WO2023035903A1 - Electroless copper plating catalyst and method for forming metal grid by using same - Google Patents

Electroless copper plating catalyst and method for forming metal grid by using same Download PDF

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WO2023035903A1
WO2023035903A1 PCT/CN2022/113510 CN2022113510W WO2023035903A1 WO 2023035903 A1 WO2023035903 A1 WO 2023035903A1 CN 2022113510 W CN2022113510 W CN 2022113510W WO 2023035903 A1 WO2023035903 A1 WO 2023035903A1
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copper plating
electroless copper
plating catalyst
hyperdispersant
present
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PCT/CN2022/113510
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French (fr)
Chinese (zh)
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王钧
李阳
江建国
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浙江鑫柔科技有限公司
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/31—Coating with metals
    • C23C18/38—Coating with copper
    • G—PHYSICS
    • G06—COMPUTING; CALCULATING OR COUNTING
    • G06F—ELECTRIC DIGITAL DATA PROCESSING
    • G06F3/00—Input arrangements for transferring data to be processed into a form capable of being handled by the computer; Output arrangements for transferring data from processing unit to output unit, e.g. interface arrangements
    • G06F3/01—Input arrangements or combined input and output arrangements for interaction between user and computer
    • G06F3/03—Arrangements for converting the position or the displacement of a member into a coded form
    • G06F3/041—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means
    • G—PHYSICS
    • G06—COMPUTING; CALCULATING OR COUNTING
    • G06F—ELECTRIC DIGITAL DATA PROCESSING
    • G06F2203/00—Indexing scheme relating to G06F3/00 - G06F3/048
    • G06F2203/041—Indexing scheme relating to G06F3/041 - G06F3/045
    • G06F2203/04103—Manufacturing, i.e. details related to manufacturing processes specially suited for touch sensitive devices

Definitions

  • the invention belongs to the field of electroless copper plating, and in particular relates to an electroless copper plating catalyst and a method for forming a metal grid by using the same.
  • Coated roll structures on flexible substrates are currently typically made from a UV-curable base layer, a middle layer containing colloidal palladium nanoparticles, and a protective layer on top.
  • Mask UV exposure was performed on the coated roll, followed by wet development to obtain a composite structure formed by a UV-cured base layer and palladium nanoparticles on the top, and then the palladium nanoparticles deposited on the UV-cured base layer were used as a catalyst for chemical copper plated.
  • Palladium-based catalysts have high catalytic activity, strong selectivity, convenient catalyst preparation, less usage, can be optimized through changes and improvements in manufacturing methods, compounded with other metals or co-catalyst active components, and can be regenerated and activated repeatedly. , long life, and the palladium metal of the spent catalyst can be recycled and reused.
  • the metal palladium nanoparticle catalyst is widely used in the field of electroless copper plating. Common methods for preparing metal nanoparticles include gas-phase chemical reaction method, precipitation method, liquid-phase reduction method, spray pyrolysis method, sol-gel method, etc. According to the different solvents, the liquid phase reduction method can be simply divided into organic solvent synthesis method and aqueous solution synthesis method. Nanoparticles prepared by organic solvent synthesis have the advantages of good crystallinity, good monodispersity, and easy control of morphology.
  • the method for preparing palladium nanoparticles in the prior art is an organic solvent synthesis method.
  • Common dispersants can be divided into three categories: inorganic dispersants, organic small molecule dispersants and hyperdispersants.
  • Hyperdispersants overcome the limitations of traditional dispersants in non-aqueous dispersion systems. Compared with other dispersants, it has the following characteristics: (1) Multi-point anchoring is formed on the particle surface, which improves the adsorption fastness and is not easy to desorb; (2) The solvation chain is longer than the lipophilic group of traditional dispersants, which can play a role Effective steric stabilization; (3) form extremely weak capsules, which are easy to move and can quickly move to the surface of the particles to play a role in wetting protection; (4) will not introduce lipophilic film on the surface of the particles, so as not to affect the quality of the final product application performance.
  • the object of the present invention is to improve the catalytic activity and stability of the existing palladium nanoparticle catalyst, and provide a palladium nanoparticle catalyst with more excellent catalytic activity and stability.
  • the inventors have unexpectedly found that the palladium nanoparticle catalyst with palladium nanoparticles of the present invention and a specific dispersant combination has more excellent catalytic activity and stability when used as an electroless copper plating catalyst, and based on this, completed the invention.
  • the present invention provides an electroless copper plating catalyst comprising palladium nanoparticles and a dispersant, wherein the dispersant is selected from polyester hyperdispersants, polyacrylate hyperdispersants and polyolefins One or more of hyperdispersants.
  • the dispersant includes at least a polyolefin hyperdispersant.
  • the polyester hyperdispersant is selected from one or more of Solsperse-3000, Solsperse-9000, Solsperse-24000, Solsperse-46000 and Solsperse-20000.
  • the polyacrylate hyperdispersant is selected from EL-vacit AB 1010, EL-vacit AB 1015, EL-vacit AB 1020, EL-vacit AB 1030, Disperse-AYD15, BYK- One or more of 358, BYK-163 and BYK-154.
  • the polyolefin hyperdispersant is selected from one or more of PVP K15, PVP K30, PVP K60 and PVP K90.
  • the weight ratio of the palladium nanoparticles to the dispersant is 0.1-10:1, preferably 0.2-5:1, more preferably 0.5-2:1.
  • the present invention also provides a method for forming a metal grid on a flexible substrate, wherein the method includes the following steps:
  • the coating is wet coating.
  • the UV curable material is a positive photoresist or a negative photoresist.
  • the present invention also provides a metal grid touch sensor, wherein the metal grid of the metal grid touch sensor is formed by the above-mentioned method.
  • the technical solution of the present invention at least includes the following advantages:
  • the electroless copper plating catalyst provided by the present invention has excellent catalytic activity, and when using the electroless copper plating catalyst of the present invention (especially when comprising polyolefin hyperdispersant in the catalyzer) to form metal copper grid lines, there is a reduction in chemical Advantages such as the starting time of plating of metal grid in the copper plating process, reducing the line width of metal copper grid lines have higher practicability; Precipitation did not occur.
  • FIG. 1 shows a flowchart of an exemplary method of forming a metal mesh according to an embodiment of the present invention.
  • Fig. 2 shows the copper metal grid sample prepared according to embodiment 1 and embodiment 3 of the present invention, the sample shown in the figure is 20 times magnification, and the copper metal grid sample prepared by embodiment 3 can be plated with copper for 5 seconds Start plating, and the copper metal grid sample that embodiment 1 prepares is plated copper 30s and just can start plating.
  • Fig. 3 shows the line width of the sample prepared according to Example 1-1 of the present invention after copper plating and development.
  • FIG. 4 shows the line widths of samples prepared according to Examples 1-2 of the present invention after copper plating and development.
  • FIG. 5 shows the line widths of samples prepared according to Examples 1-3 of the present invention after copper plating and development.
  • Fig. 6 shows the line width of the sample prepared according to Example 2-1 of the present invention after copper plating and development.
  • FIG. 7 shows the line widths of the samples prepared according to Example 2-2 of the present invention after copper plating and development.
  • FIG. 8 shows the line widths of samples prepared according to Examples 2-3 of the present invention after copper plating and development.
  • Fig. 9 shows the line width of the sample prepared according to Example 3-1 of the present invention after copper plating and development.
  • Fig. 10 shows the line width of the sample prepared according to Example 3-2 of the present invention after copper plating and development.
  • Fig. 11 shows the line widths of samples prepared according to Example 3-3 of the present invention after copper plating and development.
  • Example 12 shows the copper plating effect that can be achieved after exposure and development using the electroless copper plating catalyst of Example 3 and a photomask with a line width of 1.25 ⁇ m according to an embodiment of the present invention.
  • FIG. 13 shows test results of adhesion after copper plating using the electroless copper plating catalyst of Example 3 according to an embodiment of the present invention.
  • the present invention provides an electroless copper plating catalyst comprising palladium nanoparticles and a dispersant, wherein the dispersant is selected from polyester hyperdispersants, polyacrylate hyperdispersants and polyolefins One or more of hyperdispersants.
  • the electroless copper plating catalyst of the present invention selects one or more of polyester type hyperdispersants, polyacrylate type hyperdispersants and polyolefin hyperdispersants as dispersants, palladium can be made The nanoparticles are better wrapped and dispersed, and the obtained colloidal palladium nanoparticles have smaller particle size and stronger catalytic activity.
  • Using palladium nanoparticles with smaller particle size and stronger catalytic activity as the coating material of the second layer can reduce the plating start time of the metal grid during the electroless copper plating process.
