WO2008071061A1

WO2008071061A1 - Electromagnetic shielding film and method for producing same

Info

Publication number: WO2008071061A1
Application number: PCT/CN2007/003276
Authority: WO
Inventors: Jianchen Zhang; Xiaoli Wang; Zhixiu Cheng; Fengyong Zhang; Jing Zou
Original assignee: China Lucky Film Group Corporation; Lucky Film Co., Ltd
Priority date: 2006-12-12
Filing date: 2007-11-20
Publication date: 2008-06-19
Also published as: JP2010512653A; KR20090086630A; KR101160731B1; CN101005755B; CN101005755A

Abstract

An electromagnetic shielding film and a method for producing the same. The electromagnetic shielding film is a conductive thin film which includes a supporting body and a filament mesh formed on the supporting body, the filament mesh is formed of metal silver and metal copper plated on the metal silver. Wherein, the metal copper content is of 55-90 mass % of the total mass of the silver and copper metal, the line width of the mesh is 5-25μm, the open area ratio is of 85%-95%, and a surface resistivity is of more than 0 and less than 5Ω/sq. And the producing method includes the steps of: plating silver portion and a protecting portion of the silver portion on the supporting body, applying exposing and developing process to the mesh, the exposed portion forming the metallic silver portion, and the non-exposing portion forming the light-transmitting portion, and applying thickening and activating process to the metallic silver portion, finally the plating metal forming the metallic portion. Low surface resisitivity and good shielding effect are achieved by using the product of this application; and producing method is simple, and suitable for industrialization manufacturing.

Description

一种电磁波屏蔽膜及其制造方法 Electromagnetic wave shielding film and manufacturing method thereof

技术领域 Technical field

本发明涉及一种屏蔽膜，特别涉及一种电磁波屏蔽膜及其制造方法。背景技术 The present invention relates to a shielding film, and more particularly to an electromagnetic wave shielding film and a method of manufacturing the same. Background technique

近年来，伴随着信息化社会的快速发展，与信息相关联的设备急速发展并逐渐得到普及，各种电子设备、通信装置例如 CRT、液晶、 EL、 PDP、 FED等显示装置被广泛用于电视机、个人电脑、车站和机场的导向显示，用于提供各种信息。这些电子设备，弹球盘、自动***等电子控制游戏机、移动电话等通信装置产生的电磁波干扰（EMI)问题也愈来愈严重。 In recent years, with the rapid development of the information society, devices related to information have been rapidly developed and gradually popularized. Various electronic devices and communication devices such as CRT, LCD, EL, PDP, FED and other display devices are widely used in television. Guided display of computers, personal computers, stations and airports for providing a variety of information. Electromagnetic interference (EMI) problems caused by communication devices such as electronically controlled game machines such as pachinko disks and automatic gaming machines, and mobile phones have become more and more serious.

电磁波干扰不仅会影响周围电子设备的操作精确度，引起误操作，而且还会对人体健康产生不良影响。因此，对电磁波屏蔽材料的要求越来越高。为了适应这样的要求，人们开发出了各种透明导电性薄膜（电磁波屏蔽膜）。例如，日本专利特开平 JP9-53030、特开平 JP11-126024、特开 JP2000-294980 , 特开 JP2000- 357414、特开 JP2000-329934、特开 JP2001- 38843、特开 JP2001-47549、特开 JP2001- 51610、特开 JP2001_5711 0、特开 JP2001-60416就公开了各种屏蔽膜。然而，这些屏蔽膜普遍存在屏蔽效率低的缺点。 Electromagnetic interference not only affects the operational accuracy of surrounding electronic devices, but also causes malfunctions, and it also has adverse effects on human health. Therefore, the requirements for electromagnetic wave shielding materials are increasing. In order to meet such requirements, various transparent conductive films (electromagnetic wave shielding films) have been developed. For example, Japanese Patent Laid-Open No. JP9-53030, Japanese Patent Publication No. JP11-126024, JP-A-JP-2000-294980, JP-A-JP-2000- 357 414, JP-A-2000-329934, JP-A-2001-38843, JP-A-2001-47549, JP-A-2001- Various shielding films are disclosed in Japanese Laid-Open Patent Publication No. JP-A-2001-60416. However, these shielding films generally have the disadvantage of low shielding efficiency.

至于如何制造这些电磁波屏蔽膜材料，通常采用的方法有溅射法、蚀刻法和银络盐扩散转移法等方法。溅射法是指将金属银和铟锡氧化物（IT0) 等高折光率层直接溅射在玻璃基板上，或溅射在 PET膜片上再复合到玻璃基板上。溅射法制备的电磁波屏蔽膜，由于其透光率偏低、表面电阻偏高，限制了它的推广应用范围。蚀刻法是将铜箔贴合在透明的 PET 薄膜上，经光刻形成细线网格的铜质栅网，其制备工艺复杂，成本较高。银络盐扩散转移法是在透明 PET 薄膜上，首先涂以钯、铑等催化核，然后涂上化银乳剂，进行物理显影，再镀覆铜或镍金属膜，此方法由于残留的催化核吸收光，因此存在透光率低等问题。发明内容 As for how to manufacture these electromagnetic wave shielding film materials, methods such as a sputtering method, an etching method, and a silver complex salt diffusion transfer method are generally employed. The sputtering method means that a high refractive index layer such as metallic silver or indium tin oxide (IT0) is directly sputtered on a glass substrate, or sputtered on a PET film and then laminated on a glass substrate. The electromagnetic wave shielding film prepared by the sputtering method limits its popularization and application range due to its low light transmittance and high surface resistance. The etching method is a method of forming a copper foil on a transparent PET film by photolithography to form a copper grid of a fine-line grid, which has a complicated preparation process and high cost. The silver complex salt diffusion transfer method is carried out on a transparent PET film, first coated with a catalytic core such as palladium or ruthenium, and then coated with a silver halide emulsion for physical development, and then plated with a copper or nickel metal film due to the residual catalytic core. Suck Receiving light, there is a problem of low light transmittance. Summary of the invention

