CN100412269C - 具有改善的印刷或书写特性的型样纸 - Google Patents
具有改善的印刷或书写特性的型样纸 Download PDFInfo
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- CN100412269C CN100412269C CNB2003801088842A CN200380108884A CN100412269C CN 100412269 C CN100412269 C CN 100412269C CN B2003801088842 A CNB2003801088842 A CN B2003801088842A CN 200380108884 A CN200380108884 A CN 200380108884A CN 100412269 C CN100412269 C CN 100412269C
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- D—TEXTILES; PAPER
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- D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
- D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
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Landscapes
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Abstract
本发明涉及具有改善的印刷或书写特性的、不均匀致密着色的纸张的生产方法，以及由此方法生产的纸张。
Description
技术领域
本发明涉及具有改善的印刷或书写特性的、不均匀致密着色的纸张的生产方法，以及由此方法生产的纸张。
背景技术
即使在电子数据传输的时代，通常也需要有视觉吸引力的纸张。因此，除高纸张质量以外，造纸工业的目标还在于生产有视觉吸引效果的纸张。
在US 4,534,157中，通过喷墨嘴将油墨喷至墨辊上，然后墨辊将油墨转印至纸张上，直接在作为纸幅生产出之后在潮湿状态下对纸张印刷颜色。从而，将在纸幅上具有恒定油墨量的不规则的、分散的图案施加至其它未染色的纸张上。
在EP 601517中，利用尽可能少的油墨在白纸上印刷规则或不规则的图案。油墨仅以很小的程度渗透入纸张中。EP 601157的公开内容中还特别地给出了进入纸张中油墨的小的渗透值。因为所述纸张随后作为白纸可回收，因此，油墨必须能够容易地从纸张中除去。
EP 681060描述了不同色彩着色的纸张的生产方法，其中，将不同厚度的纤维素纤维和聚集物用于所述纸张的生产方法中，并沉积或包含入最终纸张中。在沉积或包含入纸张中之前对不同厚度的纤维素纤维或聚集物着色，然后掺入纸浆中，其纸浆本身可以有不同的颜色。
迄今为止用来生产型样纸的方法要么较为复杂，要么生产方法缓慢，要么将获得完全不同于预期效果的纸张。
EP 439363披露了一种包含去胶剂(desizing agent)或用去胶剂进行涂布的纸张，结果是，在利用墨喷式印刷对纸张进行印刷期间，可以更好地吸收油墨。去胶剂分布于纸张中或纸张上，均匀地分布在整个纸张表面上，从而获得最佳的印刷样板。
EP 518490描述了用于墨喷式印刷的油墨，所述油墨包含促进油墨渗透进入印刷纸张中的组分。
EP 439363和EP 518490共同教导通过适当地使用去胶剂，促进了极性液体如喷墨油墨向纸张结构中的渗透和向施胶纸纸张纤维中的渗透。然而，EP 439363和EP 518490均没有描述通过对纸张表面的不均匀着色而生产型样纸的方法。
为了增加原纸的印刷和书写特性，EP 1239077提出施加一具有聚亚烷氧基结构的非离子表面活性剂。
EP 732219披露了包含液体吸收基材、提供在基材上的油墨-接收层和提供在油墨-接收层上的表面层的印刷介质；所述油墨接收层包含颜料、粘合剂和阳离子物质；表面层由作为无机颗粒的阳离子超细颗粒组成。作为超细颗粒，描述了直径从1-500纳米的金属氧化物。这些颗粒形成闭合的光泽的表面层。包含在油墨接收层中的颜料是直径从0.1-20微米的无机颜料。
发明内容
本发明的目的在于获得不均匀着色的具有视觉吸引力的纸张，所述纸张具有以尽可能小的劳动力而获得的改善的印刷或书写特性。