  • the palladium nanoparticles in the electroless copper plating catalyst prepared by the present invention are more stable, and can be placed at room temperature for a longer period of time without precipitation.
  • the dispersant may at least contain a polyolefin hyperdispersant.
  • the dispersant may only comprise, or consist of, a polyolefin-based hyperdispersant.
  • the dispersant may comprise or consist of both a polyolefin hyperdispersant and a polyester hyperdispersant.
  • the dispersant may comprise or consist of both polyolefin-based hyperdispersants and polyacrylate-based hyperdispersants.
  • the dispersant may comprise or consist of polyester hyperdispersant, polyacrylate hyperdispersant and polyolefin hyperdispersant.
  • the present invention is not particularly limited to the specific types of polyester type hyperdispersant, polyacrylate type hyperdispersant and polyolefin type hyperdispersant, any polyester type hyperdispersant, polyacrylate known to the skilled person can be used type hyperdispersant and polyolefin hyperdispersant.
  • the polyester type hyperdispersant can be selected from one or more of Solsperse-3000, Solsperse-9000, Solsperse-24000, Solsperse-46000 and Solsperse-20000;
  • Polyacrylate hyperdispersant can be selected from EL-vacit AB 1010, EL-vacit AB 1015, EL-vacit AB 1020, EL-vacit AB 1030, Disperse-AYD15, BYK-358, BYK-163 and BYK-154
  • the polyolefin hyperdispersant can be selected from one or more of PVP K15, PVP K30, PVP K60 and PVP K90, but not limited thereto.
  • the present invention has no special limitation on the palladium nanoparticles and dispersant in the electroless copper plating catalyst, and can be adjusted according to the experience and actual needs of those skilled in the art.
  • the weight ratio of the palladium nanoparticles to the dispersant can be 0.1-10:1 (for example, 0.1:1, 0.2:1, 0.3:1, 0.5:1, 0.8:1 1, 1:1, 1.2:1, 1.5:1, 2:1, 3:1, 5:1 or 8:1, etc.), preferably 0.2-5:1, more preferably 0.5-2:1.
  • the present invention also provides a method for forming a metal grid on a flexible substrate, wherein the method includes the following steps:
  • FIG. 1 shows a flow chart of an exemplary method of forming a metal mesh according to an embodiment of the present invention, wherein by sequentially coating a UV curable material on one surface of a substrate, chemical A copper catalyst, and a protective layer material are plated to sequentially form a UV curable layer, a Pd nanoparticle layer, and a water-soluble protective layer on the surface of the substrate.
  • the UV curable material can be a positive photoresist or a negative photoresist.
  • the positive photoresist may preferably include a resin material that is soluble in a developer after exposure
  • the negative photoresist may preferably include a resin material that is insoluble in a developer after exposure.
  • Described developing solution is usually the aqueous solution that contains alkaline compound and surfactant, and alkaline compound can be inorganic or organic alkaline compound, and these inorganic and organic alkaline compounds can be used alone or in combination of two or more; And as surface active As an agent, at least one selected from the group consisting of nonionic surfactants, anionic surfactants and cationic surfactants can be used, and these surfactants can be used alone or in combination of two or more.
  • the UV curable material also includes a photoinitiator, for example, in one embodiment of the present invention, the photoinitiator can be selected from acetophenone compounds, benzophenone compounds, triazines At least one of the group consisting of compound, thioxanthone compound and oxime ester compound.
  • acetophenone compounds may include 2-hydroxy-2-methyl-1-phenylpropan-1-one, diethoxyacetophenone, and 2-(4-methylbenzyl)-2- (Dimethylamino)-1-(4-morpholinophenyl)butan-1-one, etc.
  • benzophenone compounds may include benzophenone, methyl o-benzoylbenzoate, 4-benzoyl-4'-methyldiphenyl sulfide, and 2,4,6-trimethyl benzophenone etc.
  • triazine compounds may include 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-triazine, 2,4-bis(trichloromethyl) Methyl)-6-(4-methoxynaphthyl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(3,4-dimethoxy phenyl)vinyl]-1,3,5-triazine and 2,4-bis(trichloromethyl)-6-2-(4-diethylamino-2-methylphenyl)ethenyl ]-1,3,5-triazine etc.
  • thioxanthone compounds may include 2-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, and 1-chloro-4-propoxythioxanthone xanthone etc.
  • oxime ester compounds may include o-ethoxycarbonyl- ⁇ -oxyimino-1-phenylpropan-1-one, 1,2-octanedione, 1-(4-phenylthio)benzene base and 2-(o-benzoyl oxime), etc.
  • the Pd nano particle layer as the second layer is the electroless copper plating catalyst of the present invention, and is the key to the technology of forming the metal grid on the flexible substrate of the present invention. Since the components and contents of the electroless copper plating catalyst of the present invention have been described in detail in the previous section, the characteristics of the electroless copper plating catalyst will not be described in detail in this section to avoid unnecessary redundancy.
  • the protective layer material of the third layer mainly plays a protective role in the exposure stage, and then it will be washed away by the developer in the development stage.
  • the protective layer material can be made using conventional protective layer materials in the art.
  • the protective layer material may be a water-soluble material, so that it can be dissolved in an aqueous developer solution during the development stage.
  • the coating methods of the above three coating materials can preferably be carried out by wet coating, that is, the UV curable material in liquid or solution form, the electroless copper plating catalyst, and the protective layer material can be sequentially coated on one surface of the substrate.
  • step (2) the substrate coated with UV curable material, electroless copper plating catalyst, and protective layer material in sequence is exposed to ultraviolet rays and a mask with a desired pattern is set therebetween, thereby forming a desired pattern on the substrate. pattern. Subsequently, during development, the UV curable material and the protective layer material that are not cured may be removed during development, as described above.
  • step (3) since the protective layer material has been removed, the palladium nanoparticle layer is at the top layer and can be used as a catalyst for copper plating, so this step only needs to carry out copper plating on the pattern, such as using electroless copper plating
  • the way can be, so as to form the required metal grid.
  • the present invention also provides a metal grid touch sensor, wherein the metal grid of the metal grid touch sensor is formed by the method for forming the metal grid as described above.
  • the electroless copper plating catalyst provided by the present invention has excellent catalytic activity, and when using the electroless copper plating catalyst of the present invention (especially when comprising polyolefin hyperdispersant in the catalyst) to form metallic copper grid lines , it has the advantages of reducing the plating time of the metal grid in the electroless copper plating process, reducing the line width of the metal copper grid line, and has higher practicability; and the electroless copper plating catalyst of the present invention has excellent stability and can be used at room temperature It can be left for a longer period of time without precipitation.
  • a negative photoresist coating containing Irgacure 907 was coated on one surface of a flexible substrate using a coating wire bar, and then dried in an oven at a temperature of 70° C. for 120 seconds to obtain a coating with a thickness of 800 nm;
  • the top of the photoresist film is coated with a palladium-containing nanoparticle catalyst coating prepared as above, and then coated with a layer of water-soluble material for protecting the above two coatings, and then exposed with ultraviolet light having a peak wave of 314nm;
  • the substrate is rinsed with an alkaline developer to remove the water-soluble protective coating and the uncured negative photoresist coating, and the resulting sample is immersed in an electroless copper plating solution to grow a copper grid, which contains palladium
  • the nanoparticle catalyst plays the role of catalyzing the copper plating reaction.
  • Copper plating is carried out in a method similar to Example 1, except that the copper plating catalyst is prepared as follows: get 90% solvent, 4% palladium acetate, and 6% dispersant B by mass components and mix and heat to 105 ° C, stir After 2h, the resulting mixed solution was mixed with pure water and a surfactant to obtain a palladium-containing nanoparticle catalyst coating, wherein the solvent was ethyl lactate, B was a hyperdispersant PVP K30, and the surfactant was a fluorosurfactant.
  • the solvent was ethyl lactate
  • B was a hyperdispersant PVP K30
  • the surfactant was a fluorosurfactant.
  • Copper plating is carried out in a method similar to Example 1, except that the copper plating catalyst is prepared as follows: get 90% solvent, 4% palladium acetate, 1% dispersant A, 5% dispersant B by mass components and mix Heating to 105°C, stirring for 2 hours, taking the resulting mixed solution, mixing it with pure water and a surfactant to prepare a catalyst coating, wherein the solvent is ethyl lactate, A is the hyperdispersant Solsperse46000, and B is the hyperdispersant PVP K30.
  • the active agent is a fluorosurfactant.
  • Example 1-1 Take three groups of metallic copper grid samples prepared according to the steps of Example 1, named as Example 1-1, Example 1-2, and Example 1-3, and measure metallic copper under a 2.5D two-dimensional manual image measuring instrument Grid line width.
