷却
实施例 2
通过丝网印刷的方法在上述承载纸张上印刷不同种颜色的油墨层, 形成期 望的图案装饰画面。 油墨中调墨油的成份请见实施例 1。
装饰画面印刷完毕后, 在承载层上印些可剥离的封面油。 封面油的印刷面 积要略大于承载图案层的面积。 封面油含有如下成份:
封面油 (Covercoat)
芳香烃混合溶剂 (Shellsol A1 ) 60.8 %
邻苯二甲酸二异壬酯 (DINP2 ) 4.5 %
丙烯酸共聚物 (DEGALAN LP 62-053) 34.0 %
BYK 0884 0.7 % 1, A型, 沸点范围 摄氏 165度到 185度;
2, 增塑剂;
3, Degalan LP 62-05, 制造商 EVONIK;
4, 分散剂 BYK 088 , ALTANA CHEMIE 。 烘干后的花纸会延伸 17%到 23%。
实施例 3色浆
陶瓷色料 (121235 型, FERRO ) , 蓝色, 含氧化钴和硼硅酸铅色粉。 把它 与实施例 1中的调墨油混合后, 就会形成色浆。
颜料 75.25%;
调墨油 24.75%。
实施例 4 花纸的应用
干燥后, 人工将花纸画面部分与承载纸张剥离, 并浸泡在水和乙醇的混合 溶液中 (例如 5%的丁二醇溶液) 1分钟, 然后贴于白瓷盘, 接下来用肖氏硬度 为 65的橡胶滚轴陶瓷刮刀刮去贴花纸与盘子间的水印, 使其变得平整无痕。
以上内容是结合具体的优选实施方式对本发明所作的进一步详细说明, 不 能认定本发明的具体实施只局限于这些说明。 对于本发明所属技术领域的普通 技术人员来说, 在不脱离本发明构思的前提下, 还可以做出若干简单推演或替 换, 都应当视为属于本发明的保护范围。

Claims

权利要求书
1. 一种易剥离陶瓷贴花, 其特征是: 包括可剥离支承底材, 固定于支撑底 材且可与支持底材分离的贴花色彩层, 和转印膜层, 所述的转印膜层包括以透 明凝胶的形式溶解于有机溶剂系统中的有机共聚物粘合剂。
2. 如权利要求 1所述的易剥离陶瓷贴花, 其特征是: 所述的贴花色彩层包 括多层彩色印刷油墨层, 所述的油墨层之间为共聚物材料。
3. 如权利要求 1所述的易剥离陶瓷贴花, 其特征是: 所述的可剥离支承底 材包括原纸和涂有硅酮、 氟代硅酸盐、 聚乙烯类或聚丙烯薄膜、 聚酯或其混合 物的涂层; 所述的原纸浆料为 60-300g/m2, 所述涂层为 0.3-5 g/m2
4. 如权利要求 1-3任一所述的易剥离陶瓷贴花, 其特征是: 所述的油墨层 的油墨体系包括 20-50 wt%的粘合剂, 45-65 \¥1%的溶剂, 0-15 wt%的增塑剂, 0.1 - 5 wt%的分离剂。
5. 如权利要求 4所述的易剥离陶瓷贴花, 其特征是: 所述的粘合剂为一种 或多种低极性树脂的单体均聚物或混合共聚物。
6. 如权利要求 5所述的易剥离陶瓷贴花, 其特征是: 所述的粘合剂为 (C3 - C12)-垸基丙烯酸甲酯, 或丙烯酸异辛酯, 或丙烯酰胺共聚物, 或苯乙烯-丙烯酸 酯共聚物, 或丙烯酸和甲基丙烯酰聚合物。
7. 如权利要求 6 所述的易剥离陶瓷贴花, 其特征是: 所述的粘合剂为 25-35wt%。
8. 如权利要求 5-7任一所述的易剥离陶瓷贴花, 其特征是: 所述的油墨体 系还包括 0.1-5 wt%的添加剂, 所述的添加剂为润湿剂、 分散剂、 消泡助剂或流 变剂中的一种或几种。
9. 一种易剥离陶瓷贴花加工工艺, 包括如下步骤:
1 )预制好如权利要求 1所述的涂层, 预制好如权利要求 4或 8所述的油墨 体系, 预制好如权利要求 5-7任一所述的粘合剂;
2 )将印刷有期望装饰饰样的花纸布置于可剥离支撑底材上, 涂布步骤 1预 制好的涂层;
3 ) 在涂层上涂布步骤 1预制好的油墨体系的油墨涂层; 4) 在油墨涂层上涂布步骤 1预制好的可剥离粘性涂层;
5 ) 转印于陶瓷、 玻璃、 瓷器类硅酸盐基材表面烧制成型。
PCT/CN2009/076134 2009-05-21 2009-12-28 易剥离陶瓷贴花及其加工工艺 WO2010133075A1 (zh)

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US20110243628A1 (en) * 2010-03-30 2011-10-06 Maclean Amy R Reusable cling decals for plastic toys, building bricks, and accessories and system for customizing
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