本发明的目的通过不均匀致密着色的纸张的生产方法而实现，所述方法包括：
a)以潜在的图像或图案形式将至少一种表面活性剂或表面活性剂的混合物施加至纸张上，由此，使所述表面活性剂与至少一种填料(颜料)混合，
b)通过染料溶液对所述纸张着色，和
c)对所述着色纸张进行干燥。
本发明利用了纸张施胶现象以及随后应用该现象以特定的方式在纸幅优选区域内施加适当的物质。通常，为了避免施加液体过度地向纸张结构中以及纤维(吸墨效应)中渗透，需对纸张进行施胶。在造纸机中形成纸幅之前，通过向含水纸张纤维浆液中添加施胶物质，在纸张生产期间进行施胶。施胶物质沉积至纤维上，其沉积量使最终干燥纸张获得理想的液体吸收性能。该方法称为内部施胶或机器上胶。所获得的液体吸收程度与纸张的“内部施胶度”成反比。
表面施胶可以替代机器上胶，或除机器上胶之外再进行表面施胶。在本发明中，例如通过造纸机内部的施胶压力机，将成膜物质，如加工淀粉的溶液或分散体、树胶和改性的聚合物施加至已成形的纸幅上。另外，表面施胶还有助于提高纸张的强度，因此，高-质量印刷纸常常进行机器上胶和表面施胶。然而，对于本发明的方法，表面施胶并不是至关重要的，且也可能使用没有表面施胶的纸张。
另外，不均匀致密着色的纸张的生产方法在步骤a)中可以包括施加可见的图像或图案形式的染料溶液于纸张上。
本发明的优选实施方式将在从属权利要求中加以说明。
本发明的生产方法将形成牢固着色的在纸张表面具有不同色强度的纸张。不同的色强度将产生对于眼睛表现为图像或图案的视觉效应。
所述图像或图案可以如下形式存在：代表性的图像、富于想象力的结构、印记、规则或不规则图案、网状结构或不规则的例如随机的在纸张上分布的色彩。
图像或图案可在造纸之后直接施加，即施加至仍然湿润的纸张上，或施加至先前生产的干燥的纸张上；然后通过含水染料溶液对纸张进行牢固地着色。图像或图案可施加至连续的纸幅上或单独的纸页上。优选的是，图像或图案施加至连续的纸幅上。
图像或图案可通过任何希望的方法来施加，特别是通过墨喷式印刷、胶版印刷、苯胺印刷、照相凹版印刷、利用毛毡或胶辊的印刷、用喷涂或手工的方式，最后的方法不适于工业生产。特别优选的图像或图案的施加方法是墨喷式印刷、苯胺印刷或照相凹版印刷。
图案或图像可以以潜在的图像或图案的形式或可以以可见的图像或图案的形式施加至纸张上。
为形成潜在的图像或图案，将影响含水染料溶液渗透入纸张的物质施加至纸张上，其要点在于通过促进或减少吸收而施加该物质。
这可借助所施加的物质，通过减少(去胶剂)或增加(疏水剂)由纸张施胶所取得的施胶度或疏水度来实现。
具有所述性能的每一种物质均可用于本发明的方法。优选将表面活性剂用于此用途。可以使用阴离子型、阳离子型、非离子型或两性表面活性剂。除表面活性剂以外，可以使用促进染料向纸张中渗透的物质。所述物质例如有：乙二醇醚，例如乙二醇单甲基醚，乙二醇单乙基醚，乙二醇单苯醚，二甘醇单甲基醚，二甘醇单乙基醚和二甘醇单丁基醚。
合适的去胶表面活性剂例如可选自：(1)亲水性聚二烷基硅氧烷，(2)聚亚烷基二醇，(3)聚环氧丙烷/聚环氧乙烷共聚物，(4)磷酸盐，脱水山梨醇，甘油，聚乙二醇，磺基丁二酸，磺酸或烷基胺的脂肪酯-改性的化合物，(5)脱水山梨醇酯，脂肪胺，链烷醇酰胺，蓖麻油，脂肪酸，脂肪醇的聚氧化烯-改性的化合物，(6)季醇硫酸盐化合物，(7)脂肪咪唑啉，(8)聚醚-改性的三硅氧烷，以及(9)它们的混合物。
选自上述物质的水溶性或醇溶性去胶剂的具体例子例如有：(1)聚(氧化烯)改性的(a)脱水山梨醇酯(例如，Alkamuls PSML-4(聚(氧化乙烯)脱水山梨醇单月桂酸酯)，Alkamuls PSMO-20(聚(氧化乙烯)脱水山梨醇单油酸酯)，Alkamuls PSTO-20(聚(氧化乙烯)脱水山梨醇三油酸酯)，Alkaril Chemicals)；(b)脂肪胺(例如，Alkaminox T-2，T-6(牛油脂肪胺乙氧基化物)，Alkaminox SO-5(大豆胺乙氧基化物)，AlkarilChemicals)，(Icomeen T-2，Icomeen T-15，ICI Chemicals)；(c)蓖麻油(例如，Alkasurf CO-10，Alkasurf CO-25B(蓖麻油乙氧基化物)，AlkarilChemicals)；(d)链烷醇酰胺(例如，Alkamide C-2，C-5(椰子油链烷醇酰胺乙氧基化物)，Alkaril Chemicals)；(e)脂肪酸(例如，Alkasurf 075-9，Alkasurf 0-10，Alkasurf 0-14(油酸乙氧基化物)，Alkasurf L-14(月桂酸乙氧基化物)，Alkasurf