本发明解决的技术问题是，提供一种表面电阻低、屏蔽效率高的电磁波屏蔽膜。 The technical problem to be solved by the present invention is to provide an electromagnetic wave shielding film having low surface resistance and high shielding efficiency.

本发明解决的另一技术问题是，提供这种电磁波屏蔽膜的制备方法。解决上述问题的技术方案是： Another technical problem to be solved by the present invention is to provide a method of preparing such an electromagnetic wave shielding film. The technical solution to solve the above problems is:

一种电磁波屏蔽膜，是由支持体和在其上所形成的细线栅网构成的导电性薄膜，细线栅网由金属银及其上镀覆的铜构成，其特征在于，所含铜的质量占银铜总质量的 55 % ~ 90 % , 栅网线宽 5 ~ 25μπι，开孔比 85 % ~ 95 % , 表面电阻大于 0小于 5Ω/口。 An electromagnetic wave shielding film is a conductive film composed of a support and a fine wire grid formed thereon, and the thin wire mesh is composed of metallic silver and copper plated thereon, and is characterized by containing copper The mass accounts for 55 % ~ 90 % of the total mass of silver copper, the grid line width is 5 ~ 25μπι, the opening ratio is 85% ~ 95%, and the surface resistance is greater than 0 less than 5 Ω / port.

上述电磁波屏蔽膜，所述细线栅网厚为 2. 5 ~ 8μιη。 In the electromagnetic wave shielding film, the thin wire mesh has a thickness of 2. 5 to 8 μm.

一种电磁波屏蔽膜的制造方法，它包括：在支持体上涂布银盐层及其保护层，并施以栅网曝光和显影处理过程，曝光部分形成金属银部分，未曝光部分形成透光部分，金属银部分进行加厚、活化处理，镀覆金属形成导电金属部分。 A method for manufacturing an electromagnetic wave shielding film, comprising: coating a silver salt layer and a protective layer on the support, and applying a grid exposure and development process, the exposed portion forms a metallic silver portion, and the unexposed portion forms a light transmission In part, the metallic silver portion is thickened and activated, and the metal is plated to form a conductive metal portion.

上述制备方法中，其中所述的金属银部分加厚采用银加厚或铜加厚。上述制备方法中，其中所述的活化处理采用重金属离子水溶液活化的方法。 In the above preparation method, the metal silver portion is thickened by silver thickening or copper thickening. In the above preparation method, the activation treatment is carried out by a method of activating a heavy metal ion aqueous solution.

上述制备方法中，其中所述的活化处理采用钯离子、金离子或银离子水溶液活化的方法。 In the above preparation method, the activation treatment is carried out by a method of activating palladium ions, gold ions or an aqueous solution of silver ions.

上述制备方法中，其中所述的镀覆金属采用化学镀。 In the above preparation method, the plated metal is electrolessly plated.

本发明中使用的支持体，可以是由聚对苯二曱酸乙二醇酯树脂、双乙酸酯树脂、三乙酸酯树脂、聚乙烯、聚丙烯、聚苯乙烯、聚氯乙烯树脂、聚酮醚，聚砜、聚醚砜、聚碳酸酯、聚酰胺、丙烯酸树脂或三醋酸纤维素等构成的单层或多层薄膜。从透光性、耐热性和价格等方面综合考虑，首选基材为聚对苯二曱酸乙二醇酯（PET )薄膜。 The support used in the present invention may be polyethylene terephthalate resin, diacetate resin, triacetate resin, polyethylene, polypropylene, polystyrene, polyvinyl chloride resin, A single or multilayer film composed of a polyketide, polysulfone, polyethersulfone, polycarbonate, polyamide, acrylic resin or cellulose triacetate. Comprehensive consideration in terms of light transmission, heat resistance and price, preferred The substrate is a polyethylene terephthalate (PET) film.

本发明使用的！ ¾化银乳剂可以按照在照相感光材料领域中所使用的卤化银乳剂的制造方法来制造。卤化银乳剂通常是通过将硝酸银水溶液和氯化钠或溴化钾等 1¾化物水溶液在明胶存在的条件下混合乳化而制造。 The invention is used! The silver emulsion can be produced by a method of producing a silver halide emulsion used in the field of photographic light-sensitive materials. The silver halide emulsion is usually produced by mixing and emulsifying an aqueous solution of silver nitrate and an aqueous solution of sodium chloride or potassium bromide in the presence of gelatin.