  • Example 2-1 Take three groups of metallic copper grid samples prepared according to the steps of Example 2, named as Example 2-1, Example 2-2, and Example 2-3, and measure metallic copper under a 2.5D two-dimensional manual image measuring instrument Grid line width.
  • Example 3-1 Take three groups of metallic copper grid samples prepared according to the steps of Example 3, named as Example 3-1, Example 3-2, and Example 3-3, and measure metallic copper under a 2.5D two-dimensional manual image measuring instrument Grid line width.
  • Table 1-2 and Figure 3-11 show the data of the average development line width before copper plating and the average copper grid line width after copper plating of the above nine groups of samples.
  • the samples prepared in Examples 1-3 all realized narrower development line width and metal copper grid line width.
  • the sample prepared in Example 3 has the narrowest line width of the metal copper grid line when the development line width is close.
  • the chemical catalyst provided by the present invention has the advantage of reducing the width of the metal copper grid line when the metal copper grid line is prepared by the above-mentioned method, and has higher practicability, especially when the hyperdispersant contains polyolefin When using a hyperdispersant such as PVP K30, the above effects are even better.
  • the catalyst prepared in Example 1 can be placed at room temperature for 4 days without precipitation, while the catalyst prepared in Example 3 can be placed at room temperature for 10 days without precipitation, and still has good catalytic activity.
  • the electroless copper plating catalyst of the present invention has excellent stability and can be placed at room temperature for a longer period of time without precipitation.
  • Fig. 2 shows the copper metal grid sample prepared by embodiment 1 and embodiment 3, the sample shown in the figure is 20 times magnification, and the copper metal grid sample prepared by embodiment 3 can be plated in 5 seconds , while the copper metal grid sample prepared in Example 1 could be plated after 30s of copper plating, which confirmed that the catalyst activity prepared in Example 3 was more excellent.
  • the difference between the line width after development and the line width after copper plating is about 1.6 microns, that is, the difference between the line width after copper plating and the line width after development is relatively small.
  • the difference between the line width after development and the line width after copper plating is about 1.9 microns, that is, the difference between the line width after copper plating and the line width after development is relatively small.
  • the difference between the line width after development and the line width after copper plating is about 0.4 microns, that is, the difference between the line width after copper plating and the line width after development is extremely small.

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Abstract

The present invention provides an electroless copper plating catalyst and a method for forming a metal grid by using same. The electroless copper plating catalyst contains palladium nanoparticles and a dispersant; and the dispersant is selected from one or more of a polyester-type hyperdispersant, a polyacrylate-type hyperdispersant, and a polyolefin-type hyperdispersant. The electroless copper plating catalyst provided by the present invention has excellent catalytic activity; when the electroless copper plating catalyst (in particular when the catalyst contains the polyolefin-type hyperdispersant) is used to form a metal copper grid line, the advantages of reducing a plating time of a metal grid in the electroless copper plating process, reducing a line width of the metal copper grid line, and the like are provided, and the practicability is high; and the electroless copper plating catalyst of the present invention has excellent stability, and can be placed at room temperature for a longer time without precipitation.

Description

一种化学镀铜催化剂以及使用其形成金属网格的方法A kind of electroless copper plating catalyst and the method for using it to form metal grid
相关申请的交叉引用Cross References to Related Applications
本申请要求于2021年9月10日提交的申请号为202111061206.1的中国专利申请的优先权，其全部内容通过引用并入本文。This application claims priority to Chinese Patent Application No. 202111061206.1 filed September 10, 2021, the entire contents of which are incorporated herein by reference.
技术领域technical field
本发明属于化学镀铜领域，具体地，涉及一种化学镀铜催化剂以及使用其形成金属网格的方法。The invention belongs to the field of electroless copper plating, and in particular relates to an electroless copper plating catalyst and a method for forming a metal grid by using the same.
背景技术Background technique
金属网格触摸传感的制备过程主要分为涂布、曝光、显影、镀铜、黑化等。在柔性基材上的涂布卷结构目前通常是由一层可UV固化的基层，含有胶体钯纳米颗粒的中间层和顶部的保护层制成。对涂布后的卷进行掩膜UV曝光，再进行湿法显影得到由紫外光固化基层和顶部的钯纳米颗粒形成的复合结构，然后用紫外光固化基层上沉积的钯纳米颗粒作为催化剂进行化学镀铜。The preparation process of the metal grid touch sensor is mainly divided into coating, exposure, development, copper plating, blackening, etc. Coated roll structures on flexible substrates are currently typically made from a UV-curable base layer, a middle layer containing colloidal palladium nanoparticles, and a protective layer on top. Mask UV exposure was performed on the coated roll, followed by wet development to obtain a composite structure formed by a UV-cured base layer and palladium nanoparticles on the top, and then the palladium nanoparticles deposited on the UV-cured base layer were used as a catalyst for chemical copper plated.
基于钯催化剂具有催化活性高、选择性强、催化剂制作方便、使用量少、可通过制造方法的变化和改进、与其他金属或助催化剂活性组分复配而优化性能、能够反复再生和活化使用、寿命长、废催化剂的金属钯可以回收再利用等优越性，金属钯纳米颗粒催化剂在化学镀铜领域被广泛使用。制备金属纳米颗粒常用方法有气相化学反应法、沉淀法、液相还原法、喷雾热解法、溶胶-凝胶法等。按照溶剂的不同，液相还原法可简单分为有机溶剂合成法和水溶液合成法。有机溶剂合成法制备的纳米颗粒具有结晶性好、单分散性好、形貌容易控制等优点。现有工艺中制备钯纳米颗粒方法为有机溶剂合成法。Palladium-based catalysts have high catalytic activity, strong selectivity, convenient catalyst preparation, less usage, can be optimized through changes and improvements in manufacturing methods, compounded with other metals or co-catalyst active components, and can be regenerated and activated repeatedly. , long life, and the palladium metal of the spent catalyst can be recycled and reused. The metal palladium nanoparticle catalyst is widely used in the field of electroless copper plating. Common methods for preparing metal nanoparticles include gas-phase chemical reaction method, precipitation method, liquid-phase reduction method, spray pyrolysis method, sol-gel method, etc. According to the different solvents, the liquid phase reduction method can be simply divided into organic solvent synthesis method and aqueous solution synthesis method. Nanoparticles prepared by organic solvent synthesis have the advantages of good crystallinity, good monodispersity, and easy control of morphology. The method for preparing palladium nanoparticles in the prior art is an organic solvent synthesis method.
常见的分散剂可分为三类：无机分散剂、有机小分子分散剂和超分散剂。超分散剂克服了传统分散剂在非水分散体系中的局限性。与其他分散剂相比，有以下特点：(1)在颗粒表面形成多点锚固，提高了吸附牢度，不易解吸；(2) 溶剂化链比传统分散剂亲油基团长，可起到有效的空间稳定作用；(3)形成极弱的胶囊，易于活动，能迅速移向颗粒表面，起到润湿保护作用；(4)不会在颗粒表面导入亲油膜，从而不致影响最终产品的应用性能。Common dispersants can be divided into three categories: inorganic dispersants, organic small molecule dispersants and hyperdispersants. Hyperdispersants overcome the limitations of traditional dispersants in non-aqueous dispersion systems. Compared with other dispersants, it has the following characteristics: (1) Multi-point anchoring is formed on the particle surface, which improves the adsorption fastness and is not easy to desorb; (2) The solvation chain is longer than the lipophilic group of traditional dispersants, which can play a role Effective steric stabilization; (3) form extremely weak capsules, which are easy to move and can quickly move to the surface of the particles to play a role in wetting protection; (4) will not introduce lipophilic film on the surface of the particles, so as not to affect the quality of the final product application performance.
然而，不同分散剂对钯纳米颗粒的活性及溶液稳定性有明显影响，仍然需要寻求一种具有优异催化活性及稳定性的钯纳米颗粒催化剂，从而实现制备更小线宽的铜金属网格。However, different dispersants have a significant impact on the activity and solution stability of palladium nanoparticles, and it is still necessary to find a palladium nanoparticle catalyst with excellent catalytic activity and stability, so as to achieve the preparation of copper metal grids with smaller line widths.
