[0067]为了提高热凝固速度往往是有利的至少有一个热反应性单体或预聚物在运营车辆平均不会少于3,特别是不得少于10交联群,每个有本分子。这种单体和预聚物往往具有较高的分子量,因而倾向于提高油墨的粘度。 Hence such monomers and polymers are preferably present at not more than 10% by weight on the total etch-resist ink.因此,这种单体及聚合物的最好的礼物时体重不超过10%的总蚀刻,抵制油墨。 Examples of polymers which have on average not less than 10 cross-linking groups per molecule include for example polyols, polyisocyanates, polyepoxy, polyamines and polyimines, poly(meth)acrylates and poly siloxanes.聚合物的平均不超过10交叉连接不到每分子团体有例子包括,例如多元醇,聚异氰酸酯,环氧,聚胺和polyimines,聚(甲基)丙烯酸酯和聚硅氧烷。 Examples of monomers which have on average not less than 3 cross-linking groups per molecule include for example tri, tetra, penta and hexa functional isocyanates, alcohols, amines, epoxys, (meth)acrylates, siloxanes and imines.其中的单体平均不超过3交叉连接不到每分子团体有例子包括,例如三,四,五溴和六功能异氰酸酯,醇,胺,epoxys,(甲基)丙烯酸酯,硅氧烷和亚胺。
[0068] Preferably the thermally curable ink is printed at a firing temperature of less than 100° C., more preferably less than 80° C., especially less than 50° C. and most especially at approximately 25° C. Thus a preferred ink for thermally curing etch-resist inks has a viscosity of less than 30cPs at 25° C. A preferred method for ink jet firing is using a piezo ink jet printer (rather than a thermal ink jet printer). [0068]最好的热固化油墨印刷,在不到100℃,更最好小于80℃,特别是低于50℃,最特别是烧的温度约为25℃,因此首选蚀刻的热固化油墨的抵抗油墨在25 ° C的一种喷墨发射的首选方法少于30cPs粘度使用的是压电喷墨打印机(而不是热喷墨打印机)。 Preferably piezo firing is carried out at approximately 25° C.最好压电射击过程是在大约25℃
Preferred Etch -Resist And Carrier Vehicle Ink Embodiments 首选刻蚀抵制和运营车辆油墨的体现
[0069] Although the above carrier vehicle embodiments are preferred it will be readily appreciated by those skilled in the art that a multitude of approaches within the present invention exist where aspects of on
Component Containing at Least On
[0070] The metal chelating group may be any group which can form a bond with the metal or alloy and especially with iron and ferro alloys. [0070]的金属螯合组可能是任何小组,能够形成一个与金属或合金的债券,特别是与铁和铁合金。 The surface of the metal or alloy may optionally be prepared prior to applying the etch-resist ink.在金属表面或合金可以选择之前编写应用蚀刻,抵制油墨。 This preparation can be effected by atmospheric exposure or can be the result of a chemical or physical treatment process.这样的准备,可以做到的大气环境,也可以是化学或物理处理过程的结果。 Atmospheric exposure often results in the formation of oxides (eg iron, aluminium, zinc), hydrated oxides (eg Fe 3 O 4 . xH 2 O) and carbonates (eg copper).经常暴露在大气的氧化物的生成结果(如铁,铝,锌),水合氧化物(如四氧化三铁。新华2 O)和碳酸盐(如铜)。 Examples of chemical surface treatments are acid etching (eg HCl, HNO 3 , H 2 SO 4 , H 3 PO 4 ) and oxidizer etching (eg persulphates and perborates).化学表面处理的例子有酸蚀(如盐酸, 硝酸 ,以H 2 SO 4,? 3 PO 4计 )和氧化剂蚀刻(如硫酸盐和perborates)。 Examples of physical treatments are heating, plasma exposure and irradiation.物理治疗的例子有暖气,等离子暴露和照射。 The metal chelating group or groups are capable of binding with the surface of the metal or alloy without any preparation although adhesion is often improved following such pretreatments.在金属螯合组或团体都能够处理的金属表面或没有任何准备合金虽然粘连往往有所改善等预处理约束力。
[0071] Examples of metal chelating groups include hydroxides, especially aryl or heteroaryl hydroxides such as phenolic hydroxides; amines which may be aliphatic, aryl or heteroaryl; mercaptans which may be aliphatic, aryl or heteroaryl; carboxylic acids which may be aliphatic, aryl or heteroaryl; oximes and ketoximines; acetarylamides; hydroxy silanes and silicones; N-containing heterocycles such as imidazoles, benzimidazoles, triazoles, benzotriazoles, thiazoles, isothiazoles, acid anhydrides, and more preferably acid groups (especially carboxylic acid groups, phosphoric acid groups, polyphosphoric acid groups, phosphonic acid groups, sulphuric acid groups and sulphonic acid groups). [0071]金属螯合组的例子包括氢氧化物,特别是芳基或如酚醛氢氧化物杂氢氧化物;胺可能是脂肪族,芳基或杂;硫醇可能是脂肪族,芳基或杂,这可能是脂肪族,芳基或羧酸杂;肟和ketoximines; acetarylamides;羟基硅烷和有机硅,含N,如咪唑,苯并咪唑类,三唑类,苯并三氮唑,噻唑类,isothiazoles,酸酐杂环,多最好酸组(特别是羧酸团体,磷酸,团体,多聚酸组,膦酸组,硫酸团体和磺酸组)。 Where more than on