P-7(棕榈酸乙氧基化物)，Alkaril Chemicals)；(f)脂肪酸醇(例如，Alkasurf LAN-1，LAN-3，Alkasurf TDA-6，AlkasurfSA-2(直链醇乙氧基化物)，Alkasurf NP-1，NP-11，Rexol 130(壬基苯酚乙氧基化物)，Alkasurf OP-1，OP-12(辛基苯酚乙氧基化物)，AlkasurfLA-EP-15，Alkasurf LA-EP-25，Alkasurf LA-EP-65(线性醇烷氧基化物))；(2)亲水性聚(二甲基硅氧烷)，例如，(a)具有单甲醇端基的聚(二甲基硅氧烷)(PS556，Petrarch Systems Inc.)和具有二甲醇端基的聚(二甲基硅氧烷)(PS555，PS556，Petrarch Systems Inc.)；(b)聚(二甲基硅氧烷)-b-聚(甲基硅氧烷/烯化氧)共聚物(PS 073，PS 072，PS 071，Petrarch Systems Inc.)，Alkasil HEP 182-280，Alkasil HEP148-330(AlkarilChemicals)，包含Si-C键的不可水解的共聚物；(c)聚(二甲基硅氧烷)-b-聚(氧化丙烯)-b-聚(氧化乙烯)共聚物(Alkasil NEP73-70，karil Chemicals)，含Si-O-C键的水解的共聚物；(d)聚季铵化聚(二甲基硅氧烷)共聚物(其可通过d，ω-氢聚硅氧烷与包含烯键的环氧化物的加成反应，随后使产物与二胺反应得到)；(3)脂肪咪唑啉及其衍生物，例如，(a)Alkazine-0(油基衍生物)；b)Alkazine TO(妥尔油衍生物)；(c)Alkateric 2C1B(二羧酸椰子咪唑啉钠盐)，Alkaril Chemicals；(d)Arzoline-4；(e)Arzoline-215，Baker Chemicals；(4)(a)磷酸盐的脂肪酸酯(例如，Alkaphos B6-56A，Alkaril Chemicals)；(b)脱水山梨醇(例如，Alkamuls STO(脱水山梨醇三油酸酯)，Alkamuls SML(脱水山梨醇单月桂酸酯)，Alkamuls SMO(脱水山梨醇单油酸酯)，AlkarilChemicals)；(c)甘油化合物(例如，Alkamuls GMO-45LG(甘油单油酸酯)，Alkamuls GDO(甘油基二油酸酯)，Alkamuls GTO(甘油三油酸酯)；(d)聚(乙二醇)(Alkamuls 600 DO(二油酸酯)，Alkamuls 400-ML(单月桂酸酯)，Alkamuls 600 MO(单油酸酯)，Alkamuls 600 DL(二月桂酸酯)，Alkamuls 600 DT(二牛脂)，Alkaril Chemicals)；(e)磺基丁二酸(例如，Alkasurf SS-0-75(二辛基磺基丁二酸钠)，Alkasurf SS-DA4-HE(磺基丁二酸乙氧烯化醇酯)，Alkasurf SS-L7DE(月桂酸二乙醇酰胺的磺基丁二酸酯钠)，Alkasurf SS-L-HE(月桂基磺基丁二酸钠)，AlkarilChemicals)；(f)磺酸(例如，Alkasurf CA(十二烷基苯磺酸钙)，AlkasurfIPAM(十二烷基苯磺酸异丙胺)，Alkaril Chemicals)；(g)烷基胺(例如，Alkamide SDO(大豆二乙醇酰胺)，Alkamide CDE(椰子-二乙醇酰胺)，Alkamide 2104(可可脂肪酸二乙醇酰胺)，Alkamide CMA(椰子-单乙醇酰胺)，Alkamide L9DE(月桂基二乙醇酰胺)，Alkamide L7Me(月桂基-单乙醇酰胺)，Alkamide L1PA(月桂基单异丙基酰胺)，AlkarilChemicals)；(5)季化合物，例如，(a)非聚合季铵化乙基硫酸铵(例如，Finquat CT，Cordex T-172，Finetex Corporation)；(b)季二烷基二甲基甲基硫酸酯(例如，Alkaquat DHTS(氢化动物脂))；(c)烷氧基化季铵化二-脂肪甲基硫酸酯(例如，Alkasurf DAET(动物脂衍生物))；(d)季铵化脂肪咪唑啉甲基硫酸酯(例如，Alkaquat T(动物脂衍生物)，AlkarilChemicals)；(6)亲脂性聚(氧化丙烯)与亲水性聚(氧化乙烯)的水溶性共聚物，例如，(a)甲醇-可溶的Tetronic 150R1，Pluronic L-101，Tetronic902，Tetronic 25R2(BASF Corporation)，Alkatronic