发明内容Contents of the invention
本发明的目的在于改善现有的钯纳米颗粒催化剂的催化活性和稳定性，提供一种具有更优异的催化活性及稳定性的钯纳米颗粒催化剂。经过研究后，本发明人意外地发现，具有本发明的钯纳米颗粒和特定分散剂组合的钯纳米颗粒催化剂在用作化学镀铜催化剂时具有更优异的催化活性及稳定性，并基于此完成了本发明。The object of the present invention is to improve the catalytic activity and stability of the existing palladium nanoparticle catalyst, and provide a palladium nanoparticle catalyst with more excellent catalytic activity and stability. After research, the inventors have unexpectedly found that the palladium nanoparticle catalyst with palladium nanoparticles of the present invention and a specific dispersant combination has more excellent catalytic activity and stability when used as an electroless copper plating catalyst, and based on this, completed the invention.
在一方面，本发明提供了一种化学镀铜催化剂，其包含钯纳米颗粒和分散剂，其中，所述分散剂选自聚酯型超分散剂、聚丙烯酸酯型超分散剂和聚烯烃类超分散剂中的一种或多种。In one aspect, the present invention provides an electroless copper plating catalyst comprising palladium nanoparticles and a dispersant, wherein the dispersant is selected from polyester hyperdispersants, polyacrylate hyperdispersants and polyolefins One or more of hyperdispersants.
在本发明的一个实施方式中，所述分散剂至少包含聚烯烃类超分散剂。In one embodiment of the present invention, the dispersant includes at least a polyolefin hyperdispersant.
在本发明的一个实施方式中，所述聚酯型超分散剂选自Solsperse-3000、Solsperse-9000、Solsperse-24000、Solsperse-46000和Solsperse-20000中的一种或多种。In one embodiment of the present invention, the polyester hyperdispersant is selected from one or more of Solsperse-3000, Solsperse-9000, Solsperse-24000, Solsperse-46000 and Solsperse-20000.
在本发明的一个实施方式中，所述聚丙烯酸酯型超分散剂选自EL-vacit AB 1010、EL-vacit AB 1015、EL-vacit AB 1020、EL-vacit AB 1030、Disperse-AYD15、BYK-358、BYK-163和BYK-154中的一种或多种。In one embodiment of the present invention, the polyacrylate hyperdispersant is selected from EL-vacit AB 1010, EL-vacit AB 1015, EL-vacit AB 1020, EL-vacit AB 1030, Disperse-AYD15, BYK- One or more of 358, BYK-163 and BYK-154.
在本发明的一个实施方式中，所述聚烯烃类超分散剂选自PVP K15、PVP K30、PVP K60和PVP K90中的一种或多种。In one embodiment of the present invention, the polyolefin hyperdispersant is selected from one or more of PVP K15, PVP K30, PVP K60 and PVP K90.
在本发明一个实施方式中，所述钯纳米颗粒与所述分散剂的重量比为0.1-10：1，优选为0.2-5：1，更优选为0.5-2：1。In one embodiment of the present invention, the weight ratio of the palladium nanoparticles to the dispersant is 0.1-10:1, preferably 0.2-5:1, more preferably 0.5-2:1.
在另一方面，本发明还提供了用于在柔性基板上形成金属网格的方法，其中，所述方法包括以下步骤：In another aspect, the present invention also provides a method for forming a metal grid on a flexible substrate, wherein the method includes the following steps:
(1)在所述柔性基板的一个表面上依次涂覆UV可固化材料、如上所述的化学镀铜催化剂、以及保护层材料；(1) sequentially coating UV curable material, electroless copper plating catalyst as described above, and protective layer material on a surface of the flexible substrate;
(2)将涂覆后的柔性基板进行曝光和显影过程，以按照期望的图案在所述柔性基板的表面上依次形成UV可固化层和催化层；以及(2) exposing and developing the coated flexible substrate to sequentially form a UV curable layer and a catalytic layer on the surface of the flexible substrate according to a desired pattern; and
(3)在所述图案上镀铜，从而形成所述金属网格。(3) Plating copper on the pattern to form the metal mesh.
在本发明的一个实施方式中，所述涂覆为湿法涂覆。In one embodiment of the present invention, the coating is wet coating.
在本发明的一个实施方式中，所述UV可固化材料为正性光刻胶或负性光刻胶。In one embodiment of the present invention, the UV curable material is a positive photoresist or a negative photoresist.
在另一方面，本发明还提供了一种金属网格触摸传感器，其特征在于，所述金属网格触摸传感器的金属网格通过如上所述的方法来形成。In another aspect, the present invention also provides a metal grid touch sensor, wherein the metal grid of the metal grid touch sensor is formed by the above-mentioned method.
与现有的技术方案相比，本发明的技术方案至少包括以下优点：Compared with existing technical solutions, the technical solution of the present invention at least includes the following advantages:
本发明所提供的化学镀铜催化剂具有优异的催化活性，在使用本发明的化学镀铜催化剂(特别是当催化剂中包含聚烯烃类超分散剂时)形成金属铜网格线时，具有减少化学镀铜过程中金属网格的起镀时间、降低金属铜网格线线宽等优点，具有较高实用性；并且本发明的化学镀铜催化剂具有优异的稳定性，可以常温放置更长时间而不出现沉淀。The electroless copper plating catalyst provided by the present invention has excellent catalytic activity, and when using the electroless copper plating catalyst of the present invention (especially when comprising polyolefin hyperdispersant in the catalyzer) to form metal copper grid lines, there is a reduction in chemical Advantages such as the starting time of plating of metal grid in the copper plating process, reducing the line width of metal copper grid lines have higher practicability; Precipitation did not occur.
附图说明Description of drawings
附图是用来提供对本发明的进一步理解，并且构成说明书的一部分，与下面的具体实施方式一起用于解释本发明，但并不构成对本发明的限制。在附图中：The accompanying drawings are used to provide a further understanding of the present invention, and constitute a part of the description, together with the following specific embodiments, are used to explain the present invention, but do not constitute a limitation to the present invention. In the attached picture:
图1示出了根据本发明实施方式的形成金属网格的示例性方法的流程图。FIG. 1 shows a flowchart of an exemplary method of forming a metal mesh according to an embodiment of the present invention.
图2示出了根据本发明的实施例1和实施例3制备的铜金属网格样品，图中所示样品为20倍放大，实施例3制备的铜金属网格样品镀铜5秒即可起镀，而实施例1制备的铜金属网格样品镀铜30s才能起镀。Fig. 2 shows the copper metal grid sample prepared according to embodiment 1 and embodiment 3 of the present invention, the sample shown in the figure is 20 times magnification, and the copper metal grid sample prepared by embodiment 3 can be plated with copper for 5 seconds Start plating, and the copper metal grid sample that embodiment 1 prepares is plated copper 30s and just can start plating.
图3示出了根据本发明的实施例1-1制得的样品在镀铜后和显影后的线宽。Fig. 3 shows the line width of the sample prepared according to Example 1-1 of the present invention after copper plating and development.
图4示出了根据本发明的实施例1-2制得的样品在镀铜后和显影后的线宽。FIG. 4 shows the line widths of samples prepared according to Examples 1-2 of the present invention after copper plating and development.
图5示出了根据本发明的实施例1-3制得的样品在镀铜后和显影后的线宽。FIG. 5 shows the line widths of samples prepared according to Examples 1-3 of the present invention after copper plating and development.
图6示出了根据本发明的实施例2-1制得的样品在镀铜后和显影后的线宽。Fig. 6 shows the line width of the sample prepared according to Example 2-1 of the present invention after copper plating and development.
图7示出了根据本发明的实施例2-2制得的样品在镀铜后和显影后的线宽。FIG. 7 shows the line widths of the samples prepared according to Example 2-2 of the present invention after copper plating and development.
图8示出了根据本发明的实施例2-3制得的样品在镀铜后和显影后的线宽。FIG. 8 shows the line widths of samples prepared according to Examples 2-3 of the present invention after copper plating and development.
图9示出了根据本发明的实施例3-1制得的样品在镀铜后和显影后的线宽。Fig. 9 shows the line width of the sample prepared according to Example 3-1 of the present invention after copper plating and development.
图10示出了根据本发明的实施例3-2制得的样品在镀铜后和显影后的线宽。Fig. 10 shows the line width of the sample prepared according to Example 3-2 of the present invention after copper plating and development.
图11示出了根据本发明的实施例3-3制得的样品在镀铜后和显影后的线宽。Fig. 11 shows the line widths of samples prepared according to Example 3-3 of the present invention after copper plating and development.
图12示出了根据本发明实施方式的使用实施例3的化学镀铜催化剂及线宽为1.25微米的光罩经曝光显影后可实现的镀铜效果。12 shows the copper plating effect that can be achieved after exposure and development using the electroless copper plating catalyst of Example 3 and a photomask with a line width of 1.25 μm according to an embodiment of the present invention.