[0072] Less preferred metal chelating groups are hydroxides, amines which may be aliphatic, aryl or heteroaryl; or mercaptans which may be aliphatic, aryl or heteroaryl. [0072]次选项金属螯合组的氢氧化物胺可能是脂肪族,芳基或杂;或硫醇可能是脂肪族,芳基或杂。
[0073] More preferred metal chelating groups are ketoximines; acetarylamides; hydroxy silanes and alkoxy silanes; aryl or heteroaryl hydroxides (such as phenolic hydroxides); N-containing heterocycles (preferably imidazoles, benzimidazoles, triazoles, benzotriazoles, thiazoles, isothiazoles); acid anhydrides; β-diketones, β-keto esters, β-keto aldehydes, β-keto heterocycles; and acid groups (particularly carboxylic acid, phosphoric acid, polyphosphoric acid and sulphonic acid groups). [0073]更多的首选金属螯合组ketoximines; acetarylamides;羟基烷氧基硅烷和硅烷;芳基或杂环氢氧化物(如酚醛氢氧化物);含N杂环化合物(最好咪唑,苯并咪唑类,三唑类,苯并三氮唑,噻唑类,isothiazoles);酸酐;β-二酮,β-酮酯,β-酮醛,β-酮杂环化合物;和酸组(特别是羧酸,磷酸,聚磷酸和磺酸组)。 Especially preferred metal chelant groups are β-diketones, β-keto esters, β-keto aldehydes and β-keto heterocycles.尤其是首选的金属螯合剂组β-二酮,β-酮酯,β-酮醛,β-酮杂环化合物。
[0074] An especially preferred metal chelating group is a carboxylic acid group. [0074]一个特别的首选金属螯合组是羧酸组。
[0075] On
[0076] For hot melt etch-resist inks it is preferred that the carrier vehicle is a wax or polyamide polymer containing at least on
[0077] Alternatively the metal chelating group can be present in the carrier vehicle as a long chain fatty acid. [0077]另外的金属螯合组可以存在于一个长链脂肪酸承运人车辆。 Suitable long chain fatty acids include long chain (preferably C 6-30 ) aliphatic carboxylates such as palmitates, stearates, laurates and the like.适合长链脂肪酸包括长链(最好荤6-30),如棕榈酸,硬脂酸盐,laurates等脂肪族羧酸酯。
[0078] For thermally curable etch-resist inks the thermally reactive liquid monomer preferably contains at least on
[0079] For volatile etch-resist inks the resin preferably contains at least on
[0080] Preferably the resin contains at least on
[0081] It is preferred that the amount of metal chelating groups in the final solidified etch-resist ink is not less than 1.4×10 -5 moles per g, more especially not less than 3.5×10 -5 moles per g and especially not less than 5.6×10 -5 moles per g. Preferably the amount of metal chelating groups in the solidified etch-resist ink is not greater than 4.2×10 -3 moles per g, more preferably not greater than 2.8×10 -3 moles per g and especially not greater than 1.4×10 -3 moles per g. [0081]这是倾向于的金属量螯合组的最后凝固蚀刻,油墨可不小于1.4 × 10 -5每克黑痣,更是不小于3.5 × 10 -5,特别是每克不痣小于5.6 × 10 -5摩尔每克最好的金属量螯合组的凝固蚀刻,油墨可不大于4.2 × 10 -3每克黑痣,更最好不大于2.8 × 10 -3每摩尔克,特别是不大于1.4 × 10 -3每克痣 Preferred solidified etch-resist inks contain from 1.4×10 -5 to 4.2×10 -3 moles per g, more preferably from 3.5×10 -5 to 2.8×10 -3 moles per g and especially 5.6×10 -5 to 1.4×10 -3 moles per g of metal chelating groups.首选固化刻蚀抵抗油墨含有1.4 × 10 -5?4.2 × 10 -3每克黑痣,更最好是从3.5 × 10 -5?2.8 × 10 -3每克痣,尤其是5.6 × 10 -5?1.4 × 10 -3每克痣金属螯合组。
Components Containing at Least On
[0082] As hereinbefore described acid groups and especially carboxylic acid groups are the preferred metal chelating groups. [0082]为上文所描述的基团,特别是羧酸群体是他们的首选金属螯合组。 Such groups exhibit especially good adhesion properties with iron and ferro alloys.这些群体展览用铁和铁合金,特别是良好的粘接性能。 Acid chelating groups also aid the optional removal of the etch-resist after the etching step by treatment with an alkaline aqueous medium.酸螯合组还援助了蚀刻可选去除抵制通过治疗后,蚀刻与碱性水溶液中的一步。