EGE-1(AlkarilChemicals)；(b)水溶性Tetronic 908，50R8，25R8，904，90R4，PluronicF-77，均得自BASF Corporation，以及得自Alkaril Chemicals的Alkatronic EGE 25-2和PGP 33-8；(7)聚(亚烷基二醇)及其衍生物，例如，(a)聚丙二醇(Alkapol PPG 425，Alkapol PPG-4000，AlkarilChemicals)；(b)聚(二甲基丙烯酸丙二醇酯)，聚(二丙烯酸乙二醇酯)，聚(二甲基丙烯酸乙二醇酯)，聚(乙二醇单甲醚)，聚(乙二醇二甲醚)，聚(乙二醇二缩水甘油醚)(均得自Polysciences)；(c)聚(1，4-氧化丁二醇)(Scientific Polymer Products)等等。
优选的去胶剂包括：直链醇乙氧基化物(例如，可得自AlkarilChemicals的Alkasurf LA-EP-65，LA-EP-25和LA-EP-15)，壬基苯酚乙氧基化物(例如，可得自Alkaril Chemicals的Alkasurf NP-11和可得自Hart Chemicals的Rexol 130)，辛基苯酚乙氧基化物(例如，可得自Alkaril Chemicals的Alkasurf OP-12)，油酸乙氧基化物(例如，可得自Alkaril Chemicals的Alkasurf O-14)，聚(二甲基硅氧烷)-b-聚(氧化丙烯)-b-聚(氧化乙烯)共聚物(例如，可得自Alkaril Chemicals的AlkasilNEP 73-70)，蓖麻油乙氧基化物(例如，可得自Alkaril Chemicals的Alkasurf C025B)，椰子-咪唑啉二羧酸钠盐(例如，可得自AlkarilChemicals的Alkateric 2C1B)和椰子油脂肪酸二乙醇酰胺(例如，可得自Alkaril Chemicals的Alkamid S104)。所述Alkasurf去胶剂的优点是可生物降解的。
赋予疏水性的合适的表面活性剂例如是，纸张施胶剂，如烷基丁二酸酐(ASA)，烷基烯酮二聚体(AKD)和聚烯烃(例如，SUDRANOL200，Sudeutsche Emulsions-Chemie GmbH，Mannheim，Germany)，蜡，蜡-状物质，金属皂(硬脂酸盐)，石蜡和石蜡乳剂，脂肪酸，脂肪酸(甲基)酯，脂肪醇，脂肪醇聚乙二醇醚及其硫酸盐。
在向纸张施加期间，表面活性剂以溶液、乳液或分散体的形式存在，其另外还可以包含如下所述的可溶性染料，和/或除表面活性剂以外的助剂。传统的助剂是增稠剂，例如，阿拉伯树胶，聚丙烯酸酯，聚甲基丙烯酸酯，聚乙烯醇，羟丙基纤维素，羟乙基纤维素，聚乙烯吡咯烷酮，聚乙烯醚，淀粉，多糖等等，荧光增白剂，增白猝灭剂(brightener quencher)，颜料(染色或非染色颜料，包括具有金属效应的颜料或金属)，粘合剂，防腐剂和安全性化学制品，例如，荧光物质，磷光物质或发光物质。所述表面活性剂优选以水溶液或醇溶液的形式存在。
所施加的表面活性剂在溶液、乳液或分散体中的浓度范围为0.01-30重量％，优选为0.1-25重量％，特别优选的是为0.2-15重量％。
根据本发明，所施加的溶液、分散体或乳液另外还包含至少一种填料(或颜料)，其选自金属或半金属例如镁、钙、铝、锌、铬、铁、铜、锡、铅或锰的氧化物。优选的颜料是二氧化硅、三水铝石、三羟铝石、新三水氧化铝(nordostrandite)、勃姆石、假勃姆石、水铝石、氧化铝，特别是金刚砂、氧化铝水合物、硅酸镁、碱式碳酸镁、(二)氧化钛、氧化锌、硅酸铝、碳酸钙、滑石、粘土、水滑石、无机物质如硅藻土、有机物质例如由脲-甲醛树脂、乙烯树脂、苯乙烯树脂、丙烯酸酯树脂或者它们的组合物制成的树脂颜料。
本发明的一方面在于，所用的填料具有大的表面积。然而，颗粒本身的直径为1-500纳米，优选10-100纳米。
向溶液、乳液或分散体中添加填料影响潜在的图像或图案且改善了用表面活性剂处理过的纸张部分上的印刷或书写特性。通过用表面活性剂对纸张进行处理，随后施加的油墨将分散在处理过的纸张上(渗色，洇纸)。通过同时施加表面活性剂和填料以上作用将被减弱，这是因为当同时施加填料时，为获得相同的图像或图案效应只需要很少的表面活性剂。由于只有较少量的表面活性剂，印刷或书写油墨较少地被分散。相对于固体部分(干燥)，填料和表面活性剂在所施加的溶液，乳液或分散体中的比例为：1∶0.08至1∶0.9，优选1∶0.09至1∶0.5，更优选的是1∶0.1至1∶0.4。
