TW200815545A

TW200815545A - Dispersion for application of a metal layer

Info

Publication number: TW200815545A
Application number: TW096128429A
Authority: TW
Inventors: Rene Lochtman; Jurgen Kaczun; Norbert Schneider; Jurgen Pfister; Norbert Wagner; Christoffer Kieburg; Ketan Joshi
Original assignee: Basf Ag
Priority date: 2006-08-03
Filing date: 2007-08-02
Publication date: 2008-04-01
Also published as: WO2008015167A1

Abstract

The present invention relates to a dispersion for application of a metal layer on an electrically non-conductive substrate, comprising (a) from 0.1 to 99.8% by weight, based on the total weight of components, A, B, C, and D, of an organic binder component A; (b) from 0.1 to 30% by weight, based on the total weight of components A, B, C, and D, of carbon nanotubes, as component B; (c) from 0.1 to 70% by weight, based on the total weight of components A, B, C, and D, of electrically conductive particles whose average diameter is from 0.01 to 100 μ as component C; (d) from 0 to 99.7% by weight, based on the total weight of components A, B, C, and D, of a solvent component D, and also to processes for preparation of this dispersion, to the use of this dispersion, processes for production of a metal layer on the surface of an electrically non-conductive substrate, and substrate surfaces, and also their use.

Description

200815545 九、發明說明：【發明所屬之技術領域】本發明係關於一種用於金屬層塗佈之分散液，係關於其製備方法且係關於使用該分散液於一基板上製造一金屬層之方法。本發明進一步係關於由此所塗覆之基板表面及其用途。【先前技術】200815545 IX. Description of the Invention: [Technical Field] The present invention relates to a dispersion for metal layer coating, a method for preparing the same, and a method for producing a metal layer on a substrate using the dispersion . The invention further relates to the surface of the substrate thus coated and its use. [Prior Art]

已知各種於不傳導電流之基板上製造導電金屬層之技術。舉例而言’不導電之基板（例如塑料）可在高真空中加以金屬化，但該等方法較為複雜且昂貴。塑料金屬化之常見方法在一製程中執行若干連續步驟。此處之製程藉由在表面活化步驟中使用強酸或強鹼而開始。此處通常使用對健康具有危害之物質，例如鉻酸·硫酸。隨後經由具有適當過渡金屬錯合物之溶液塗覆塑料= 面。此等者在該製程中允許活化塑料表面之金屬化。導電塗層之方法使，但該等導電漆或然而，另一種於不導電之表面上獲得用導電漆或導電膏，將其塗佈至塑料上導電貧必須對該材料具有良好黏著性。 ,〇〇捅迷（例如）包含精細分散之鐵之g 用於於不導電之表面上製造導電層之製程中的" 外，、該漆意欲包含有機溶劑及特定比例之黏合劑。然而，伞所周知，因為分散金屬顆粒並未經j 成連貫導電層，所以該等導 4 t 入為寻V冤漆僅具有相對較率。該等層之電暮盡u、，t ¥革因此亚未達到具可比厚度之金j 122438.doc 200815545 被等電導率。層内金屬顏料含量之增加亦將導致電導率之私加，但問題常常存在於此，例如導電層對塑料表面之不充刀的黏著力或相對重金屬顆粒於漆中之不良分散性。Various techniques for fabricating a conductive metal layer on a substrate that does not conduct current are known. For example, a non-conducting substrate (e.g., plastic) can be metallized in a high vacuum, but such methods are complicated and expensive. A common method of plastic metallization performs several successive steps in a single process. The process here begins by using a strong acid or a strong base in the surface activation step. Health-hazardous substances such as chromic acid and sulfuric acid are usually used here. The plastic = face is then applied via a solution with the appropriate transition metal complex. These allow the metallization of the activated plastic surface during the process. The method of conducting the coating allows, but the conductive paint or the conductive paste obtained on the non-conductive surface is applied to the plastic. The conductive poor must have good adhesion to the material. In the process of manufacturing a conductive layer on a non-conducting surface, for example, the lacquer is intended to contain an organic solvent and a specific proportion of the binder. However, umbrellas are well known because they disperse metal particles and do not have a coherent conductive layer, so that the conductivity is only relatively high. The electricity of these layers is exhausted, and the leather is not equal to the gold with a comparable thickness. An increase in the amount of metallic pigment in the layer will also result in a private addition of conductivity, but problems often exist, such as the non-knife adhesion of the conductive layer to the plastic surface or the poor dispersion of relatively heavy metal particles in the paint.