图13示出了根据本发明实施方式的使用实施例3的化学镀铜催化剂的镀铜后附着力的测试结果。FIG. 13 shows test results of adhesion after copper plating using the electroless copper plating catalyst of Example 3 according to an embodiment of the present invention.
具体实施方式Detailed ways
以下对本发明的具体实施方式进行详细说明。应当理解的是，此处所描述的具体实施方式仅用于说明和解释本发明，并不用于限制本发明。Specific embodiments of the present invention will be described in detail below. It should be understood that the specific embodiments described here are only used to illustrate and explain the present invention, and are not intended to limit the present invention.
在本文中所披露的范围的端点和任何值都不限于该精确的范围或值，这些范围或值应当理解为包含接近这些范围或值的值。对于数值范围来说，各个范围的端点值之间、各个范围的端点值和单独的点值之间，以及单独的点值之间可以彼此组合而得到一个或多个新的数值范围，这些数值范围应被视为在本文中具体公开。Neither the endpoints nor any values of the ranges disclosed herein are limited to such precise ranges or values, and these ranges or values are understood to include values approaching these ranges or values. For numerical ranges, between the endpoints of each range, between the endpoints of each range and individual point values, and between individual point values can be combined with each other to obtain one or more new numerical ranges, these values Ranges should be considered as specifically disclosed herein.
除非另有定义，本文使用的所有术语(包括技术和科学术语)具有与本发明所属领域的普通技术人员通常理解的相同的含义。还应当理解，诸如在通常使用的字典中定义的那些术语应该被解释为具有与它们在相关技术的上下文中的含义一致的含义，并且不会以理想化或过度形式化的含义来解释，除非在此明确地定义。Unless otherwise defined, all terms (including technical and scientific terms) used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. It should also be understood that terms such as those defined in commonly used dictionaries should be interpreted to have a meaning consistent with their meaning in the context of the relevant art, and not to be interpreted in an idealized or overly formalized meaning unless clearly defined here.
在一方面，本发明提供了一种化学镀铜催化剂，其包含钯纳米颗粒和分散剂，其中，所述分散剂选自聚酯型超分散剂、聚丙烯酸酯型超分散剂和聚烯烃类超分散剂中的一种或多种。In one aspect, the present invention provides an electroless copper plating catalyst comprising palladium nanoparticles and a dispersant, wherein the dispersant is selected from polyester hyperdispersants, polyacrylate hyperdispersants and polyolefins One or more of hyperdispersants.
经过研究后发现，当本发明的化学镀铜催化剂选用聚酯型超分散剂、聚丙烯酸酯型超分散剂和聚烯烃类超分散剂中的一种或多种作为分散剂时，能够使得钯纳米颗粒被更好地包裹分散，得到的胶体钯纳米颗粒粒径更小，催化活更强。将粒径更小，催化活更强的钯纳米颗粒作为第二层的涂覆材料，可以减少化学镀铜过程中金属网格的起镀时间。同时，本发明制备的化学镀铜催化剂中的钯纳米颗粒稳定性更强，可以常温放置更长时间不出现沉淀。After research, it is found that when the electroless copper plating catalyst of the present invention selects one or more of polyester type hyperdispersants, polyacrylate type hyperdispersants and polyolefin hyperdispersants as dispersants, palladium can be made The nanoparticles are better wrapped and dispersed, and the obtained colloidal palladium nanoparticles have smaller particle size and stronger catalytic activity. Using palladium nanoparticles with smaller particle size and stronger catalytic activity as the coating material of the second layer can reduce the plating start time of the metal grid during the electroless copper plating process. At the same time, the palladium nanoparticles in the electroless copper plating catalyst prepared by the present invention are more stable, and can be placed at room temperature for a longer period of time without precipitation.
在本发明的一个优选实施方式中，所述分散剂可以至少包含聚烯烃类超分散剂。例如，在一个具体实施方式中，所述分散剂可以仅包含聚烯烃类超分散剂、或由其组成。在另一个具体实施方式中，所述分散剂可以包含聚烯烃类超分散剂和聚酯型超分散剂两者、或由其组成。在另一个具体实施方式中，所述分散剂可以包含聚烯烃类超分散剂和聚丙烯酸酯型超分散剂两者、或由其组成。在另一个具体实施方式中，所述分散剂可以包含聚酯型超分散剂、聚丙烯酸酯型超分散剂和聚烯烃类超分散剂三者、或由其组成。In a preferred embodiment of the present invention, the dispersant may at least contain a polyolefin hyperdispersant. For example, in a specific embodiment, the dispersant may only comprise, or consist of, a polyolefin-based hyperdispersant. In another specific embodiment, the dispersant may comprise or consist of both a polyolefin hyperdispersant and a polyester hyperdispersant. In another specific embodiment, the dispersant may comprise or consist of both polyolefin-based hyperdispersants and polyacrylate-based hyperdispersants. In another specific embodiment, the dispersant may comprise or consist of polyester hyperdispersant, polyacrylate hyperdispersant and polyolefin hyperdispersant.
本发明对聚酯型超分散剂、聚丙烯酸酯型超分散剂和聚烯烃类超分散剂的具体种类没有特别的限制，可以使用技术人员所知晓的任何聚酯型超分散剂、聚丙烯酸酯型超分散剂和聚烯烃类超分散剂。在本发明的一个优选实施方式中，所述聚酯型超分散剂可以选自Solsperse-3000、Solsperse-9000、Solsperse-24000、Solsperse-46000和Solsperse-20000中的一种或多种；所述聚丙烯酸酯型超分散剂可以选自EL-vacit AB 1010、EL-vacit AB 1015、EL-vacit AB 1020、EL-vacit AB 1030、Disperse-AYD15、BYK-358、BYK-163和BYK-154中的一种或多种；所述聚烯烃类超分散剂可以选自PVP K15、PVP K30、PVP K60和PVP K90中的一种或多种，但不限于此。The present invention is not particularly limited to the specific types of polyester type hyperdispersant, polyacrylate type hyperdispersant and polyolefin type hyperdispersant, any polyester type hyperdispersant, polyacrylate known to the skilled person can be used type hyperdispersant and polyolefin hyperdispersant. In a preferred embodiment of the present invention, the polyester type hyperdispersant can be selected from one or more of Solsperse-3000, Solsperse-9000, Solsperse-24000, Solsperse-46000 and Solsperse-20000; Polyacrylate hyperdispersant can be selected from EL-vacit AB 1010, EL-vacit AB 1015, EL-vacit AB 1020, EL-vacit AB 1030, Disperse-AYD15, BYK-358, BYK-163 and BYK-154 One or more of; the polyolefin hyperdispersant can be selected from one or more of PVP K15, PVP K30, PVP K60 and PVP K90, but not limited thereto.
另外，本发明对所述化学镀铜催化剂中钯纳米颗粒和分散剂也没有特别的限制，可以根据本领域技术人员的经验以及实际需要进行调整。在本发明的一个优选实施方式中，所述钯纳米颗粒与所述分散剂的重量比可以为0.1-10：1(例如0.1：1、0.2：1、0.3：1、0.5：1、0.8：1、1：1、1.2：1、1.5：1、2：1、3： 1、5：1或8：1等)，优选为0.2-5：1，更优选为0.5-2：1。In addition, the present invention has no special limitation on the palladium nanoparticles and dispersant in the electroless copper plating catalyst, and can be adjusted according to the experience and actual needs of those skilled in the art. In a preferred embodiment of the present invention, the weight ratio of the palladium nanoparticles to the dispersant can be 0.1-10:1 (for example, 0.1:1, 0.2:1, 0.3:1, 0.5:1, 0.8:1 1, 1:1, 1.2:1, 1.5:1, 2:1, 3:1, 5:1 or 8:1, etc.), preferably 0.2-5:1, more preferably 0.5-2:1.
在另一方面，本发明还提供了一种用于在柔性基板上形成金属网格的方法，其中，所述方法包括以下步骤：In another aspect, the present invention also provides a method for forming a metal grid on a flexible substrate, wherein the method includes the following steps:
(1)在所述柔性基板的一个表面上依次涂覆UV可固化材料、如上所述的化学镀铜催化剂、以及保护层材料；(1) sequentially coating UV curable material, electroless copper plating catalyst as described above, and protective layer material on a surface of the flexible substrate;
(2)将涂覆后的柔性基板进行曝光和显影过程，以按照期望的图案在所述柔性基板的表面上依次形成UV可固化层和催化层；以及(2) exposing and developing the coated flexible substrate to sequentially form a UV curable layer and a catalytic layer on the surface of the flexible substrate according to a desired pattern; and
(3)在所述图案上镀铜，从而在柔性基板上形成所述金属网格。(3) Plating copper on the pattern to form the metal grid on the flexible substrate.