[0083] The acid group or groups in the component in the carrier vehicle may be in the salt form but are preferably in the free acid form. [0083],酸组中或在运营商的汽车部件集团可能会在盐的形式,但最好是在游离酸形式。 Preferred salts forms include mono valent metal salts (eg sodium, potassium and lithium salts) as well as ammonium, substituted ammonium, quaternary ammonium, pyridinium and benzalkonium salts.首选盐的形式包括单价金属盐类(如钠,钾,锂盐)以及氨,取代铵,季铵盐,吡啶和苯扎盐。 Such salts are not strongly chelating with the acid functional group and we have found the process of the present invention results in the etch-resist inks having improved adhesion to metal and alloy surfaces when such salts are used.这种盐不坚决与酸螯合官能团,我们已经找到了在本发明的蚀刻结果的过程中,抵抗油墨附着力得到了提高金属和合金的表面时,这种盐的使用。
[0084] It is preferred that at least on
[0085] In some embodiments where adhesion and alkali removability need to be independently controlled it is preferable that the carrier vehicle comprises two or more types of metal chelating groups wherein at least on
The Colorant 该着色
[0086] The colorant, when present, is preferably a pigment and may be organic or inorganic including those pigments with surface modification which facilitates self dispersion in the etch-resist ink. [0086]着色剂,如果存在,是最好的颜料,可能是有机或无机包括与表面改性这有助于在蚀刻自我分散的颜料墨水抗拒。 The pigment may be from any of the recognised classes of pigments described, for example, in the Third Edition of the Colour Index (1971) and subsequent revisions of and supplements thereto under the chapter headed "Pigments".这种色素可能是从认可的颜料类的任何描述,例如,在颜色索引(1971年)和和补充文件的后续修订第三版在标题为“颜料”的一章。 Examples of inorganic pigments are titanium dioxide, Prussian blue, cadmium sulphide, iron oxides, vermillion, ultramarine and the chrome pigments, including chromates, molybates and mixed chromates and sulphates of lead, zinc, barium, calcium and mixtures and modifications thereof which are commercially available as greenish-yellow to red pigments under the names primrose, lemon, middle, orange, scarlet and red chromes.无机颜料的例子有二氧化钛,普鲁士蓝,硫化镉,氧化铁,朱红色的,群青和铬颜料,包括铬,molybates和混合铬和铅的硫化物,锌,钡,钙和混合物和修改其商业性可作为黄绿色的名称下淡黄色,柠檬,中,橙色,红色和红色至红色颜料chromes。 Examples of organic pigments are those from the azo, diazo, condensed azo, thioindigo, indanthrone, isoindanthrone, anthanthrone, anthraquinone, isodibenzathrone, triphendioxazine, quinacridone and phthalocyanine series, especially copper phthalocyanine and its nuclear halogenated derivatives, and also lakes of acid, basic and mordent dyes.有机颜料的例子是从偶氮染料,偶氮,浓缩偶氮,硫靛染料,阴丹士林,isoindanthrone,anthanthrone,蒽醌,isodibenzathrone,triphendioxazine,喹吖啶酮和酞菁的系列,特别是铜酞菁及其核卤化衍生物,也是酸,基本湖泊和波音染料。 Carbon black, although strictly inorganic, behaves more like an organic pigment in its dispersing properties.碳黑色,虽然严格无机,表现更像是一个在其分散性有机颜料。 Preferred organic pigments are phthalocyanines, especially copper phthalocyanines, monoazos, diazos, indanthrones, anthanthrones, quinacridones and carbon blacks.首选有机颜料酞菁染料,特别是铜酞菁染料,monoazos,diazos,indanthrones,anthanthrones,quinacridones和炭黑。
[0087] A preferred colour of colourant for the etch-resist ink is blue. [0087]了着色剂的蚀刻首选的颜色是蓝色的墨水抵制。
[0088] The pigment is typically incorporated into the etch-resist ink jet ink composition by milling it together with on
[0089] The ratio of dispersant to dispersant synergist is typically from 1:1 to 10:1 by weight and is preferably about 5:1 by weight. [0089]分散剂分散剂增效剂的比例通常是从1:1到10:1的重量和最好是5:1左右的重量。 The total amount of dispersant and dispersant synergist to pigment may vary over wide limits and is typically from 50% to 150% by weight relative to the weight of colorant.分散剂和颜料分散剂的增效剂,以总金额可能会有所不同,并在广泛的范围通常在50%的重量相对于着色剂的重量为150%。 The amount of colorant in the etch-resist ink is preferably not greater than 4 parts, more preferably not greater than 3 parts and especially not greater than 2 parts by weight.在蚀刻量着色剂,抗油墨最好不超过4件,更最好不超过3个部分,特别是不超过2重量部分大得多。