DlA 1 521 1 52為此提出將包含黏合劑且包含精細分散之鐵的導電漆塗佈於不導電之表面上，且隨後藉由無電流法塗佈銀層或銅層於該導電漆上。可隨後藉由無電流法或電鍍去塗佈另—層。又，高鐵含量有利於獲得足夠之電導率，但其同樣造成相對重金屬顆粒於導電漆中之分散性問題。 ' 基於導電有機聚合物之塗覆提供另一種塗佈導電層至不導電表面之方法。舉例而言，DE 198 41 804描述藉由噴墨 P刷於一襯底上製造由聚伸烷基二氧基噻吩構成之導電結構。$而’該製程之缺點為，導電聚合物對許多襯底材料之黏者力往往係不夠的，同時電導率在較長距離内過低。另-缺點為所得層之耐化學性較弱，此使藉由電錢法進行金屬化不可行。 -種同樣已知用於提供具有電導率(藉由電鍍法進行金屬化的必而剛提）之塑料的方法為將碳奈米管（通常亦稱為碳奈米纖維)併入塑料中。胃等導電碳奈米管亦具有以； &勢’低重里（例如與金屬粉末相比較）及通常提高塑料韋刀性（參見例如US 2_/0025515 A1)。製造包含碳奈米管之塑料的缺點為：成本相對較高，碳奈米管之併入多半困難且塑料混合物之流動性通常降低（若整個塑料已為該等顆粒所填充時）。 122438.doc 200815545 DE 1 02 5 9 498 A1揭示不僅包令料斗立报彳或W a 偟…“立形式之碳(諸如碳黑〆 ’土）而且匕含碳奈米纖維之導電敎鄕安“π ¥冤熟塑性塑津4。該公開 *中所仏述之塑料混合物不僅具有電導率而且動性、良好表面品質以及較、又抓覆。，、尤其適用於靜電塗就藉由電鑛法進行金屬化而言，該等聚合物混合物之缺點為金屬化通常僅為極其緩慢、外，其Μ道+山係不可行的。此卜基於導電碳黑及/或基於碳奈米管之分散液不具有足乂用於Β午多塗覆應用之流動性。 :等由先前技術已知之製程之其他缺或電鍍法進行今屬卟而+社 Α …、电/瓜/麦 -性及… 層的不良黏著性以及均 ^ A ^ U rb ，、在於蛉電顆粒已嵌埋基貝材枓中且因此該等顆粒可剝®认/ 口P分顆粒在表面處為 j用的，從而導致就藉由盔電屬化而言該等顆粒令僅f Μ/或電鑛法進行金小㈣m半^ ^刀顆粒可利用。此當使用極均勾連續金屬其成問題。此使得此ρ,Γ 其困㈣實際上何能，且因匕口亥衣私不可靠0該影變其之氧化芦而、隹 Θ甚至由於任何存在於導電顆粒上心乳化層而進一步加劇。先前已知之製程的另一缺點鍍法進行金屬化較為緩慢於：.、、、電流法及/或電中，因此對於藉由無電流法及;:電在表面處為可利用且可用/，'又法進行金屬化而言因之—#在;^⑴ 長核之顆粒數目較少。其原在於^例如）塗佈印刷分散液時，重金屬顆粒陷 i22438.d〇i 200815545 人基質材料中而導致僅少數金屬顆粒保留於表面處。【發明内容】本發明之-目標為詳言之使用導電漆或導電分散液提供用於不導電基板之均句且連續金屬覆層的優化系統，愈已 . %系統相比較而言’該兩者具有由低重量、良好黏著性、 • A散性與流動性及高電導率以及快速金屬化性組成的改良特性組合。 • I發明之另—目標為提供—種可於-襯底上製造導電結構化或非結構化表面之替代性方法，該等表面為均勻且連續導電性的。因此，已發現一種用於塗佈一金屬層於一不導電基板上之分散液，其包含：、、’且知A Bc及D之總重量計，〇 ·〗至9 9 · 8重量。/。之有機黏合劑組份A ; 、、、伤A B、c及D之總重量計，〇 · 1至3 〇重量。/。之碳奈 • 米管作為組份B ; c以、’且伤A、B、C及D之總重量計，〇·!至7〇重量％之平均直徑為0.01至100 μηΊ的導電顆粒作為組份c ; d以、、且仞A、Β、C及D之總重量計，〇至99·7重量％之溶劑 . 組份D。卜已I現用於製備該分散液之方法以及該分散液之用途、用於在一不導電基板之表面上製備一金屬層之方法及基板表面以及其用途。本么明之分散液對於詳言之使用導電漆或導電分散液提 122438.doc 200815545 供用於不導電基板之金屬覆層的優化系統而言係重要的，當與已知糸統相比較時，該兩者具有由低重量、良好黏著性、分散性、流動性及高電導率組成的改良特性組合。【實施方式】本發明之分散液以及其他本發明之物品、方法及用途描述如下。本發明之用於塗佈金屬層於不導電基板上之分散液包含：（以組份A、B、C及D之總重量計，其總共為1〇〇重量 %) a· 0.1至99.8重量％、較佳2至87 5重量％、尤其較佳々至⑽ 重量％之組份A ; b.0.1至30重量％、較佳〇 5至2〇重量％、尤其較佳工至^重量％之組份B ; C. 0.1至70重量％、較佳2至65重量％、尤其較佳4至55重量 %之組份C ;及 d· 0至99.7重量％、較佳10至95.5重量％、尤其較佳。至” 重量％之組份D。本發明之分散液可包含除所提及之組份A至D以外之以下組份中的至少一者： e·以組份A-D之總重量計，0.1至20重量％、較佳〇·5至1〇重量％、尤其較佳1至6重量％之分散劑組份ε ;以及 f ·以組伤A - D之總重量計’〇.1至40重量％、較佳〇,5至3〇重里〇/〇、尤其較佳1至1 0重量％之至少一種其他添加劑F。本發明之分散液之個別組份描述如下： i22438.doc 200815545For this purpose, DlA 1 521 1 52 proposes to apply a conductive lacquer comprising a binder and comprising finely dispersed iron to a non-conducting surface, and subsequently coating a silver or copper layer on the conductive lacquer by a currentless method. The additional layer can then be applied by a currentless method or electroplating. Moreover, the high iron content is beneficial for obtaining sufficient electrical conductivity, but it also causes the problem of dispersibility of relatively heavy metal particles in the conductive paint. Coating based on conductive organic polymers provides another method of coating a conductive layer to a non-conductive surface. For example, DE 198 41 804 describes the production of electrically conductive structures composed of polyalkylene dioxythiophenes by means of an inkjet P brush on a substrate. The disadvantage of the process is that conductive polymers tend to be insufficient for many substrate materials, and the conductivity is too low over long distances. Another disadvantage is that the chemical resistance of the resulting layer is weak, which makes metallization by the electricity money method infeasible. A method which is also known for providing plastics having electrical conductivity (which must be just mentioned by metallization) is to incorporate carbon nanotubes (also commonly referred to as carbon nanofibers) into plastics. Conductive carbon nanotubes such as the stomach also have a low potential (e.g., compared to metal powders) and generally improve the plasticity of the plastic (see, for example, US 2_/0025515 A1). Disadvantages of making plastics containing carbon nanotubes are: relatively high cost, incorporation of carbon nanotubes is often difficult and the fluidity of the plastic mixture is generally reduced (if the entire plastic has been filled with the particles). 