对于步骤(1)，图1示出了根据本发明实施方式的形成金属网格的示例性方法的流程图，其中通过在基板的一个表面上依次涂覆UV可固化材料、如上所述的化学镀铜催化剂、以及保护层材料从而在所述基板的该表面上依次形成UV可固化层、Pd纳米颗粒层和水溶性保护层。For step (1), FIG. 1 shows a flow chart of an exemplary method of forming a metal mesh according to an embodiment of the present invention, wherein by sequentially coating a UV curable material on one surface of a substrate, chemical A copper catalyst, and a protective layer material are plated to sequentially form a UV curable layer, a Pd nanoparticle layer, and a water-soluble protective layer on the surface of the substrate.
对于作为第一层(或称为基础层)的UV可固化材料，所述UV可固化材料可以为正性光刻胶或负性光刻胶。在一个实施方式中，所述正性光刻胶可以优选地包含曝光后可溶于显影液的树脂材料，并且所述负光刻胶可以优选地包含曝光后不溶于显影液的树脂材料。所述显影液通常是含有碱性化合物和表面活性剂的水溶液，碱性化合物可以是无机或有机碱性化合物，这些无机和有机碱性化合物可以单独使用或两种以上组合使用；而作为表面活性剂，可以使用选自由非离子表面活性剂、阴离子表面活性剂和阳离子表面活性剂所组成的组中的至少一种，这些表面活性剂可以单独使用，也可以两种以上组合使用。As for the UV curable material as the first layer (or referred to as base layer), the UV curable material can be a positive photoresist or a negative photoresist. In one embodiment, the positive photoresist may preferably include a resin material that is soluble in a developer after exposure, and the negative photoresist may preferably include a resin material that is insoluble in a developer after exposure. Described developing solution is usually the aqueous solution that contains alkaline compound and surfactant, and alkaline compound can be inorganic or organic alkaline compound, and these inorganic and organic alkaline compounds can be used alone or in combination of two or more; And as surface active As an agent, at least one selected from the group consisting of nonionic surfactants, anionic surfactants and cationic surfactants can be used, and these surfactants can be used alone or in combination of two or more.
另外，所述UV可固化材料中还包含光引发剂，例如，在本发明的一个实施方式中，所述光引发剂可以选自由苯乙酮类化合物、二苯甲酮类化合物、三嗪类化合物、噻吨酮类化合物和肟酯类化合物组成的组中的至少一种。苯乙酮类化合物的具体实例可以包括2-羟基-2-甲基-1-苯基丙-1-酮、二乙氧基苯乙酮和2-(4-甲基苄基)-2-(二甲基氨基)-1-(4-吗啉代苯基)丁-1-酮等。二苯甲酮类化合物的具体实例可以包括二苯甲酮、邻苯甲酰基苯甲酸甲酯、4-苯甲酰基-4'-甲基二苯基硫醚和2,4,6-三甲基二苯甲酮等。三嗪类化合物的具体实例可以包括2,4-双(三氯甲基)-6-(4-甲氧基苯基)-1,3,5-三嗪、2,4-双(三氯甲基)-6-(4-甲氧基萘 基)-1,3,5-三嗪、2,4-双(三氯甲基)-6-[2-(3,4-二甲氧基苯基)乙烯基]-1,3,5-三嗪和2,4-双(三氯甲基)-6-2-(4-二乙基氨基-2-甲基苯基)乙烯基]-1,3,5-三嗪等。噻吨酮类化合物的具体实例可以包括2-异丙基噻吨酮、2,4-二乙基噻吨酮、2,4-二氯噻吨酮和1-氯-4-丙氧基噻吨酮等。肟酯类化合物的具体实例可以包括邻乙氧基羰基-α-氧基亚氨基-1-苯基丙-1-酮、1,2-辛二酮、1-(4-苯硫基)苯基和2-(邻苯甲酰肟)等。In addition, the UV curable material also includes a photoinitiator, for example, in one embodiment of the present invention, the photoinitiator can be selected from acetophenone compounds, benzophenone compounds, triazines At least one of the group consisting of compound, thioxanthone compound and oxime ester compound. Specific examples of acetophenone compounds may include 2-hydroxy-2-methyl-1-phenylpropan-1-one, diethoxyacetophenone, and 2-(4-methylbenzyl)-2- (Dimethylamino)-1-(4-morpholinophenyl)butan-1-one, etc. Specific examples of benzophenone compounds may include benzophenone, methyl o-benzoylbenzoate, 4-benzoyl-4'-methyldiphenyl sulfide, and 2,4,6-trimethyl benzophenone etc. Specific examples of triazine compounds may include 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-triazine, 2,4-bis(trichloromethyl) Methyl)-6-(4-methoxynaphthyl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(3,4-dimethoxy phenyl)vinyl]-1,3,5-triazine and 2,4-bis(trichloromethyl)-6-2-(4-diethylamino-2-methylphenyl)ethenyl ]-1,3,5-triazine etc. Specific examples of thioxanthone compounds may include 2-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, and 1-chloro-4-propoxythioxanthone xanthone etc. Specific examples of oxime ester compounds may include o-ethoxycarbonyl-α-oxyimino-1-phenylpropan-1-one, 1,2-octanedione, 1-(4-phenylthio)benzene base and 2-(o-benzoyl oxime), etc.
作为第二层的Pd纳米颗粒层即为本发明的化学镀铜催化剂，是本发明的在柔性基板上形成金属网格技术的关键。由于前述部分已经对本发明的化学镀铜催化剂的组分和含量等进行了详细描述，在本部分中将不再对所述化学镀铜催化剂的特征进行详细描述，以避免不必要的冗余。The Pd nano particle layer as the second layer is the electroless copper plating catalyst of the present invention, and is the key to the technology of forming the metal grid on the flexible substrate of the present invention. Since the components and contents of the electroless copper plating catalyst of the present invention have been described in detail in the previous section, the characteristics of the electroless copper plating catalyst will not be described in detail in this section to avoid unnecessary redundancy.
作为第三层的保护层材料，其主要是在曝光阶段起到保护作用，随后在显影阶段也会被上述显影液洗去。根据本发明，所述保护层材料可以使用本领域中常规的保护层材料来进行。在一个优选的实施方式中，所述保护层材料可以为水溶性材料，以使其能够在显影阶段溶于含水的显影液中。As the protective layer material of the third layer, it mainly plays a protective role in the exposure stage, and then it will be washed away by the developer in the development stage. According to the present invention, the protective layer material can be made using conventional protective layer materials in the art. In a preferred embodiment, the protective layer material may be a water-soluble material, so that it can be dissolved in an aqueous developer solution during the development stage.
根据本发明，对上述三种涂覆材料的涂覆方式可以优选地采用湿法涂覆的方式进行，即可以将液体或溶液形式的UV可固化材料、化学镀铜催化剂、以及保护层材料依次涂覆在所述基板的一个表面上。According to the present invention, the coating methods of the above three coating materials can preferably be carried out by wet coating, that is, the UV curable material in liquid or solution form, the electroless copper plating catalyst, and the protective layer material can be sequentially coated on one surface of the substrate.
对于步骤(2)，即将依次涂覆有UV可固化材料、化学镀铜催化剂、以及保护层材料的所述基板暴露于紫外线并在其间设置具有期望图案的掩模，从而在基板上形成期望的图案。随后，在显影过程中，如上所述，未被固化的所述UV可固化材料和所述保护层材料可以在显影过程中被去除。For step (2), the substrate coated with UV curable material, electroless copper plating catalyst, and protective layer material in sequence is exposed to ultraviolet rays and a mask with a desired pattern is set therebetween, thereby forming a desired pattern on the substrate. pattern. Subsequently, during development, the UV curable material and the protective layer material that are not cured may be removed during development, as described above.
对于步骤(3)，由于保护层材料已经被去除，此时钯纳米颗粒层处于最上层，可以作为镀铜的催化剂，因此该步骤只需在所述图案上进行镀铜、例如采用化学镀铜的方式即可，从而形成所需的金属网格。For step (3), since the protective layer material has been removed, the palladium nanoparticle layer is at the top layer and can be used as a catalyst for copper plating, so this step only needs to carry out copper plating on the pattern, such as using electroless copper plating The way can be, so as to form the required metal grid.
在另一方面，本发明还提供了一种金属网格触摸传感器，所述金属网格触摸传感器的金属网格通过如上所述的形成金属网格的方法来形成。In another aspect, the present invention also provides a metal grid touch sensor, wherein the metal grid of the metal grid touch sensor is formed by the method for forming the metal grid as described above.