对本发明中所使用的 1¾化银组成而言，优选为氯化银，即组成中含有 For the silver composition of the 13⁄4 used in the present invention, silver chloride is preferred, that is, the composition contains

50%或更多的氯离子，可以含有碘离子和溴离子。优选颗粒尺寸为 0. 1 ~ l OOOnm, 更优选为 1- 200nm。卤化银的晶体形状不受限制，可以是立方体、八面体、球体、扁平颗粒或薄片状挛晶。 50% or more of chloride ions, which may contain iodide and bromide. Preferably, the particle size is from 0.1 to 1 OOOnm, more preferably from 1 to 200 nm. The crystal shape of the silver halide is not limited and may be a cube, an octahedron, a sphere, a flat particle or a flaky twin.

为了获得较高的反差， |¾化银乳剂中需掺杂金属离子，特别是过渡金属离子如铑和铱。铑离子和铱离子有不同的配位体化合物，配位体包括氰根离子、卤素离子、硫氰酸根离子、亚硝酰基离子、水和氢氧根离子等。每摩尔银的优选用量为 Ι ίΤ - Ι Ο— ²摩尔，更优选用量为 10— ⁹ ~ 10— ³摩尔。 In order to obtain a higher contrast, metal ions are doped in the |3⁄4 silver emulsion, especially transition metal ions such as ruthenium and osmium. The cerium ion and the cerium ion have different ligand compounds, and the ligand includes a cyanide ion, a halogen ion, a thiocyanate ion, a nitrosyl ion, water, and a hydroxide ion. Preferred amount per mol of silver for Ι ίΤ - Ι Ο- ² mol, and more preferably in an amount of ^10-9 - ^10-3 mol.

在本发明中，涂布银盐层和保护层等时，可采用浸涂、挤压涂、滑动涂敷（s l ide coat ing ), 帘涂、棒涂、气刀涂敷、辊涂、照相凹版涂敷、喷涂等涂布方式进行涂布。本发明中优选上述涂布法设置成为通常的连续、 - 均匀的涂层。 In the present invention, when coating a silver salt layer, a protective layer, or the like, dip coating, extrusion coating, slide coating, curtain coating, bar coating, air knife coating, roll coating, and photography may be employed. Coating is performed by a coating method such as gravure coating or spray coating. In the present invention, it is preferred that the above coating method be provided as a usual continuous, uniform coating.

本发明中使用的曝光光源可以为紫外灯或高压汞灯等。借助于该曝光光源将带有网格图案的模板印制到卤化银胶片上，或用激光将网格图案扫描在卤化银胶片上。 The exposure light source used in the present invention may be an ultraviolet lamp or a high pressure mercury lamp or the like. The template with the grid pattern is printed onto the silver halide film by means of the exposure light source, or the grid pattern is scanned on the silver halide film with a laser.

本发明中卤化银乳剂层曝光后需进行显影，可以使用传统照相材料中的显影技术，显影剂不受限制，但优选使用高反差显影剂，如市售的 D-19、 D- 72、 D-1 D- 8和 G-48等。曝光显影后形成金属银部分和透光部分。 In the present invention, the silver halide emulsion layer is subjected to development after exposure, and development techniques in a conventional photographic material can be used. The developer is not limited, but it is preferable to use a high contrast developer such as commercially available D-19, D-72, D. -1 D- 8 and G-48, etc. A metal silver portion and a light transmitting portion are formed after exposure and development.

本发明中金属银部分进行加厚、活化处理，镀覆金属形成导电金属部分。导电金属部分的金属颗粒可以是铜、铝、镍、铁、金、钴、钯等金属颗粒。但从导电性和成本来综合考虑，导电金属部分优选为铜。 In the present invention, the metallic silver portion is thickened and activated, and the metal is plated to form a conductive metal portion. The metal particles of the conductive metal portion may be metal particles such as copper, aluminum, nickel, iron, gold, cobalt, palladium or the like. However, from the viewpoint of conductivity and cost, the conductive metal portion is preferably copper.

本发明中使用的加厚可以采用银加厚或铜加厚，银加厚工艺是用一种还原剂将可溶性银盐溶液中的金属银离子还原成金属银，生成很细的银慢慢沉积在适当的位置。这种金属银在金属部分的沉积速度比在非银的透明区的沉积要快的多，基本上是以与银含量成正比的方式沉积的。因此使用银加厚可以使银镀敷或沉积在银细线图案部分，基本上不沉积到支持体的透明部分。铜加厚目的同银加厚相同，对银细线图案部分进行粗化，加厚液的组成包括下列成分：二价铜离子，一种酸才艮离子，例如：石克酸根离子、硝酸根离子、醋酸根离子等离子；一种卤素离子，例如氯离子、溴离子、碘离子等离子。银加厚和铜加厚温度一般为室温，加厚时间控制在 10秒 -30 分钟之内，优选为 1分钟 -20分钟。 The thickening used in the present invention can be thickened by silver or thickened by copper, and the silver thickening process is used with one kind of The original agent reduces the metallic silver ions in the soluble silver salt solution to metallic silver, and the fine silver is slowly deposited in a suitable position. This metallic silver deposits in the metal portion much faster than in the non-silver transparent region, and is deposited substantially in proportion to the silver content. Therefore, silver thickening can be used to plate or deposit silver on the silver thin line pattern portion, and substantially not deposited on the transparent portion of the support. The copper thickening purpose is the same as the silver thickening, and the silver thin line pattern portion is roughened. The composition of the thickening liquid includes the following components: divalent copper ions, an acid cerium ion, for example: sulphate ion, nitrate Ion, acetate ion plasma; a halogen ion, such as chloride ion, bromide ion, iodide ion plasma. The silver thickening and copper thickening temperature is generally room temperature, and the thickening time is controlled within 10 seconds to 30 minutes, preferably 1 minute to 20 minutes.