所施加的填料(颜料)优选是非-着色的，更优选是透明的，并且它们具有不能获得反射或光分散的小的直径。颗粒优选的平均直径小于0.1μm。因此，所述颜料在含水体系中形成胶体溶液。
特别优选的是阳离子填料，即指所述颜料在其表面上具有正电荷。在其表面上具有负电荷的那些填料如二氧化硅，如果对其进行表面处理使表面负电荷变成正电荷的话，也可以使用。在阳离子表面上的正电荷将起增加与下面染色浴的负电荷染料的结合的作用。在该优选的实施方案中，非离子表面活性剂以与阳离子填料混合的混合物的形式使用。
可用作表面活性剂助剂的增稠剂的浓度以整个溶液、乳液或分散体计，为0-5重量％的范围，优选为0.01-2.5重量％，特别优选的是为0.05-2.5重量％。
为了在最终纸张上获得进一步的特定效果，还可以在相同的纸张表面上同时施加赋予-去胶和疏水性的表面活性剂。
为产生可见的图像或图案，可使用任何希望的染料溶液。优选使用碱性直接染料或酸性直接染料或这些染料混合物的水溶液。合适染料溶液的例子是通常的印刷油墨，所述油墨例如包含蒽醌-，单偶氮-，重氮-，酞菁-，氮杂-(18)-轮烯-和甲
(formazan)-铜盐络合染料。合适染料的例子是如下进一步提及的用于染浴的染料溶液的那些染料，包括含如下所述的颜料或基于所述颜料的染料。
染料的浓度范围为0.1-30重量％，优选1.0-20重量％，特别优选的是2.0-10重量％。
潜在的或可见的图像或图案可施加至纸张的一面或两面上，以使最终的纸张至少在一面上具有比纸张表面的未处理区域更为强烈或更不强烈的色彩。
在潜在的或可见的图像或图案施加至纸张上之后，纸张在染料溶液的辅助下在步骤(b)中被牢固地着色。着色如下进行以使在造纸机内部或者外部，通过传统的纸张涂布装置和方法，例如，施胶、压膜，刮刀式涂胶机、刮刀、辊或喷雾将染料溶液施加至纸张上；或者通过借助合适印刷方法，如墨喷式印刷、胶版印刷、苯胺印刷、照相凹版印刷或借助毛毡或胶辊的印刷将染料溶液施加至纸张的整个表面上；通过喷雾或在染浴中对纸张的槽法着色而进行所述着色。优选的是，在染料水溶液中通过浸涂法对纸张进行染色。
用于这些用途的任何市售的染料溶液均可用于本发明。染料溶液通常包含浓度范围为0.1-40重量％，优选为0.1-35重量％，特别优选为0.1-30重量％的染料。染料溶液的浓度可根据各自所要取得的希望的效果来确定(随后希望的图像的强度)。相应的实验可通过本领域技术人员简单的试验而进行。
在浸涂方法中，在施加潜在的或可见的图像或图案之后，将纸张浸于染料水溶液中，然后挤压并干燥。槽法着色可利用施胶或未施胶纸幅或纸页来进行。借助槽法着色可以获得高亮度的浓烈色彩。该方法另外的优点在于：即使少量也能够在高效操作下被着色。
如果潜像在纸张着色之前施加的话，在着色处理期间，纸张将根据对纸张进行预处理的物质以更大或更小的程度在预处理区域内吸收颜料。
在用去胶剂预处理过的区域中的增强的油墨接收性将赋予最初以潜像形式施加图像或图案的纸张以与纸张被着色的颜色相同颜色的更强的色调。因此，随后显示“正的”图像或图案的颜色强度可通过所施加去胶剂的用量和/或去胶剂的组分来改变。
如果在纸张着色之前施加疏水剂的话，在纸张着色之后，最初以潜像形式施加的图像或图案将以与纸张被着色的颜色相同颜色的较弱的色调显像。在本发明中，随后显示“负的”图像或图案的颜色强度也可通过所施加疏水剂的用量和/或疏水剂的组分来改变。
为产生潜像，也可能将去胶物质和疏水物质并行施加至相同的纸张上，以致使最终的纸张具有“正的”和“负的”图像或图案。
为了获得所描述效果之一，在施加影响吸墨性能的物质之后，必需对纸张进行着色。
如果在纸张着色之前施加可见的图像或图案的话，随后对纸张着色将增强先前所施加图像或图案的色彩，由此，也能够取得特殊的效果，即对纸张不均匀致密的着色。仅当带有可见图像的纸张另外地进行着色时，才能够获得所述的效果。
通常的含水染料溶液可用于对纸张的着色。这些染料溶液可以包含碱性染料和/或酸性染料和/或直接染料。合适染料溶液的例子是包含蒽醌-，单偶氮-，重氮-，酞菁-，氮杂-(18)-轮烯-和甲