122438.doc 200815545 DE 1 02 5 9 498 A1 reveals that not only the hoppers are reported or a “... "the form of carbon (such as carbon black 〆 ' soil) and the conductive 敎鄕 containing carbon nanofibers" π ¥冤熟塑塑塑4. The plastic mixture described in this publication * has not only electrical conductivity but also movability, good surface quality, and relatively good grip. Especially suitable for electrostatic coating In the case of metallization by electro-mineralization, the disadvantage of such polymer mixtures is that metallization is usually only extremely slow, and the ramp + mountain system is not feasible. The dispersion based on conductive carbon black and/or carbon nanotube-based tubes does not have sufficient fluidity for use in noon coating applications. : Other defects or electroplating methods of the processes known in the prior art are carried out today. +, ..., electric / melon / wheat - sex and ... layers of poor adhesion and both ^ A ^ U rb, The particles have been embedded in the base material and thus the particles are peelable and the P particles are used at the surface, so that the particles are only f Μ/ by the helmet electricization. Or the electric ore method for gold small (four) m half ^ ^ knife particles can be used. This is a problem when using a continuous hook metal. This makes this ρ, Γ sleepy (4) practical, and because the 匕亥衣衣衣该该该该该该该该该该该该该该该该该该该该该该该该该该该该该氧化氧化氧化氧化氧化氧化氧化氧化氧化氧化Another disadvantage of the previously known processes is that the metallization is slower than: ., ,, current, and/or electricity, and thus is available and available by means of a currentless method; 'The method of metallization is due to -# in; ^(1) The number of particles in the long core is small. The original is that, for example, when a printing dispersion is applied, heavy metal particles are trapped in the human matrix material, resulting in only a few metal particles remaining at the surface. SUMMARY OF THE INVENTION The object of the present invention is to provide an optimized system for providing uniform and continuous metal coatings for non-conductive substrates using conductive paints or conductive dispersions in detail, and the system is comparatively The combination of improved properties consisting of low weight, good adhesion, A diffuse and fluidity, high electrical conductivity and fast metallization. • Another object of the invention is to provide an alternative method of fabricating a conductive structured or unstructured surface on a substrate that is uniform and continuously conductive. Accordingly, a dispersion for coating a metal layer on a non-conductive substrate has been found which comprises: , and is known to have a total weight of A Bc and D, from 〇 · to 9 9 · 8 by weight. /. The total weight of the organic binder component A; , , , and the injured A B, c, and D, 〇 · 1 to 3 〇 weight. /. The carbon nanotubes as the component B; c, and the total weight of the wounds A, B, C and D, 〇·! to 7〇% by weight of the conductive particles having an average diameter of 0.01 to 100 μηΊ as a group Part c; d is a solvent of 99.7% by weight based on the total weight of 仞A, Β, C and D. Component D. A method for preparing the dispersion and a method for preparing the dispersion, a method for preparing a metal layer on the surface of a non-conductive substrate, and a substrate surface and use thereof. The present dispersion is important for the use of conductive paints or conductive dispersions in detail for the optimization of metal coatings for non-conducting substrates, when compared to known systems, Both have a combination of improved properties consisting of low weight, good adhesion, dispersibility, flowability and high electrical conductivity. [Embodiment] The dispersion of the present invention and other articles, methods and uses of the present invention are described below. The dispersion for coating a metal layer on a non-conductive substrate of the present invention comprises: (in total, 1% by weight based on the total weight of components A, B, C and D) a· 0.1 to 99.8 by weight %, preferably 2 to 87 5 wt%, particularly preferably 々 to 10 parts by weight of component A; b. 0.1 to 30 wt%, preferably 〇5 to 2 wt%, especially preferably to wt% Component B; C. 0.1 to 70% by weight, preferably 2 to 65% by weight, particularly preferably 4 to 55% by weight of component C; and d·0 to 99.7% by weight, preferably 10 to 95.5% by weight Especially preferred. To "% by weight of component D. The dispersion of the invention may comprise at least one of the following components other than the components A to D mentioned: e. based on the total weight of the components AD, 0.1 to 20% by weight, preferably 〇5 to 1% by weight, particularly preferably 1 to 6% by weight of the dispersant component ε; and f·by weight of the total weight of the group A-D '〇.1 to 40% by weight %, preferably 〇, 5 to 3 〇〇 / 〇, particularly preferably 1 to 10% by weight of at least one other additive F. The individual components of the dispersion of the invention are described below: i22438.doc 200815545