[0090] Preferably the amount of colorant in the etch-resistant ink is from 0.01 to 4 parts, more preferably from 0.1 to 3 parts and especially from 0.1 to 2 parts by weight. [0090]最好在etch中的着色剂数量耐油墨是从0.01至4部分,从0.1到3件以上,最好,尤其是从0.1到2重量部分。
Surfactant 表面
[0091] The surfactant, when present, may be any surface-active material which aids the homogeneity of the ink and/or provides desirable surface tension and wetting properties to the resultant ink. [0091]表面活性剂,如果存在,可以是任何表面活性物质的艾滋病油墨的均匀性和/或提供理想的表面张力和润湿性能,以由此产生的墨水。 The surfactant may also be selected to adjust the firing characteristics of the ink composition within the desired limits.表面活性剂也可以选择调整所需的限度内的油墨组成的射击特点。 The surfactant is preferably anionic and especially non-ionic and is preferably aliphatic in nature, optionally containing silicon and/or fluorine atoms.在阴离子表面活性剂是最好的,尤其是非离子,是最好的性质脂肪,可以选择含有硅和/或氟原子。
[0092] Surfactants in inks often bloom to the surface of the solidified ink and cause a mottled or matte appearance. [0092]表面活性剂在墨水往往盛开的固化油墨,造成斑驳或无光的外观表面。 This surfactant bloom may also result in reduced resistance of the etch-resist ink to the conditions of metal or alloy etching.这种表面活性剂盛开也可能导致的蚀刻减少了阻力,抵抗油墨的金属或合金蚀刻条件。 Thus it is preferred that the surfactant contains at least on
[0093] Such reactive surfactants chemically bond especially strongly with carrier vehicles comprising on
[0094] Preferably the surfactant has on
[0095] The etch-resist ink preferably has a surface tension of from 20 to 40 and especially from 25 to 35 mN/m at a temperature of 25° C. Preferably the surface tension is measured by a Du Nouy ring method. [0095]蚀刻,油墨可最好是有一个从20到40的表面张力,尤其是从25到35分钟/米为25 ° C的温度最好是表面张力是由都努伊环的方法来衡量。
[0096] The amount of surfactant in the etch-resist ink is preferably from 0.0 to 1.00 parts and especially from 0.01 to 0.7 parts by weight. [0096]的表面活性剂的蚀刻数额油墨可最好是从0.0到1.00地区,特别是从0.01至0.7按重量部分。
Other Etch -Resist Ink Adjuvants 其他刻蚀抗油墨助剂
[0097] The etch-resist ink may contain other adjuvants which are suitable for use in ink jet printing ink compositions in addition to components A) to C) specified above. [0097]蚀刻,抵制墨水可能包含它是在喷墨打印除了部分油墨成分使用合适的a)至c)上面指定的其他助剂。 Such adjuvants include slip modifiers, thixotropic agents, anti-foaming agents, plasticizers, antioxidants, stabilisers, gloss agents, fungicides, bactericides, organic and/or inorganic filler particles, levelling agents, opacifiers and antistatic agents.这种佐剂包括防滑改性剂,触变剂,抗泡剂,增塑剂,抗氧化剂,稳定剂,光泽剂,杀真菌剂,杀菌剂,有机和/或无机填充物颗粒,平整剂,乳浊剂和抗静电剂。
Preferences for Etch -Resist Inks 为蚀刻偏好 ,抗油墨
[0098] Preferred etch-resist inks are filtered through a filter having a pore size of 10 microns, more preferably 5 microns and especially 1 micron to remove particles which might block an ink jet nozzle. [0098]首选蚀刻,抵制正在经历一个具有10微米孔径过滤器,最好在5微米以上,尤其是1微米过滤去除油墨粒子,可能会阻止一个喷墨喷嘴。
[0099] Preferably the viscosity of the etch-resist ink is from 8 to 15 cPs (mPas) at the firing temperature. [0099]最好的蚀刻粘度油墨可从8日至15氯化石蜡(海洋保护区时,烧成温度)。
Metal or Alloy 金属或合金
[0100] The metal or alloy can be any of those suitable for Photochemical Machining (PCM) and includes metals and their alloys from group IA, group IIA, group IIIB, group IVB, group VB, group VIB, the transition metals, the lanthanides and actinides of the Periodic Table according to Mendeleof, as published for example on the front inside cover of BASIC INORGANIC CHEMISTRY, COTTON/WILKINSON/GAUS, second Ed, ISBN 0-471-85151-5. [0100]金属或合金可以是那些对光刻加工(的PCM)适合任何和包括金属和保险业从集团,集团国际投资协定,组IIIB部,组IVB部,Vb组,组VIB的,过渡金属,镧系合金和锕系元素的周期表根据Mendeleof,作为在里面的基础无机化学,棉/威尔金森覆盖前面的例子出版/高斯,第二版,书号0-471-85151-5。