-铜盐络合染料的溶液。合适染料的具体例子在EP-A559324第4页第25-53行中提及。特别是三苯并二噁嗪，Bernacid Red 2BMN；Pontamine BrilliantBond Blue A；Pontamine；食品黑2；Carodirect Turquoise FBL SupraConc.(直接蓝199)，得自Carolina Color and Chemical；Special FastTurquoise 8GL Liquid(直接蓝86)，得自Mobay Chemical；IntrabondLiquid Turquoise GLL(直接蓝86)，得自Crompton and Knowles；Cibracron Brilliant Red Brilliant Red 38-A(活性红4)，得自AldrichChemical；Drimarene Brilliant Red X-2B(活性红56)，得自Pylam，Inc.；Levafix Brilliant Red E-4B，得自Mobay Chemical；Levafix BrilliantRed E-6BA，得自Mobay Chemical；Procion Red H8B(活性红31)，得自ICI America；Pylam Certified D & C Red #28(酸性红92)，得自Pylam；Direct Brill Pink B Ground Crude，得自Crompton & Knowles；Cartasol Gelb GTF，得自Sandoz，Inc.；Tartrazine Extra Conc.(FD & CGelb #5，酸性黄23)，得自Sandoz；Carodirect Yellow RL(直接黄86)，得自Carolina Color and Chemical；Cartasol Yellow GTF Liquid Special110，得自Sandoz，Inc.；D & C Yellow #10(酸性黄3)，得自Tricon；Yellow Shade 16948，得自Tricon，Basacid Black X34，得自BASF，Carta Black 2GT，得自Sandoz，Inc.；Direct Brilliant PinkB(Crompton-Knolls)；Kayanol Red 3BL(Nippon Kayaku Company)；Levanol Brilliant Red 3BW(Mobay Chemical Company)；LevadermLemon Yellow(Mobay Chemical Company)；Spirit Fast Yellow 3G；Sirius Supra Yellow GD 167；Cartasol Brilliant Yellow 4GF(Sandoz)；Pergasol Yellow CGP(Ciba-Geigy)；Dermacarbon 2GT(Sandoz)；Pyrazol Black BG(ICI)；Morfast Black Conc A(Morton-Thiokol)；DiazolBlack RN Quad(ICI)；Luxol Blue MBSN(Morton-Thiokol)；SevronBlue 5GMF(ICI)；Basacid Blue 750(BASF)；Bernacid Red，得自Berncolors，Poughkeepsie，NY；Pontamine Brilliant Bond Blue；Berncolor A.Y.34；Telon Fast Yellow 4GL-175；BASF Basacid Black SE0228；得自ICI的Pro-Jet系列，包括Pro-Jet Gelb I(直接黄86)，Pro-JetMagenta I(酸性红249)，Pro-Jet Cyan I(直接蓝199)，Pro-Jet Schwarz I(直接黑168)，Pro-Jet Yellow1-G(直接黄132)，Aminyl Brilliant Red F-B，得自Sumitomo Chemical Co.(Japan)，得自Hoechst的“不含盐”染料的the Duasyn line，如Duasyn Direct Schwarz HEF-SF(直接黑168)，Duasyn Schwarz RL-SF(活性黑31)，Duasyn Direct Gelb 6G-SF VP216(直接黄157)，Duasyn Brilliant Gelb GL-SF VP220(活性黄37)，DuasynAcid Yellow XX-SF VP413(酸性黄23)，Duasyn Brilliant Rot F3B-SFVP218(活性红180)，Duasyn Rhodamine B-SF VP353(酸性红52)，Duasyn Direct Turkisblau FRL-SF VP368(直接蓝199)，Duasyn AcidBlue AE-SF VP344(酸性蓝9)等等，以及这些染料的混合物。