組份A 有機黏合劑組份A為黏合劑或黏合劑混合 =有，顏料一定基團的黏合劑、：在3成之4合物及其衍生物、天然存在之樹脂及合成樹 =其何生物、天然橡膠、合成橡膠、蛋白質、纖生物:乾性及非乾性油及其類似物。該等黏合劑可作並，必須）為以化學方式或以物理方式固化之物冑，例如空氣固化、輻射固化或熱固化物質。黏合劑組份A較佳為聚合物或聚合物混合物。作為組份A，較佳之聚合物為ABS(丙烯腈-丁二烯)；ASA(㈣腈_苯乙稀·丙烯酸_);丙烤酸化丙缚酸酉曰’㈣樹脂；乙酸炫基乙稀基醋；伸燒基_乙酸乙歸睹共聚物’尤其亞甲基-乙酸乙烯醋、伸乙基_乙酸乙埽酿、 :丁基-乙酸乙烯_ ;伸烷基·乙烯基氯共聚物；胺基樹脂’聚搭樹脂及酉同樹脂；纖維素及纖維素衍生物，尤盆广基纖維素、諸如乙酸纖維素§|、丙酸纖維㈣、丁酸纖= 素酉旨之纖維素酉旨、纖維素醚、幾基燒基纖維素、石肖酸織维素；環氧丙稀酸酉旨；環氧樹脂；改質環氧樹脂，例如雙官能或多官能雙齡A或雙紛F樹脂、環氧㈣清漆樹月旨、漠化環氧樹脂、環脂族環氧樹脂；脂族環氧樹脂、縮水甘油醚、乙烯基醚、乙烯-丙烯酸共聚物；烴類樹脂； _S(存在丙烯酸酉旨單元之透明abs);三聚氰胺樹脂順丁烯一酸酐共聚物；甲基丙烯酸酯，（若適當時)胺官能化之曱基丙稀酸醋；天然橡勝；合成橡膠；氣化橡膠；天然 122438.doc 200815545 存在之樹脂；松香；蟲膠；酚系樹脂；聚酯；聚酯樹脂，Component A The organic binder component A is a binder or a binder mixture = a binder with a certain pigment group, a compound of 3 to 4 and its derivatives, a naturally occurring resin and a synthetic tree = Biological, natural rubber, synthetic rubber, protein, fiber biology: dry and non-drying oils and their analogues. These binders may be and must be chemically or physically cured, such as air cured, radiation cured or thermally cured materials. The binder component A is preferably a polymer or a mixture of polymers. As component A, a preferred polymer is ABS (acrylonitrile-butadiene); ASA ((tetra) nitrile-styrene-acrylic acid _); propylene-acidated propyl hydrazide' (tetra) resin; acetoacetate Base vinegar; stretching base _ acetic acid ethyl ruthenium copolymer 'especially methylene-vinyl acetate vinegar, ethyl acetonate acetate, butyl-vinyl acetate _; alkyl-vinyl chloride copolymer; Amine-based resin 'polymerized resin and bismuth resin; cellulose and cellulose derivatives, uranyl cellulose, such as cellulose acetate §|, propionic acid fiber (four), butyric acid fiber = cellulose 酉Purpose, cellulose ether, aryl cellulose, lycopene phthalic acid; epoxy acrylate; epoxy resin; modified epoxy resin, such as bifunctional or multi-functional double age A or double F resin, epoxy (four) varnish tree, desertification epoxy resin, cycloaliphatic epoxy resin; aliphatic epoxy resin, glycidyl ether, vinyl ether, ethylene-acrylic acid copolymer; hydrocarbon resin; _S ( Transparent abs with acrylic acid unit; melamine resin maleic anhydride copolymer; methacrylate, if appropriate amine The acrylic acid group can turn Yue vinegar; wins natural rubber; synthetic rubbers; gasification rubbers; 122438.doc 200815545 existence of natural resins; rosins; shellac; phenol resins; polyester; polyester resin,