本发明中活化的目的是在透明支持体的银细线图案表面形成有利于化学镀铜充分的活性点，以加速化学镀铜的速度。活化可采用公知的方法进行，如敏化 -活化两步处理法，即首先用氯化亚锡水溶液进行敏化处理，然后再用氯化钯、三氯化金或硝酸银水溶液进行活化处理；胶体钯活化法等。本发明由于前期进行了银加厚或铜加厚，因此可直接应用重金属离子进行活化，即用氯化^!巴、三氯化金或硝酸银水溶液进行活化。 The purpose of the activation in the present invention is to form a sufficient active point on the surface of the silver fine line pattern of the transparent support to facilitate the chemical copper plating to accelerate the speed of electroless copper plating. The activation can be carried out by a known method, such as a sensitization-activation two-step treatment, that is, first sensitization treatment with an aqueous solution of stannous chloride, followed by activation treatment with palladium chloride, gold trichloride or silver nitrate aqueous solution; Colloidal palladium activation method, etc. Since the invention has been subjected to silver thickening or copper thickening in the early stage, it can be directly activated by heavy metal ions, that is, activated by chlorination, aluminum trichloride or silver nitrate aqueous solution.

本发明中镀覆金属采用化学镀形成导电金属部分。传统的化学镀技术可以使用。例如印刷电路板化学镀技术。化学镀首选为化学镀铜。化学镀铜是将经上述各种处理方法处理后的有充分活性点的银细线图案的透明支持体放到镀铜液中进行化学镀铜。化学镀铜液一般由铜盐、络合剂、还原剂和其它添加剂组成。铜盐提供被沉积的铜离子，可以用石 Τυ酸铜、醋酸铜或氯化铜等可溶性铜盐。还原剂是将镀液中的可溶性的铜离子还原成金属铜沉积在透明支持体的银细线图案上形成金属铜镀层，还原剂可采用曱醛、硼氢酸钠、次磷酸钠等物质。络合剂是防止在碱性中发生氢氧化铜沉淀产生，将铜离子变成络合离子状态，有利于细化晶粒，也有利于提高沉积速度及溶液的稳定性，改善化学镀层的性能。常用的络合剂有酒石酸盐、 EDTA , 拧檬酸盐、三乙醇胺、环己二胺四乙酸或乙二胺等。一般采用单一络合剂，也有采用混合络合剂的。铜镀液的不稳定性是化学镀铜液的最大缺点，所以一般引入稳定剂，例如 α、 α -联吡啶、三吡啶、硫脲、巯基苯骈噻唑。另外还加入非离子型表面活性剂或阴离子型表面活性剂改善镀层性质，如加入聚乙二醇（Μ=1 000 )，聚氧乙烯烷基酚醚等。 In the present invention, the plated metal is electrolessly plated to form a conductive metal portion. Traditional electroless plating techniques can be used. For example, printed circuit board electroless plating technology. Electroless plating is preferred for electroless copper plating. Electroless copper plating is a transparent support in which a silver fine line pattern having a sufficient active point after being treated by the above various treatment methods is placed in a copper plating solution to perform electroless copper plating. Electroless copper plating solutions generally consist of a copper salt, a complexing agent, a reducing agent, and other additives. The copper salt provides deposited copper ions, and a soluble copper salt such as copper sulphate, copper acetate or copper chloride can be used. The reducing agent reduces the soluble copper ions in the plating solution to metal copper and deposits on the silver fine line pattern of the transparent support to form a metal copper plating layer. The reducing agent may be a substance such as furfural, sodium borohydride or sodium hypophosphite. The complexing agent prevents the precipitation of copper hydroxide in the alkaline state, turns the copper ion into a complex ion state, is beneficial to refine the crystal grains, is also beneficial to increase the deposition rate and stability of the solution, and improve the performance of the electroless plating layer. . Commonly used complexing agents are tartrate, EDTA, citrate, triethanolamine, cyclohexanediaminetetraacetic acid or ethylenediamine. Generally using a single complexing agent, There are also mixed complexing agents. The instability of the copper plating bath is the biggest disadvantage of the electroless copper plating solution, so stabilizers such as α, α-bipyridine, tripyridine, thiourea, and mercaptobenzothiazole are generally introduced. In addition, a nonionic surfactant or an anionic surfactant is added to improve the plating properties, such as polyethylene glycol (Μ=1 000), polyoxyethylene alkylphenol ether, and the like.

化学镀铜几乎都以曱醛作还原剂，但曱醛有毒，且易挥发，污染环境，危害人体健康。 Electroless copper plating almost uses furfural as a reducing agent, but furfural is toxic and volatile, polluting the environment and endangering human health.

本发明同时研究了用曱醛和次磷酸钠作还原剂，次磷酸钠的氧化反应必须在催化表面上发生，反应不被沉积的铜催化，因此镀液中需加入少量镍离子作自催化剂，使自催化反应得以继续进行。 The present invention simultaneously studies the use of furfural and sodium hypophosphite as a reducing agent. The oxidation reaction of sodium hypophosphite must occur on the catalytic surface, and the reaction is not catalyzed by the deposited copper. Therefore, a small amount of nickel ions is required as a self-catalyst in the plating solution. The autocatalytic reaction is allowed to continue.