另外可使用包含颜料或基于颜料(染色或非染色颜料)的染料，所述颜料包括具有金属效果的颜料或金属。
染料的浓度取决于制造商，并且另外还取决于所使用的颜色但这并不限制本发明。
此外，染料溶液可包含添加剂，如醇，增稠剂，湿强剂，荧光增白剂，防腐剂，安全性化学制品，粘合剂和颜料(染料或非-染色颜料，例如碳酸钙)。用于染料溶液的助剂特别是阿拉伯树胶，聚丙烯酸酯盐，聚甲基丙烯酸酯盐，聚乙烯醇，羟丙基纤维素，羟乙基纤维素，聚乙烯吡咯烷酮，聚乙烯醚，淀粉，多糖等等。此外，同样可以包含用于油墨的通常的添加剂。所述通常的添加剂在EP-A518490第4页第55行至第5页第9行中提及。
借助如下实施例更详细地说明本发明的方法，但本发明并不局限于在此所描述的实施方案。
实施例
在改良型长网造纸机上生产定量为105克/平方米的纸张。纸浆组分由80重量％针叶木硫酸盐纸浆和20重量％桉树硫酸盐纸浆组成。利用松香胶和明矾对纸张进行施胶。将1％的三聚氰胺/甲醛树脂用作湿强剂。在本实施例中使用的纸张没有表面施胶。
非纤维添加剂的规定百分数以纤维含量为基础。纸页取自由此生产的纸张，并在施加装置例如Fineliner(Rotring Rapidograph，0.35毫米直径)，竹笔或刷子的帮助下，以手写字符的形式手工地将去胶物质(实施例1)或疏水剂(实施例2)或两者(实施例3)施加至所述的纸页上。在实施例4中，将可见图像施加至纸张上。以此方式处理的纸页通过浸入染料溶液中而着色，然后利用吸收性纸垫挤压并干燥。
实施例1-8
利用去胶剂和填料施加潜像：
将如上所述表面活性剂的水溶液施加至纸页上。通过将纸页浸入1.0重量％的Cartasol Blau 3RF水溶液(Sandoz Chemikalien AG，BasleClariant(德国)GmbH，Lorrach)中而进行随后的着色。潜在的字符十分清晰可见并且显现“正的”图像，其具有与整个纸张被着色的颜色相同的颜色的强色调。
在对纸张进行干燥之后，将某些字符书写或印刷至纸张上，并用肉眼测定结果。
所使用的化合物是：
TEGOPREN 5847：聚醚-改性的三硅氧烷(非离子表面活性剂，得自GOLDSCHMIDT)
HYDROPALAT 120 EXP：EO/PO-改性的脂肪醇，改性的脂肪醇聚乙二醇醚(非离子表面活性剂，得自COGNIS/Henkel)，
TYLOSE H 30000 YP2：羟乙基纤维素(非离子增稠剂，得自CLARIANT)
TYLOSE H 60000 YP2：羟乙基纤维素(非离子增稠剂，得自CLARIANT)
WALOCEL CRT 30000：羧甲基纤维素钠(阴离子增稠剂，得自Wolff Walsrode，BAYER)
LUDOX CL：作为填料/颜料的带有正颗粒电荷的胶态二氧化硅(得自Grace Davison)。
Claims (15)
1. 不均匀致密着色的纸张的生产方法，所述方法包括：a)以潜在的图像或图案形式将至少一种表面活性剂施加至纸张上，其中，在施加至纸张之前，使所述表面活性剂与至少一种填料混合，所述填料选自金属或半金属的氧化物、无机物质或有机物质以及它们的组合，b)通过染料溶液对所述纸张着色，和c)对所述着色纸张进行干燥。
2. 如权利要求1所述的方法，其中，利用喷墨式印刷、胶版印刷、苯胺印刷、照相凹版印刷、或借助毛毡或胶辊的印刷，用喷涂或手工的方式施加所述表面活性剂和填料产生所述潜在的图像或图案。
3. 如权利要求1或2所述的方法，其中，所述金属或半金属选自镁、钙、铝、锌、铬、铁、铜、锡、铅和锰。
4. 根据权利要求1或2的方法，其中，所述填料选自二氧化硅、三水铝石、三羟铝石、新三水氧化铝、勃姆石、假勃姆石、水铝石、氧化铝、金刚砂、氧化铝水合物、硅酸镁、碱式碳酸镁、一氧化钛、二氧化钛、氧化锌、硅酸铝、碳酸钙、滑石、粘土、水滑石或硅藻土。
5. 根据权利要求1或2的方法，其中，所述填料选自由脲-甲醛树脂、乙烯树脂、苯乙烯树脂、丙烯酸酯树脂或者它们的组合物制成的树脂颜料。
6. 如权利要求1或2所述的方法，其中，所施加的表面活性剂有助于水溶性染料渗透入纸张中。
7. 如权利要求1或2所述的方法，其中，所施加的表面活性剂减少水溶性染料渗透入纸张中。
8. 如权利要求1或2所述的方法，其中，在步骤a)中，同时施加有助于水溶性染料渗透入纸张的表面活性剂和减少水溶性染料渗透入纸张的表面活性剂。
9. 如权利要求1或2所述的方法，其中，在步骤a)中，所述施加在连续的纸幅上进行。
10. 如权利要求1或2所述的方法，其中，在步骤b)中使用含水染料溶液。