諸如苯酯樹脂；聚颯；聚醚颯；聚醯胺；聚醯亞胺；聚笨胺；聚吼咯；聚對苯二甲酸丁二醇酯（PBT);聚碳酸酯（例如來自 Bayer MaterialScience AG之 Makrolon®);聚酯丙稀酸S旨；聚鍵丙稀酸g旨；聚乙稀；聚乙細-σ塞吩；聚蔡二甲酸乙二酯；聚對苯二甲酸乙二酯（PET);乙二醇改質-聚對苯二曱酸乙二酯（PETG);聚丙烯；聚曱基丙烯酸甲酉旨 (PMMA);聚苯醚（ppo);聚苯乙烯（PS)、聚四氟乙稀 (PTFE);聚四氫呋喃；聚醚（例如聚乙二醇、聚丙二醇）；聚乙烯基化合物，尤其聚氣乙烯（PVC)、PVC共聚物、 PVdC、聚乙酸乙烯酯以及此等之共聚物、聚乙烯醇（若適 ‘日守王部分水解形式）、聚乙稀縮酸、聚乙酸乙烯自旨、聚乙稀σ比略啶酮、聚乙烯基醚、聚丙烯酸乙烯基酯及聚甲基丙稀酸乙烯基酯（呈溶液及分散液形式）以及此等之共聚物、聚丙烯酸酯及聚苯乙烯共聚物；聚苯乙烯（衝擊改質或非衝擊改質）；非交聯或與異氰酸酯交聯之聚胺基甲酸酯；聚胺基曱酸酯丙烯酸酯、苯乙烯系-丙烯酸系共聚物笨乙稀-丁一烯散段共聚物（例如來自BASF gesellschaft之 Styroflex⑧或 Styrolux®、來自 CPC之 K*Such as phenyl ester resin; polyfluorene; polyether oxime; polyamine; polyimine; poly-amine; polypyrrole; polybutylene terephthalate (PBT); polycarbonate (eg from Bayer MaterialScience AG's Makrolon®); polyester acrylate S; polyaddition acrylic acid; polyethylene; poly-fine-σ thiophene; poly-calyte; polyethylene terephthalate (PET); ethylene glycol modification - polyethylene terephthalate (PETG); polypropylene; polymethyl methacrylate (PMMA); polyphenylene ether (ppo); polystyrene (PS) , polytetrafluoroethylene (PTFE); polytetrahydrofuran; polyether (such as polyethylene glycol, polypropylene glycol); polyvinyl compounds, especially polyethylene (PVC), PVC copolymer, PVdC, polyvinyl acetate and Such copolymers, polyvinyl alcohol (if appropriate, the partial hydrolysis of the Japanese Guardian), polyacetic acid, polyvinyl acetate, polyethylene, sigridinone, polyvinyl ether, polyacrylic acid Vinyl esters and vinyl methacrylates (in the form of solutions and dispersions) and copolymers, polyacrylates and polystyrene copolymers thereof; Ethylene (impact modified or non-impact modified); non-crosslinked or crosslinked with isocyanate; polyamine phthalate acrylate, styrene-acrylic copolymer stupid-butyl A olefinic copolymer (eg Styroflex 8 or Styrolux® from BASF gesellschaft, K* from CPC)