[0101] Suitable metals and alloys include aluminium, bronze, beryllium, chromium, columbium, constantan, copper and copper alloys, gold, nickel and nickel alloys, lead, magnesium, molybdenum, niobium, platinum, silver, stainless steel, mild steel, tin, titanium, tungsten, vanadium, zinc and zirconium. [0101]适用于金属和合金包括铝,铜,铍,铬,铌,镍铜合金,铜及铜合金,金,镍和镍合金,铅,镁,钼,铌,铂,银,不锈钢,低碳钢,锡,钛,钨,钒,锌,锆。 Preferred metals and alloys are stainless steel, mild steel, beryllium, beryllium copper, copper; Iconel, Kovar, Monel and other nickel alloys especially Ferro nickel alloys such as Invar and alloy 42; nickel, aluminium, brass, molybdenum and titanium.首选金属和合金,不锈钢,低碳钢,铍,铍铜,铜; Iconel,镍钴合金,蒙乃尔等,特别是铁镍合金,如殷钢和镍合金42合金,镍,铝,铜,钼,钛。 Iron and ferro alloys are especially preferred.铁和铁合金特别首选。
[0102] Prior to applying the etch-resist ink to the metal or alloy, the metal surface is preferably cleaned. [0102]之前运用蚀刻,油墨可对金属或合金,金属表面最好是清洁。 Suitable cleaning methods known in the art include rinsing in organic solvent, rinsing with aqueous detergent solution, mechanical abrasion such as sand-blasting, micro-etching with aqueous acids (eg HCl and H 2 SO 4 ) and aqueous oxidative cleaning with, for example, persulphate or perborate.适当的清洗在艺术已知的方法包括在有机溶剂,与水清洗剂溶液冲洗,机械磨损,如喷砂,微蚀刻与水酸(如盐酸和H 2 SO 4计 )和水的氧化清洗,例如, ,过硫酸钾或过硼酸盐。
Printing Process 印刷工艺
[0103] The etch-resist ink may be applied to the metal or alloy surface using any suitable ink jet printing processes. [0103]蚀刻,抵制油墨可应用于金属或合金表面使用任何合适的喷墨印刷的过程。 In these processes ink is fired from an ink jet printer, preferably at a firing temperature of from 10 C. to 150 C. Printing can be performed, for example, by a thermal ink jet printer or an electrostatic ink jet printer but preferably the printer is a piezo ink jet printer.在这些过程中油墨是从一架喷墨打印机,最好是从10长到150长印刷可以进行,例如,烧成温度,由热喷墨打印机或喷墨打印机静电但最好的打印机是一种压电喷墨打印机。 Printing may be carried out either continuously or by a drop of demand (DOD) process.印刷的工作,可连续或由需求下降(国防部)的过程。 The thickness of the ink jet printed etch-resist can be varied widely according to the specific requirements of the metal or alloy and etchant used.在喷墨印刷蚀刻厚度,抵御可以根据不同的广泛的金属或合金和使用蚀刻剂的具体要求。 Preferably the etch-resist ink is applied as a layer of from 1 to 50 microns thick. In some cases it is advantageous to vary the thickness of the etch-resist over the metal or alloy surface.最好是蚀刻,抗油墨的应用是作为一个从1到50微米厚的一层。在某些情况下,有利于不同的蚀刻厚度抵制在金属或合金表面。 This can facilitate greater versatility and control in the etch step.这可以促进在蚀刻步骤更为灵活和控制。 In the case of hot melt inks the etch-resist ink is heated prior to and during firing to melt and liquefy the ink.在热熔胶油墨蚀刻案件油墨可加热前和在发射融化和液化墨水。
Solidification Step 凝固步
[0104] The solidification step may be performed by any means known in the art other than by exposure of the etch-resist ink to actinic light and/or particle beam radiation sources. [0104]的凝固步骤可能会以任何方式出名的艺术品,而不是由其他蚀刻曝光,抵制油墨作用光和/或粒子束辐射源进行。 That is to say solidification cannot be by exposure to actinic light, particle beam radiation or a combination of actinic light and particle beam radiation.这就是说凝固不能被暴露在光化光,辐射或粒子光束的作用光辐射和粒子光束的组合。 Preferably solidification is achieved by heating, by evaporation of at least on
Etching Step 蚀刻步骤
[0105] After solidification of the etch-resist ink the metal or alloy is subjected to a chemical etching process to remove those parts of the metal or alloy which are not protected by the solidified etch-resist ink. The removal of this metal or alloy results in the desired etch pattern. The etching may be restricted to the surface or may fully penetrate the metal or alloy. [0105]蚀刻后凝固,油墨可在金属或合金都需经过化学蚀刻工艺,以消除那些对金属或合金零件不属于由固化蚀刻,油墨可保护。这项金属切除或合金在所需的蚀刻模式的结果。凹槽蚀刻可能只限于表面或可完全穿透金属或合金。