11. 如权利要求10所述的方法，其中步骤b)中的所述着色如下进行：在造纸机内部或外部，利用传统的纸张涂布装置和方法，或者通过借助合适的印刷方法，将染料溶液施加至纸张的整个表面上；或者通过喷雾或槽法着色进行所述着色。
12. 如权利要求11所述的方法，其中所述的纸张涂布方法包括通过施胶、压膜、刮刀式涂胶机、刮刀、辊或喷雾将染料溶液施加至纸张上。
13. 如权利要求11所述的方法，其中所述的印刷方法包括喷墨式印刷、胶版印刷、苯胺印刷、照相凹版印刷或借助毛毡或胶辊的印刷。
14. 如权利要求1或2所述的方法，其中，所述图像或图案是图形、印记、规则或不规则的图案、网状结构或任何希望的不均匀的色彩分布。
15. 如权利要求1-14任一项所述的方法获得的纸张。
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| DE10111115A1 (de) * | 2001-03-08 | 2002-10-02 | Technocell Dekor Gmbh & Co Kg | Rohpapier mit verbesserter Bedruckbarkeit |
| ATE312238T1 (de) * | 2003-01-15 | 2005-12-15 | M Real Oyj | Gemustertes papier mit verbesserten druck- und beschriftungseigenschaften |
| EP1522629A1 (de) * | 2003-10-08 | 2005-04-13 | M-real Oyj | Beschichtetes Papier als Druckstoff |
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2003
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- 2003-12-19 WO PCT/EP2003/014624 patent/WO2004063465A1/en active Application Filing
- 2003-12-19 CN CNB2003801088842A patent/CN100412269C/zh not_active Expired - Fee Related
- 2003-12-19 US US10/542,463 patent/US7591926B2/en not_active Expired - Fee Related
- 2003-12-19 CA CA002507818A patent/CA2507818A1/en not_active Abandoned
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Patent Citations (1)
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|---|---|---|---|---|
| CN1539043A (zh) * | 2001-08-01 | 2004-10-20 | �����ķ-�Ӷ�˹�� | 图案纸 |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2004063465A1 (en) | 2004-07-29 |
| ATE312238T1 (de) | 2005-12-15 |
| DE60302642T2 (de) | 2006-08-10 |
| JP2006513331A (ja) | 2006-04-20 |
| US7591926B2 (en) | 2009-09-22 |
| HK1085249A1 (en) | 2006-08-18 |
| EP1439263B1 (en) | 2005-12-07 |
| US20060185807A1 (en) | 2006-08-24 |
| JP4695396B2 (ja) | 2011-06-08 |
| EP1439263A1 (en) | 2004-07-21 |
| AU2003296689A1 (en) | 2004-08-10 |
| CA2507818A1 (en) | 2004-07-29 |
| CN1738944A (zh) | 2006-02-22 |
| DE60302642D1 (de) | 2006-01-12 |
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