Resin )，蛋白質，例如酪蛋白；SIS ; SPS嵌段共聚物；一禾M月日、雙馬來酿亞胺-三嗪樹脂（BT)、氰酸s旨樹脂 (CE) %丙基化聚苯_ CAppE)。兩種或兩種以上聚合物之混合物亦可形成有機黏合劑組份A。作為、、且伤A，較佳之聚合物為丙稀酸自旨、丙烯酸樹脂、 122438.doc 200815545 物、甲基丙稀酸_、甲“稀酸樹脂、三聚氰、聚伸烧基、聚酸亞胺、環氧樹脂、改質環如雙官能或多官能㈣A或雙齡F樹脂、環氧齡二::㈣、漠化環氧樹脂、環脂族環氧樹脂)、脂族環 ?“、縮水甘油鍵、乙稀基醚及齡系樹脂、聚胺基甲酸 _ :聚酿、聚乙烯縮醛、聚乙酸乙烯§旨1苯乙烯、聚苯 :烯/、♦物、聚苯乙烯 '丙烯酸酯、苯乙稀· 丁二烯嵌段共Resin), protein, such as casein; SIS; SPS block copolymer; Yihe M-day, Bismaleimide-triazine resin (BT), cyanate s-resin (CE) % propylated poly Benzene _ CAppE). A mixture of two or more polymers may also form the organic binder component A. As a, and injury A, the preferred polymer is acrylic acid, acrylic resin, 122438.doc 200815545, methyl acrylate, _, "dilute acid resin, melamine, polyalkylene, poly Acid imine, epoxy resin, modified ring such as bifunctional or polyfunctional (IV) A or double age F resin, epoxy age two:: (four), desertified epoxy resin, cycloaliphatic epoxy resin), aliphatic ring? ", glycidyl bond, ethylene ether and age resin, polyurethane _: poly brew, polyvinyl acetal, polyvinyl acetate § 1 styrene, poly benzene: ene /, ♦, polystyrene 'Acrylate, styrene-butadiene block