[0106] The chemical etching may be carried out by any means appropriate to the metal or alloy concerned. [0106]的化学蚀刻可进行任何适当的手段对金属或合金关注。 Table 2 summarises the preferred etchants for preferred metals and alloys.表2总结为首选的金属和合金的首选腐蚀剂。
TABLE -US-00002 TABLE 2 Metal Common etchants* Temperature ° C. Stainless steel 35-42 °Be FeCl 3 35-55 (many grades) Mild steel 35-42 °Be FeCl 3 35-55 Beryllium copper 30-42 °Be FeCl 3 or 40-55 ammoniacal copper or 33 °Be acidic CuCl 2 Copper and copper 30-42 °Be FeCl 3 or 40-55 alloys ammoniacal copper or 33 °Be acidic CuCl 2 Inconel and other 38-42 °Be FeCl 3 or 45-55 high nickel alloys conc nitric/conc hydrochloric acid/water 1:1:3 Aluminium 20% NaOH 60-90 or conc hydrochloric 20-65 acid/water 1:4 55 or alkaline potassium ferricyanide Brass 30-42 °Be FeCl 3 or 40-55 ammoniacal copper or 33 °Be acidic CuCl 2 Molybdenum Alkaline potassium 55 ferricyanide 40-55 or 40 °Be Fe(NO 3 ) 3 Titanium 10-50% HF 30-50 (optionally with HNO 3 ) *The concentration of etchant (column 2) is measured in Degrees Baume (°Be) where: °Be = 145 (SG - 1/SG); and SG is the specific gravity (density) of the solution. 表美- 00002表2金属共同腐蚀剂*温度° C的不锈钢35-42 °成为氯化铁三 35-55(许多年级)低碳钢35-42 °成为氯化铁三 35-55铍铜30-42 °成为氯化铁3或40-55氨铜或33 °是酸性CuCl的2铜及铜30-42 °成为氯化铁三或40-55合金氨铜或33 °是酸性CuCl的2镍铬铁合金和其他38-42 °成为三氯化铁3或45-55高镍合金浓硝酸/浓盐酸/水1时01分03秒铝20%的NaOH浓盐酸60-90或20-65酸/水1:4 55或氰化钾铜30-42 °碱性钾成为三氯化铁3或40-55氨铜或33 °是酸性CuCl的二钾55钼碱性铁氰化钾40-55或40 °成为铁Fe(NO 3)3钛10-50%的HF 30-50(与硝酸可选)*的浓度对侵蚀剂(栏2)测量波美度(°成为)其中:°成为= 145(法兴- 1/SG);和SG是比重(密度的解决方案)。
[0107] Etching is typically carried out at a temperature from 20 to 100° C. (preferably between 25 and 60° C.) and includes spraying or dipping where the metal or alloy may be contacted with the chemical etchant in either the horizontal or vertical position. [0107]蚀刻通常是工作在从20日的温度在100 ° C(最好是25至60摄氏度),包括喷洒或浸泡在金属或合金可能与无论是在水平或接触化学蚀刻剂垂直位置。 Spraying is preferred, especially where the metal or alloy is in the vertical position since this allows for quicker removal of the chemical etchant containing removed metal and/or alloy.喷涂是首选,尤其是在金属或合金的,因为这更快含有的化学去除金属蚀刻剂和/或合金的撤消,允许垂直位置。 The speed of etching may be accelerated by agitating the chemical etchant, for example using sonic agitation.在蚀刻速度可能加速搅拌化学腐蚀剂,例如使用声波搅拌。
Post Etch Treatment 邮政蚀刻处理
[0108] After the metal or alloy has been etched the chemical etchant is preferably rinsed with an organic solvent or more preferably with water to remove traces of the chemical etchant. [0108]在金属或合金,自此铭刻的化学腐蚀剂,是最好的冲洗,并用有机溶剂或水多,最好以消除化学腐蚀剂的痕迹。
Optional Removal of the Etch -Resist Ink 可选的蚀刻去除油墨可
[0109] The solidified etch-resist ink may be left in place on the surface of the metal or alloy. [0109]蚀刻的固化,油墨可可能留在原位上的金属或合金表面。 According to a second aspect of the present invention there is provided a metal or alloy partially coated with a solidified etch-resist ink obtained by the process according to the first aspect of the present invention.根据本发明的第二个方面是提供了有金属或合金的凝固部分蚀刻,抵挡的过程中获得的按本发明的第一个方面油墨涂层。
[0110] The solidified etch-resist ink may be removed after etching. Preferably removal is achieved by chemical treatment and more preferably removal is by treatment with an alkaline medium. [0110]蚀刻的固化,油墨可蚀刻后可能会取消。最好清除将会被更多的化学处理和清除,最好成绩仍然是一个碱性介质中的待遇。 Alkaline removal is especially effective with etch-resist inks which contain on
[0111] Typically alkaline treatment is performed at a temperature from 0 to 100° C., preferably 40 to 60° C. to remove the etch-resist ink. [0111]通常碱处理,是完成的温度从0到100℃,最好是40到60℃消除蚀刻,抵制油墨。
[0112] Alternative (less preferred) methods for removing the solidified etch-resist ink include solvent stripping, heating, abrasion, ultrasound, burning/oxidizing, cutting and plasma treating.凝固去除蚀刻[0112]另类(不太喜欢)方法抗拒油墨包括溶剂清洗,加热,耐磨损,超声波,燃烧/氧化,切割和等离子治疗。 Solvent stripping can be performed in non-polar aprotic solvents (eg aromatic solvents and halogenated solvents) or in polar aprotic solvents (eg Dimethyl sulphoxide, dimethyl formamide, N-methylpyrrolidone etc).溶剂可以进行剥离,在非极性非质子溶剂(如芳烃溶剂和卤化溶剂),或在极性非质子溶剂(如二甲基亚砜,二甲基甲酰胺,N -甲基吡咯烷酮等)。