本发明中，显影后的金属部分和镀覆金属后的导电金属部分需进行氧化处理。例如，氧化处理可以除去透明区域沉积的少量金属，使得透明区的透光率接近 100°/。。 In the present invention, the developed metal portion and the metal-plated conductive metal portion are subjected to oxidation treatment. For example, the oxidation treatment removes a small amount of metal deposited in the transparent region, so that the transmittance of the transparent region is close to 100 ° /. .

为了提高导电金属部分的反差，同时为了防止褪色，需对铜表面进行黑化处理。黑化处理可以使用在印刷线路板领域使用的方法。如在下述水溶液中在 95 °C条件下处理两分钟，溶液组分包括：氯化钠（31 g/L )，氢氧化钠 ( 15g/L ), 磷酸三钠（12g/L )。 In order to improve the contrast of the conductive metal portion, and to prevent fading, the copper surface needs to be blackened. The blackening process can use the method used in the field of printed wiring boards. Treated in the following aqueous solution at 95 °C for two minutes, the solution components include: sodium chloride (31 g / L), sodium hydroxide (15 g / L), trisodium phosphate (12 g / L).

如上所述制造的电磁波屏蔽膜，作为细线图案，如果使细线宽度变小而使开口率变大，则虽然透光性提高但导电性却下降，相反如果使细线宽度变大，则透光性下降、导电性变高。因此优选线宽为 5-25微米，细线在纵横方向上以格子状设置。 When the aperture ratio is increased and the aperture ratio is increased as the thin line pattern is formed as described above, the transmittance is improved, but the conductivity is lowered, and if the width of the thin line is increased, The light transmittance is lowered and the conductivity is increased. Therefore, it is preferable that the line width is 5 to 25 μm, and the thin lines are arranged in a lattice shape in the longitudinal and lateral directions.

镀覆金属后的导电金属部分的组成，主要由金属铜和金属银构成，另外含有少量的金属钯和 /或金属镍。金属铜的质量占金属总重的 50-90°/。。 The composition of the conductive metal portion after plating the metal is mainly composed of metallic copper and metallic silver, and additionally contains a small amount of metallic palladium and/or metallic nickel. The quality of metallic copper is 50-90°/ of the total weight of the metal. .

镀覆金属后的细线图案的厚度可以根据所希望的特性而任意地改变，但优选 2. 5 - 8. 0微米，如果比该范围薄，则有时会得不到所希望的表面电阻值，如果比该范围厚，则虽没有问题，但即使降低镀覆作业的效率也难于期待有表面电阻值降低的效果。另外，本发明的电磁波屏蔽膜，在 30MHz ~ 1 000 MHz的广泛频带范围可以得到 30dB以上的屏蔽效果或在高于上述范围的频带范围可得到良好的屏蔽效果。 The thickness of the fine line pattern after plating the metal may be arbitrarily changed according to desired characteristics, but is preferably 2. 5 - 8. 0 μm. If it is thinner than this range, the desired surface resistance value may not be obtained. If it is thicker than this range, there is no problem, but even if the efficiency of the plating operation is lowered, it is difficult to expect an effect of lowering the surface resistance value. Further, the electromagnetic wave shielding film of the present invention can obtain a shielding effect of 30 dB or more in a wide frequency range of 30 MHz to 1 000 MHz or a good shielding effect in a frequency band range higher than the above range.

有益效果 Beneficial effect

本发明提供的电磁波屏蔽膜，其表面电阻低，屏蔽效果好；其制备方法工艺简单，适合工业化生产。具体实施方式 The electromagnetic wave shielding film provided by the invention has low surface resistance and good shielding effect; and the preparation method thereof is simple in process and suitable for industrial production. detailed description

下面结合具体实施例对本发明作进一步说明，但不局限于此。 The present invention will be further described below in conjunction with specific embodiments, but is not limited thereto.

实施例 1 Example 1

1. 制备卤化银乳剂剂。化银乳齐 ί的组分为溴碘化银乳剂，其中溴化银为 98%摩尔％和碘化银为 2%摩尔％。乳剂平均粒径为 0. 09微米，乳剂中掺杂 K₂I rC

K₃RhBr₆。乳剂进一步用四氯金酸钾和硫代硫酸钠进行硫金增感。然后涂布在 PET 薄膜上，涂布银量为 4. 0克 /平方米，干燥。 . 1. Preparation of a silver halide emulsion. The composition of the silver milk emulsion is a silver bromoiodide emulsion in which silver bromide is 98% by mole and silver iodide is 2% by mole. The average particle size of the emulsion is 0. 09 microns, doped K ₂ I rC in the emulsion

K ₃ RhBr ₆ . The emulsion was further sulphur-stimulated with potassium tetrachloroaurate and sodium thiosulfate. Then, it was coated on a PET film, and the amount of silver applied was 4.0 g/m 2 and dried. .

2. 曝光、显影 2. Exposure, development

上述涂布样片干燥后用紫外光进行曝光，曝光使用线宽 /间距 =285微米 /15微米的网格模板，用下述显影剂进行显影，然后用 F-5定影剂定影，用去离子水冲洗净，制得银网格影像，其线宽 /间距 =15微米 /285微米。 The coated samples were dried and exposed to ultraviolet light, and exposed using a grid template having a line width/pitch = 285 μm / 15 μm, developed with the following developer, and then fixed with F-5 fixing agent, using deionized water. Rinse thoroughly to produce a silver grid image with line width/pitch = 15 microns / 285 microns.