综上所述，本发明所提供的化学镀铜催化剂具有优异的催化活性，在使用本发明的化学镀铜催化剂(特别是当催化剂中包含聚烯烃类超分散剂时)形成 金属铜网格线时，具有减少化学镀铜过程中金属网格的起镀时间、降低金属铜网格线线宽等优点，具有较高实用性；并且本发明的化学镀铜催化剂具有优异的稳定性，可以常温放置更长时间而不出现沉淀。In summary, the electroless copper plating catalyst provided by the present invention has excellent catalytic activity, and when using the electroless copper plating catalyst of the present invention (especially when comprising polyolefin hyperdispersant in the catalyst) to form metallic copper grid lines , it has the advantages of reducing the plating time of the metal grid in the electroless copper plating process, reducing the line width of the metal copper grid line, and has higher practicability; and the electroless copper plating catalyst of the present invention has excellent stability and can be used at room temperature It can be left for a longer period of time without precipitation.
实施例Example
实施例1Example 1
按质量组分取90％的溶剂、4％醋酸钯、6％分散剂A混合加热至105℃，搅拌2h后取所得混合液与纯水和表面活性剂混合，制得含钯纳米颗粒催化剂涂液，其中，溶剂为乳酸乙酯，A为超分散剂Solsperse46000，表面活性剂为含氟表面活性剂。Take 90% solvent, 4% palladium acetate, and 6% dispersant A according to the mass components, mix and heat to 105° C., stir for 2 hours, take the resulting mixed solution and mix it with pure water and surfactant to prepare palladium-containing nanoparticle catalyst coating. Liquid, wherein, the solvent is ethyl lactate, A is the hyperdispersant Solsperse46000, and the surfactant is a fluorosurfactant.
使用涂布线棒在柔性基板的一个表面上涂覆含有Irgacure 907的负性光刻胶涂层，然后在烘箱中于70℃的温度下干燥120秒，以得到厚度为800nm的涂层；在光刻胶膜的顶部涂一层如上制备的含钯纳米颗粒催化剂涂层，然后再涂一层水溶性材料用于保护上述两个涂层，之后使用具有峰波为314nm的紫外光进行曝光；曝光后，使用碱性显影液冲洗基板以去除水溶性保护涂层及未固化的负性光刻胶涂层，所得样品浸入化学镀铜液中以生长铜网格，在所述过程中含钯纳米颗粒催化剂起到催化镀铜反应的作用。A negative photoresist coating containing Irgacure 907 was coated on one surface of a flexible substrate using a coating wire bar, and then dried in an oven at a temperature of 70° C. for 120 seconds to obtain a coating with a thickness of 800 nm; The top of the photoresist film is coated with a palladium-containing nanoparticle catalyst coating prepared as above, and then coated with a layer of water-soluble material for protecting the above two coatings, and then exposed with ultraviolet light having a peak wave of 314nm; After exposure, the substrate is rinsed with an alkaline developer to remove the water-soluble protective coating and the uncured negative photoresist coating, and the resulting sample is immersed in an electroless copper plating solution to grow a copper grid, which contains palladium The nanoparticle catalyst plays the role of catalyzing the copper plating reaction.
实施例2Example 2
以与实施例1类似的方法进行镀铜，不同之处在于，镀铜催化剂如下制备：按质量组分取90％的溶剂、4％醋酸钯、6％分散剂B混合加热至105℃，搅拌2h后取所得混合液与纯水和表面活性剂混合，制得含钯纳米颗粒催化剂涂料，其中，溶剂为乳酸乙酯，B为超分散剂PVP K30，表面活性剂为含氟表面活性剂。Copper plating is carried out in a method similar to Example 1, except that the copper plating catalyst is prepared as follows: get 90% solvent, 4% palladium acetate, and 6% dispersant B by mass components and mix and heat to 105 ° C, stir After 2h, the resulting mixed solution was mixed with pure water and a surfactant to obtain a palladium-containing nanoparticle catalyst coating, wherein the solvent was ethyl lactate, B was a hyperdispersant PVP K30, and the surfactant was a fluorosurfactant.
实施例3Example 3
以与实施例1类似的方法进行镀铜，不同之处在于，镀铜催化剂如下制备：按质量组分取90％的溶剂、4％醋酸钯、1％分散剂A、5％分散剂B混合加热至105℃，搅拌2h后取所得混合液与纯水和表面活性剂混合，制得催化剂涂料，其中，溶剂为乳酸乙酯，A为超分散剂Solsperse46000，B为超分散剂PVP K30，表面活性剂为氟表面活性剂。Copper plating is carried out in a method similar to Example 1, except that the copper plating catalyst is prepared as follows: get 90% solvent, 4% palladium acetate, 1% dispersant A, 5% dispersant B by mass components and mix Heating to 105°C, stirring for 2 hours, taking the resulting mixed solution, mixing it with pure water and a surfactant to prepare a catalyst coating, wherein the solvent is ethyl lactate, A is the hyperdispersant Solsperse46000, and B is the hyperdispersant PVP K30. The active agent is a fluorosurfactant.
测试例test case
取三组按照实施例1步骤制得的金属铜网格样品，命名为实施例1-1、实施例1-2、实施例1-3，在2.5D二次元手动影像测量仪下测量金属铜网格线条宽度。Take three groups of metallic copper grid samples prepared according to the steps of Example 1, named as Example 1-1, Example 1-2, and Example 1-3, and measure metallic copper under a 2.5D two-dimensional manual image measuring instrument Grid line width.
取三组按照实施例2步骤制得的金属铜网格样品，命名为实施例2-1、实施例2-2、实施例2-3，在2.5D二次元手动影像测量仪下测量金属铜网格线条宽度。Take three groups of metallic copper grid samples prepared according to the steps of Example 2, named as Example 2-1, Example 2-2, and Example 2-3, and measure metallic copper under a 2.5D two-dimensional manual image measuring instrument Grid line width.
取三组按照实施例3步骤制得的金属铜网格样品，命名为实施例3-1、实施例3-2、实施例3-3，在2.5D二次元手动影像测量仪下测量金属铜网格线条宽度。Take three groups of metallic copper grid samples prepared according to the steps of Example 3, named as Example 3-1, Example 3-2, and Example 3-3, and measure metallic copper under a 2.5D two-dimensional manual image measuring instrument Grid line width.
将上述9组样品镀铜之前的显影线宽平均值和镀铜后的金属铜网格线条宽度平均值的数据如下表1-2和图3-11所示。Table 1-2 and Figure 3-11 show the data of the average development line width before copper plating and the average copper grid line width after copper plating of the above nine groups of samples.
表1显影后平均线宽Table 1 average line width after development
Figure PCTCN2022113510-appb-000001
Figure PCTCN2022113510-appb-000001
表2镀铜后平均线宽Table 2 Average line width after copper plating
Figure PCTCN2022113510-appb-000002
Figure PCTCN2022113510-appb-000002
根据表1和表2中的数据可以看出，由实施例1-3制得的样品均实现了较窄的显影线宽和金属铜网格线线宽。特别地，在显影线宽接近的情况下，实施例3制得的样品的金属铜网格线线宽最窄。这充分证实了本发明提供的化学催化剂在按上述方法制备金属铜网格线时，具有降低金属铜网格线线宽的优点，具有较高实用性，特别是当超分散剂中包含聚烯烃类超分散剂例如PVP K30时，上述效果更佳优异。According to the data in Table 1 and Table 2, it can be seen that the samples prepared in Examples 1-3 all realized narrower development line width and metal copper grid line width. In particular, the sample prepared in Example 3 has the narrowest line width of the metal copper grid line when the development line width is close. This has fully confirmed that the chemical catalyst provided by the present invention has the advantage of reducing the width of the metal copper grid line when the metal copper grid line is prepared by the above-mentioned method, and has higher practicability, especially when the hyperdispersant contains polyolefin When using a hyperdispersant such as PVP K30, the above effects are even better.
同时，通过观察得到，实施例1制备的催化剂可以常温放置4天内不出现沉淀，而实施例3制备的催化剂可以常温放置10天内不出现沉淀，且依然具有良好的催化活性。由此，证实了本发明的化学镀铜催化剂具有优异的稳定性，可以常温放置更长时间而不出现沉淀。At the same time, it can be observed that the catalyst prepared in Example 1 can be placed at room temperature for 4 days without precipitation, while the catalyst prepared in Example 3 can be placed at room temperature for 10 days without precipitation, and still has good catalytic activity. Thus, it is confirmed that the electroless copper plating catalyst of the present invention has excellent stability and can be placed at room temperature for a longer period of time without precipitation.