[0113] Thus according to a third aspect of the present invention there is provided a metal or alloy obtained by the process according to the first aspect of the present invention wherein the solidified etch-resist ink has been removed after etching. [0113]因此,根据本发明的第三方面,提供了有金属或进程取得根据本发明的第一个方面其中蚀刻的凝固合金抵抗油墨蚀刻后已被删除。
Non -Etchable Support 非 Etchable支持
[0114] In embodiments where a non-etchable support has been used, said support is preferably removed at some point after etching. [0114]在体现一种是非etchable支持已被使用,表示支持,最好是在某个时候蚀刻后移除。 The non-etchable support is preferably a non-metallic material, more preferably a ceramic, glass, wood, textile, wax, paper, plastics material or rubber material.非etchable支持是最好的非金属材料,更最好是陶瓷,玻璃,木材,纺织,蜡,纸,塑料材料或橡胶材料。
Preferred Articles 推荐文章
[0115] According to a fourth aspect of the present invention there is provided an article made by the process according to the first aspect of the present invention having a chemically etched surface pattern or design. [0115]根据本发明的第四个方面有提供过程中作出了根据本有一个化学腐蚀的表面图案或设计发明的第一个方面的文章。 Examples of specific articles are a grid, a filter, a graticule, a mesh, a light chopper disc, a heat sink plate, a heater element, a screen, colour TV mask, a diaphragm, a shim, a gasket, a washer, a spring, a cog, a link, a probe, a magnetic recording head, a circuit lead frame, an encoder disc, an item of jewelry, a rule, a scale, a clutch plate, an emitter contact, a micro reactor, a suspension lead, an ink jet nozzle plate, a stencil, a razor foil, a bearing, an edge filter, a logo, a nameplate, a decorative plaque, an instrument case, a box, an enclosure and a potentiometer case made by the process of the present invention. Especially preferred articles are those wherein the etchant fully penetrated the metal or alloy in the article具体条款的例子有一个网格,过滤器,一标线,一个网格,一辆轻型直升机光盘,散热片板,一个加热元件,屏幕,彩色电视面具,膜片,一个垫片,垫圈,洗衣机,春天,一个齿轮,一个链接,一个探测器,磁性记录磁头,电路引线框架,编码器光盘,一饰物,一种规则,一个规模,一个离合器片,一个发射联络时,微型反应堆,项目一暂停铅,1喷墨喷嘴板,模具,剃须刀片,轴承,一个边缘滤波器,一个标志,一个铭牌,装饰牌匾,一个仪器的情况,一个盒子,一个外壳和一个电位案件过程中作出了本发明的。尤其是首选的文章是那些其中的腐蚀剂充分渗透到金属或合金的文章
[0116] The present invention is further illustrated by the following non-limiting examples. [0116]本发明进一步受到以下非限制的例子加以说明。 Unless otherwise stated all parts are by weight.除非另有规定的所有部分都按重量。
EXAMPLES 实例
Example 1 示例 1
Etch -Resist Ink (1) 刻蚀油墨可(1)
Preparation of a Thermally Curable Etch -Resist Ink which Comprises Water 一个热固化刻蚀制备油墨可组成水
Preparation of Polymer A 制备聚合物薄膜
[0117] Polymer A is a acrylic copolymer containing 70% by weight of methacrylic acid and 30% by weight of methyl methacrylate prepared by a catalytic chain transfer method to give a polymer having a number averaged molecular weight of approximately 600 as measured by GPC. [0117]聚合物A是丙烯酸共聚物其含有甲基丙烯酸重量70%,按重量的30%甲基丙烯酸甲酯的催化链转移的方法准备给予聚合物具有的平均人数约600分子量为由GPC测定。
[0118] An Etch-resist ink (1) was prepared by mixing water (72 parts), aqueous ammonia solution having a specific gravity of 0.88 (12 parts), Polymer A (12 parts) and Primid® XL552 (4 parts). [0118]一个刻蚀抵抗油墨(1)是由混合水(72件),氨水溶液具有特定的比重为0.88(12件),聚合物甲(12件)和Primid ® XL552(4件)编写的。 Primid® XL552 is a hydroxyl alkyl amide cross-linker supplied by EMS Chemie. Primid ® XL552是羟基烷基酰胺交叉通过EMS化学供应连接器。 Etch-resist ink (1) was printed using a HP deskjet 5500 ink jet printer in the form of a rectangle on