显影液的组成 Developer composition

无水亚硫酸钠 100克 Anhydrous sodium sulfite 100 g

对苯二酚 30. 0克 Hydroquinone 30. 0 g

菲尼酮 1. 5克 Phenidone 1. 5 g

氢氧化钠 25. 0克 Sodium hydroxide 25. 0 g

溴化钾 3. 5克苯并*** 1· 0克 Potassium bromide 3. 5 g Benzotriazole 1·0 g

加水至 1 , 0升 Add water to 1,0 liters

3. 加厚处理 3. Thickening treatment

1号储备液 Reserve No. 1

硝酸银 91. 5克 Silver nitrate 91. 5 g

去离子水加至 1. 0升 Deionized water is added to 1. 0 liters

2号储备液 Reserve No. 2

硫氰酸铵 160. 0克 Ammonium thiocyanate 160. 0 g

硫代硫酸钠 160. 0克 Sodium thiosulfate 160. 0 g

加水至 1. 0升 Add water to 1. 0 liters

将 100毫升 1号溶液緩缓加入 100毫升 2号溶液中，同时搅拌。然后加入 25毫升含 5%至 1 0%亚硫酸钠的 1 0%连苯三酚溶液和 50毫升 1 0%氨水。将上述得到的银质网格样片浸入上述溶液中加厚 5. 0分钟，水洗。 100 ml of No. 1 solution was slowly added to 100 ml of No. 2 solution while stirring. Then, 25 ml of a 10% pyrogallol solution containing 5% to 10% sodium sulfite and 50 ml of 10% ammonia water were added. The silver mesh sample obtained above was immersed in the above solution for a thickening of 0.5 minutes, and washed with water.

4. 活化处理 4. Activation treatment

将上述样片在 0. 5%的氯化钯水溶液中活化 0. 5分钟。然后水洗，进行化学镀铜。 5分钟。 The sample was activated in 0.5% aqueous palladium chloride solution for 0.5 minutes. Then wash with water and perform electroless copper plating.

5.化学镀铜 5. Electroless copper plating

经上述处理的样片在下述镀液中进行化学镀铜，用氢氧化钠调节镀液的 pH值为 12. 5，在 25 °C条件下镀铜 5分钟，水洗干燥，得到本发明的样片，结果见表 1。 The sample treated as described above was subjected to electroless copper plating in the following plating solution, and the pH of the plating solution was adjusted to 12.5 with sodium hydroxide. The copper was plated at 25 ° C for 5 minutes, washed with water to obtain a sample of the present invention. The results are shown in Table 1.

化学镀铜液：名称含量 ( mM/L ) Electroless copper plating: Name Content ( mM / L )

硫酸铜 60 Copper sulfate 60

三乙醇胺 180 Triethanolamine 180

亚铁*** 0. 002 Potassium ferrocyanide 0. 002

联吡啶 0. 01 3 Bipyridine 0. 01 3

曱醛溶液 235 实施例 2 Furfural solution 235 Example 2

1. 制备卤化银乳剂 1. Preparation of silver halide emulsion

按照在照相感光材料领域中所使用的 ι¾化银乳剂的制造方法来制备乳剂。化银乳剂的组分为氯溴化银乳剂，其中氯化银为 70%摩尔％和溴化银为 30°/»摩尔。 /。。乳剂平均粒径为 0. 23微米，乳剂中掺杂 K₂I rCl₆和！ [₃RhBr₆。乳剂进一步用四氯金酸钾和硫代硫酸钠进行硫金增感。然后涂布在 PET 薄膜上，涂布银量为 3. 0克 /平方米，干燥。 The emulsion is prepared in accordance with a method for producing an yttrium silver emulsion used in the field of photographic light-sensitive materials. The composition of the silver halide emulsion is a silver chlorobromide emulsion in which silver chloride is 70% by mole and silver bromide is 30°/» mole. /. . The average particle size of the emulsion is 0.23 microns, and the emulsion is doped with K ₂ I rCl ₆ and! [ ₃ RhBr ₆ . The emulsion was further sulphur-stimulated with potassium tetrachloroaurate and sodium thiosulfate. Then, it was coated on a PET film, and the amount of silver applied was 3.0 g/m 2 , and dried.

2. 曝光、显影 2. Exposure, development

上述涂布样片干燥后用紫外光进行曝光，曝光使用线宽 /间距 =200微米 / 12微米的网格模板，用下述显影剂进行显影，然后用 F-5定影剂定影，用去离子水冲洗净，制得银网格影像，其线宽 /间距 =12微米 /200微米。 The coated samples were dried and exposed to ultraviolet light, and exposed using a grid template having a line width/pitch = 200 μm / 12 μm, developed with the following developer, and then fixed with F-5 fixing agent, using deionized water. Rinse off to produce a silver grid image with line width/pitch = 12 microns / 200 microns.