另外，图2示出了实施例1和实施例3制备的铜金属网格样品，图中所示样品为20倍放大，实施例3制备的铜金属网格样品镀铜5秒即可起镀，而实施例1制备的铜金属网格样品镀铜30s才能起镀，这证实了实施例3制备的催化剂活性更加优异。In addition, Fig. 2 shows the copper metal grid sample prepared by embodiment 1 and embodiment 3, the sample shown in the figure is 20 times magnification, and the copper metal grid sample prepared by embodiment 3 can be plated in 5 seconds , while the copper metal grid sample prepared in Example 1 could be plated after 30s of copper plating, which confirmed that the catalyst activity prepared in Example 3 was more excellent.
如图3-5所示，对于实施例1制备的样品，显影后线宽与镀铜后线宽差值在1.6微米左右，即镀铜后线宽与显影后线宽差值较小。As shown in Figures 3-5, for the sample prepared in Example 1, the difference between the line width after development and the line width after copper plating is about 1.6 microns, that is, the difference between the line width after copper plating and the line width after development is relatively small.
如图6-8所示，对于实施例2制备的样品，显影后线宽与镀铜后线宽差值在1.9微米左右，即镀铜后线宽与显影后线宽差值较小。As shown in Figures 6-8, for the sample prepared in Example 2, the difference between the line width after development and the line width after copper plating is about 1.9 microns, that is, the difference between the line width after copper plating and the line width after development is relatively small.
如图9-11所示，对于实施例3制备的样品，显影后线宽与镀铜后线宽差值在0.4微米左右，即镀铜后线宽与显影后线宽差值极小。As shown in Figures 9-11, for the sample prepared in Example 3, the difference between the line width after development and the line width after copper plating is about 0.4 microns, that is, the difference between the line width after copper plating and the line width after development is extremely small.
如图12所示，取实施例3方法制备的催化剂制成的涂布样品，使用设计线宽为1.25微米的光罩曝光后进行显影镀铜，做到的最小铜网格线线宽为1.5微米，体现了本发明的新化学镀铜催化剂具有更强催化性能的特点，同时有助于减少镀铜后线宽。As shown in Figure 12, take the coated sample made of the catalyst prepared by the method in Example 3, use a photomask with a designed line width of 1.25 microns to expose and then develop copper plating, and the minimum copper grid line width achieved is 1.5 microns. Micron, which reflects the characteristics that the new electroless copper plating catalyst of the present invention has stronger catalytic performance, and at the same time helps to reduce the line width after copper plating.
如图13所示，取实施例3方法制备的催化剂制成的涂布样品，在镀铜后使用3M 610胶带贴在金属铜网格线上，用手指按压至全部贴紧，然后快速将胶带撕下，无铜线掉落，证明其镀铜后附着力良好。As shown in Figure 13, take the coated sample made of the catalyst prepared by the method in Example 3, stick it on the metal copper grid line with 3M 610 adhesive tape after copper plating, press it with your fingers until it is completely attached, and then quickly put the adhesive tape on Tear it off, no copper wires fall off, which proves that it has good adhesion after copper plating.
以上详细描述了本发明的优选实施方式，但是，本发明并不限于上述实施方式中的具体细节，在本发明的技术构思范围内，可以对本发明的技术方案进行多种简单变型，这些简单变型均属于本发明的保护范围。The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited to the specific details in the above embodiments. Within the scope of the technical concept of the present invention, various simple modifications can be made to the technical solutions of the present invention. These simple modifications All belong to the protection scope of the present invention.
另外需要说明的是，在上述具体实施方式中所描述的各个具体技术特征，在不矛盾的情况下，可以通过任何合适的方式进行组合，为了避免不必要的重复，本发明对各种可能的组合方式不再另行说明。In addition, it should be noted that the various specific technical features described in the above specific embodiments can be combined in any suitable way if there is no contradiction. The combination method will not be described separately.
此外，本发明的各种不同的实施方式之间也可以进行任意组合，只要其不违背本发明的思想，其同样应当视为本发明所公开的内容。In addition, various combinations of different embodiments of the present invention can also be combined arbitrarily, as long as they do not violate the idea of the present invention, they should also be regarded as the disclosed content of the present invention.

Claims (10)

  1. 一种化学镀铜催化剂，其包含钯纳米颗粒和分散剂，其中，所述分散剂选自聚酯型超分散剂、聚丙烯酸酯型超分散剂和聚烯烃类超分散剂中的一种或多种。An electroless copper plating catalyst, which comprises palladium nanoparticles and a dispersant, wherein the dispersant is selected from one or more of a polyester type hyperdispersant, a polyacrylate type hyperdispersant and a polyolefin hyperdispersant Various.
  2. 根据权利要求1所述的化学镀铜催化剂，其中，所述分散剂至少包含聚烯烃类超分散剂。The electroless copper plating catalyst according to claim 1, wherein the dispersant includes at least a polyolefin hyperdispersant.
  3. 根据权利要求1或2所述的化学镀铜催化剂，其中，所述聚酯型超分散剂选自Solsperse-3000、Solsperse-9000、Solsperse-24000、Solsperse-46000和Solsperse-20000中的一种或多种。The electroless copper plating catalyst according to claim 1 and 2, wherein, the polyester type hyperdispersant is selected from one of Solsperse-3000, Solsperse-9000, Solsperse-24000, Solsperse-46000 and Solsperse-20000 or Various.
  4. 根据权利要求1或2所述的化学镀铜催化剂，其中，所述聚丙烯酸酯型超分散剂选自EL-vacit AB 1010、EL-vacit AB 1015、EL-vacit AB 1020、EL-vacit AB 1030、Disperse-AYD15、BYK-358、BYK-163和BYK-154中的一种或多种。The electroless copper plating catalyst according to claim 1 or 2, wherein the polyacrylate type hyperdispersant is selected from EL-vacit AB 1010, EL-vacit AB 1015, EL-vacit AB 1020, EL-vacit AB 1030 One or more of , Disperse-AYD15, BYK-358, BYK-163 and BYK-154.
  5. 根据权利要求1或2所述的化学镀铜催化剂，其中，所述聚烯烃类超分散剂选自PVP K15、PVP K30、PVP K60和PVP K90中的一种或多种。Electroless copper plating catalyst according to claim 1 and 2, wherein, said polyolefin hyperdispersant is selected from one or more in PVP K15, PVP K30, PVP K60 and PVP K90.
  6. 根据权利要求1所述的化学镀铜催化剂，其中，所述钯纳米颗粒与所述分散剂的重量比为0.1-10：1，优选为0.2-5：1，更优选为0.5-2：1。The electroless copper plating catalyst according to claim 1, wherein the weight ratio of the palladium nanoparticles to the dispersant is 0.1-10:1, preferably 0.2-5:1, more preferably 0.5-2:1 .
  7. 一种用于在柔性基板上形成金属网格的方法，其中，所述方法包括以下步骤：A method for forming a metal grid on a flexible substrate, wherein the method comprises the steps of:
    (1)在所述柔性基板的一个表面上依次涂覆UV可固化材料、根据权利要求1-6中任一项所述的化学镀铜催化剂、以及保护层材料；(1) coating UV curable material, electroless copper plating catalyst according to any one of claims 1-6, and protective layer material sequentially on a surface of the flexible substrate;
    (2)将涂覆后的柔性基板进行曝光和显影过程，以按照期望的图案在所述柔性基板的表面上依次形成UV可固化层和催化层；以及(2) exposing and developing the coated flexible substrate to sequentially form a UV curable layer and a catalytic layer on the surface of the flexible substrate according to a desired pattern; and
    (3)在所述图案上镀铜，从而形成所述金属网格。(3) Plating copper on the pattern to form the metal mesh.
  8. 根据权利要求7所述的方法，其中，所述涂覆为湿法涂覆。The method of claim 7, wherein the coating is a wet coating.
  9. 根据权利要求7所述的方法，其中，所述UV可固化材料为负性光刻胶。The method of claim 7, wherein the UV curable material is a negative tone photoresist.
  10. 一种金属网格触摸传感器，其特征在于，所述金属网格触摸传感器的 金属网格通过根据权利要求7-9中任一项所述的方法来形成。A metal grid touch sensor, characterized in that the metal grid of the metal grid touch sensor is formed by the method according to any one of claims 7-9.
PCT/CN2022/113510 2021-09-10 2022-08-19 Electroless copper plating catalyst and method for forming metal grid by using same WO2023035903A1 (en)

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CN115386865A (en) * 2022-08-30 2022-11-25 江苏软讯科技有限公司 Low-stress chemical copper plating liquid medicine and preparation method of metal grid conducting film
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