[0119] The Etch-resist ink (1) on the printed film was thermally cured by heating the film to a temperature of 150° C. for 1 hour. [0119]蚀刻,抵御对薄膜的印刷油墨(1)是热加热1小时的电影达150 ° C的温度治愈。 Copper was etched from the unprinted areas of the PEN film using an etchant bath containing a ferric chloride etchant solution of strength 42° Baume supplied by RS.铜蚀刻从PEN薄膜的未印刷领域使用的蚀刻剂浴含有三氯化铁蚀刻剂的力量解决42 °波美由RS供应。 The etching was performed for 10 mins at a temperature of 50° C. The thermally cured Etch-resist ink (1) was then removed from the etched PEN film using an aqueous solution of 2.5% by weight caustic at a temperature of 50° C. for 10 mins.蚀刻是进行了10分钟,以50 ° C的温度热固化刻蚀抵抗油墨(1),不再是从蚀刻PEN薄膜,以50 ° C的温度使用苛性以重量为2.5%水溶液。为10分钟。
[0120] The resultant etched film was rinsed with water and dried in air at 25° C. [0120]由此产生蚀刻电影是用水冲洗和干燥的空气在25 ° C
[0121] The resultant etched film showed a completely unetched area of copper where the original Etch-resist ink (1) print had previously been. Areas where no etch-resist ink was ever present showed full etching of the copper with none remaining in such areas. [0121]由此产生蚀刻的影片中,铜完全未腐蚀× 100范围,有关的原始腐蚀,抗油墨(1)印刷以前。蚀刻看不到的地方,油墨可现在却从未充分显示了铜蚀刻有没有在这些剩余地区。
Example 2 示例 2
Etch -Resist Ink (2) 刻蚀油墨可(2)
Preparation of a Thermally Curable Etch -Resist Ink which is Free from Water 一个热固化刻蚀制备油墨可这是免费的水
[0122] An Etch-resist ink (2) was prepared by mixing 1-methyl-2-pyrrolidinone (84 parts), Primid® XL 552 (4 parts) and Polymer A (12 parts), obtained as described in Example 1. [0122]一个刻蚀抵制油墨(2)是由混合1 -甲基- 2 -吡咯烷酮(84件),Primid ®加大码552(4件)和聚合物甲(12件),准备获取的示例1描述。
[0123] Etch-resist ink (2) was printed in the form of a rectangle on
[0124] The print was thermally cured by heating the board to a temperature of 180° C. for 1 hour. [0124]印制的热治愈加热1小时的董事会,以一个180 ° C的温度。
[0125] Copper was etched from the unprinted areas of the FR4 board using an etchant bath containing a ferric chloride etchant solution of strength 42° Baume supplied by RS. [0125]铜被蚀刻从FR4电路板的未印刷领域使用的蚀刻剂浴含有三氯化铁蚀刻剂的力量解决42 °波美由RS供应。 The etching was performed for 10 mins at a temperature of 50° C.蚀刻是进行了10分钟,以50 ° C的温度
[0126] The thermally cured Etch-resist ink (2) was then removed from the unetched areas of copper by immersing the film in an aqueous solution of 5% by weight caustic at a temperature of 50° C. The resultant etched FR4 board was rinsed with water and dried by air at 25° C. [0126]的热固化刻蚀抵抗油墨(2)然后从铜的未腐蚀× 100区除名的沉浸在了5%水溶液的电影,由重量烧碱为50 ° C的温度由此产生的FR4电路板蚀刻水冲洗和干燥的空气在25 ° C
[0127] The resultant etched board showed a complete area of copper in the areas where the Etch-resist ink (2) had previously been. [0127]由此产生蚀刻板显示等领域的完整的铜领域的刻蚀抵抗油墨(2)以前。 Areas where no etch-resist ink was ever present showed full etching of the copper with none remaining in such areas.蚀刻看不到的地方,抵制墨水始终存在充分显示了铜蚀刻与这些领域尚存没有。
Example 3 示例 3
Etch -Resist Ink (3) 刻蚀油墨可(3)
A Hot Melt Etch -Resist Ink 阿热熔胶刻蚀油墨可
[0128] The black hot melt ink was removed from a Tectonics 3800 printer cartridge, to give Etch-resist ink (3). [0128]黑热熔油墨从3800打印机墨盒构造拆除,给刻蚀抵抗油墨(3)。
[0129] Etch-resist ink (3) was coated in the form of a rectangle on
[0130] Copper was etched from the uncoated areas of the FR4 board using an etchant bath containing a ferric chloride etchant solution of strength 42° Baume supplied by RS. [0130]铜被蚀刻从FR4电路板的涂层领域的腐蚀剂浴使用含有三氯化铁蚀刻剂的力量解决42 °波美由RS供应。 The etching was performed for 10 mins at a temperature of 50° C.蚀刻是进行了10分钟,以50 ° C的温度
[0131] After etching the Etch-resist ink (3) had suffered no damage and remained well, adhered to the FR4 copper surface. [0131]抵制腐蚀后蚀刻油墨(3)有没有损坏,保持良好,坚持的FR4铜表面。 No undercutting could be seen.任何削弱可以看到。 Areas where no etch-resist ink was ever present showed full etching of the copper with none remaining in such areas.蚀刻看不到的地方,抵制墨水始终存在充分显示了铜蚀刻与这些领域尚存没有。
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