显影液的组成： The composition of the developer:

无水亚^ <酸钠 100克 Anhydrous sulphate

对苯二酚 12. 0克 Hydroquinone 12. 0g

米吐尔 2· 0克 Mitur 2·0 g

碳酸納 75克 Carbonate 75g

溴化钾 4. 0克 Potassium bromide 4. 0 g

碘化钾 0. 02克 Potassium iodide 0. 02 g

加水至 1. 0升 Add water to 1. 0 liters

3.加厚处理 3. Thickening treatment

(1) 硫酸铜 45克 (1) Copper sulfate 45 g

氯化钠 1 0克 Sodium chloride 10 g

加水至 1. 0升 Add water to 1. 0 liters

将 45克硫酸铜、 10克氯化钠加到 1. 0升的水中，搅拌，得到加厚液。将上述得到的银质网格样片浸入上述加厚液加厚 3. 0分钟，水洗。 45 g of copper sulfate and 10 g of sodium chloride were added to 1.0 liter of water and stirred to obtain a thickening liquid. The immersion of the above-mentioned silver-colored grid sample was immersed in the thickening liquid for 3. 0 minutes, and washed with water.

(2) 下列溶液要在临使用前混合 (2) The following solutions should be mixed before use.

A液：氯化亚锡 28克 Solution A: Stannous chloride 28 g

水 250ml Water 250ml

B液：氢氧化钠 22克 Solution B: Sodium hydroxide 22 g

水 750ml Water 750ml

使用前，将 B液加入到 A液中，将上述铜液中处理的样片在此溶液中放置 3分钟，水洗。 Before use, the solution B was added to the solution A, and the sample treated in the above copper solution was placed in the solution for 3 minutes and washed with water.

4.活化处理： 4. Activation treatment:

将上述样片在 2%的硝酸水溶液中活化 2分钟。然后水洗，进行化学镀铜。 The above plaque was activated in a 2% aqueous solution of nitric acid for 2 minutes. It is then washed with water and electroless copper plating.

5.化学镀铜： 5. Electroless copper plating:

化学镀铜工艺同例 1 , 结果见表 1。实施例 3 The electroless copper plating process is the same as in Example 1. The results are shown in Table 1. Example 3

1. 制备卤化银乳剂 1. Preparation of silver halide emulsion

同实施例 2。 Same as Embodiment 2.

2. 曝光、显影 2. Exposure, development

上述涂布样片干燥后用紫外光进行曝光，曝光使用线宽 /间距 =320微米 /25微米的网格模板，用例 1中的显影剂进行显影，然后用 F-5定影剂定影，用去离子水冲洗净，制得银网格影像，其线宽 /间距 =25微米 /320微米。 The coated samples were dried and exposed to ultraviolet light, and exposed using a grid template having a line width/pitch = 320 μm / 25 μm, developed with the developer of Example 1, and then fixed with an F-5 fixing agent, using deionized The water was rinsed off to obtain a silver grid image with a line width/space = 25 microns / 320 microns.

3. 加厚处理 3. Thickening treatment

同实施例 2。 Same as Embodiment 2.

4. 活化处理 4. Activation treatment

将上述加厚处理的样片在 0. 1%的氯化钯水溶液中活化 3分钟。然后水洗，进行化学镀铜。 5. 化学镀铜 The above-mentioned thickened treated sample was activated in an aqueous solution of 0.1% palladium chloride for 3 minutes. It is then washed with water to perform electroless copper plating. 5. Electroless copper plating

经上述处理的样片在下述镀液中进行化学镀铜，用氢氧化钠调节镀液的 pH值为 9. 0 , 在 35 °C条件下镀铜 30分钟。水洗干燥，得到本发明的样片，结果见表 1。 The sample treated as described above was subjected to electroless copper plating in the following plating solution, and the pH of the plating solution was adjusted to 9.0 with sodium hydroxide, and copper was plated at 35 ° C for 30 minutes. The sample of the present invention was obtained by washing with water and dried. The results are shown in Table 1.

化学镀铜液： Electroless copper plating solution:

实施例 4

Example 4

1. 制备卤化银乳剂 1. Preparation of silver halide emulsion

同实施例 2。 Same as Embodiment 2.

2. 曝光、显影 2. Exposure, development

上述涂布样片干燥后用紫外光进行曝光，曝光使用线宽 /间距 =200微米 /5微米的网格模板，用实施例 1中的显影剂进行显影，然后用 F-5定影剂定影，用去离子水冲洗净，制得银网格影像，其线宽 /间距 =5 微米 /200微米。 The coated sample was dried and exposed to ultraviolet light, and exposed to a grid template having a line width/pitch=200 μm/5 μm, developed with the developer of Example 1, and then fixed with an F-5 fixing agent. Rinse with deionized water to obtain a silver grid image with line width/pitch = 5 microns / 200 microns.

3.加厚处理 3. Thickening treatment

同实施例 1。 Same as Embodiment 1.

4.活化处理 4. Activation treatment

将上述加厚处理的样片在 1 %的硝酸银水溶液中活化 3分钟。然后水洗，进行化学镀铜。 5.化学镀铜 The above-mentioned thickened sample was activated in a 1% aqueous solution of silver nitrate for 3 minutes. It is then washed with water to perform electroless copper plating. 5. Electroless copper plating

经上述处理的样片在下述镀液中进行化学镀铜，用氢氧化钠调节镀液的 pH值为 9. 5，在 40°C条件下镀铜 30分钟。水洗干燥，得到本发明的样片，结果见表 1。 The sample treated as described above was subjected to electroless copper plating in the following plating solution, and the pH of the plating solution was adjusted to 9.5 with sodium hydroxide, and copper was plated at 40 ° C for 30 minutes. The sample of the present invention was obtained by washing with water and dried. The results are shown in Table 1.

化学镀铜液： Electroless copper plating solution:

表 1: 样片性能表

Table 1: Sample Performance Table

性能测定方法：

Performance measurement method:

1. 用电阻测定仪来测出表面电阻值； 1. Use a resistance meter to measure the surface resistance value;

2.用光学显微镜、扫描电镜来测定本发明样品的导电性金属线宽，求出开孔率。 2. The conductive metal line width of the sample of the present invention was measured by an optical microscope or a scanning electron microscope to determine the opening ratio.

Claims

权利要求书 Claim

1.一种电磁波屏蔽膜，是由支持体和在其上所形成的细线栅网构成的导电性薄膜，细线栅网由金属银及其上镀覆的铜构成，其特征在于，所含铜的质量占银铜总质量的 55 % ~ 90 % , 栅网线宽 5 ~ 25μπι, 开孔比 85 % ~ 95 % , 表面电阻大于 0小于 5Ω/口。 An electromagnetic wave shielding film comprising a support and a thin wire mesh formed thereon, the fine wire grid being composed of metallic silver and copper plated thereon, characterized in that The quality of copper is 55 % ~ 90 % of the total mass of silver copper, the line width of the grid is 5 ~ 25μπι, the opening ratio is 85% ~ 95%, and the surface resistance is greater than 0 less than 5Ω / port.

2. 根据权利要求 1所述的电磁波屏蔽膜，其特征是，其中所述的电磁波屏蔽膜的细线栅网厚为 2. 5 ~ 8μπι。 The electromagnetic wave shielding film according to claim 1, wherein the electromagnetic shielding film has a fine wire mesh thickness of 2. 5 to 8 μm.

3.根据权利要求 1 所述的电磁波屏蔽膜，其特征是，所述支持体是由聚对苯二曱酸乙二醇酯树脂、双乙酸酯树脂、三乙酸酯树脂、聚乙烯、聚丙浠、聚苯乙烯、聚氯乙烯树脂、聚酮醚，聚砜、聚醚砜、聚碳酸酯、聚酰胺、丙烯酸树脂或三醋酸纤维素构成的单层或多层薄膜。 The electromagnetic wave shielding film according to claim 1, wherein the support is polyethylene terephthalate resin, diacetate resin, triacetate resin, polyethylene, A single or multilayer film of polypropylene, polystyrene, polyvinyl chloride resin, polyketide, polysulfone, polyethersulfone, polycarbonate, polyamide, acrylic or cellulose triacetate.

4.一种制造如权利要求 1至 3 中任意一项所述电磁波屏蔽膜的方法，其特征是，它按如下步骤进行：在支持体上涂布银盐层及其保护层，并施以栅网曝光和显影处理过程，曝光部分形成金属银部分，未曝光部分形成透光部分，金属银部分进行加厚、活化处理，镀覆金属形成导电金属部分。 A method of producing an electromagnetic wave shielding film according to any one of claims 1 to 3, characterized in that it is carried out as follows: coating a silver salt layer and a protective layer on the support, and applying In the grid exposure and development process, the exposed portion forms a metallic silver portion, the unexposed portion forms a light transmitting portion, the metallic silver portion is thickened, activated, and the plated metal forms a conductive metal portion.

5. 根据权利要求 4所述的电磁波屏蔽膜的制造方法，其特征是，其中所述的金属银部分的加厚处理采用银加厚或铜加厚。 The method of manufacturing an electromagnetic wave shielding film according to claim 4, wherein the thickening treatment of the metallic silver portion is performed by using a silver thickening or a copper thickening.

6.根据权利要求 4 所述的电磁波屏蔽膜的制造方法，其特征是，其中所述的活化处理采用重金属离子水溶液活化的方法。 The method of producing an electromagnetic wave shielding film according to claim 4, wherein the activation treatment is carried out by a method of activating a heavy metal ion aqueous solution.

7.根据权利要求 4 所述的电磁波屏蔽膜的制造方法，其特征是，其中所述的活化处理采用钯离子、金离子或银离子水溶液活化的方法。 The method of producing an electromagnetic wave shielding film according to claim 4, wherein the activation treatment is performed by a method of activating palladium ions, gold ions or an aqueous solution of silver ions.

8.根据权利要求 4所述的电磁波屏蔽膜的制造方法，其特征是，其中所述的镀覆金属采用化学镀。 The method of manufacturing an electromagnetic wave shielding film according to claim 4, wherein the plating metal is electroless plated.

9.根据权利要求 8所述的电磁波屏蔽膜的制造方法，其特征是，其中所述的化学镀为化学镀铜。 The method of producing an electromagnetic wave shielding film according to claim 8, wherein the electroless plating is electroless copper plating.

10.根据权利要求 4所述的电磁波屏蔽膜的制造方法，其特征是，涂布银盐层和保护层时，采用下述涂布方式：浸涂、挤压涂、滑动涂敷、帘涂、棒涂、气刀涂敷、辊涂、照相凹版涂敷、喷涂。 The method of producing an electromagnetic wave shielding film according to claim 4, wherein when the silver salt layer and the protective layer are applied, the following coating methods are employed: dip coating, extrusion coating, sliding coating, curtain coating , bar coating, air knife coating, roll coating, gravure coating, spray coating.