聚物、伸烷基-乙酸乙烯_及乙烯基氯共聚物、聚醯胺以及此等之共聚物。在印刷電路板之製造中，用於分散液之較佳組份a為熱 =化或輻射固化樹脂，例如改質環氧樹脂，諸如雙官能或 ^官能雙酚A或雙酚F樹脂、環氧酚醛清漆樹脂、溴化環氧 =脂、環脂族環氧樹脂；脂族環氧樹脂、縮水甘油醚、氰酉文酉曰、乙稀基喊、㈣樹脂、聚醯亞胺、三聚氰胺樹脂及胺基Μ脂、聚胺基甲酸酯、聚酯以及纖維素衍生物。組份ΒPolymers, alkyl-vinyl acetate- and vinyl chloride copolymers, polyamines, and copolymers thereof. In the manufacture of printed circuit boards, the preferred component a for the dispersion is a thermal or chemically curable resin, such as a modified epoxy resin, such as a bifunctional or functional bisphenol A or bisphenol F resin, a ring. Oxygen novolac resin, brominated epoxy=lipid, cycloaliphatic epoxy resin; aliphatic epoxy resin, glycidyl ether, cyanide oxime, ethyl sulfonate, (iv) resin, polyimine, melamine resin And amine ruthenium, polyurethane, polyester and cellulose derivatives. Component

本發明之分散液包含碳奈米管作為組份Β。碳奈米管及其製備為熟習此項技術者所知且已描述於例如仍 2005/0 1 86378 A1之文獻中。可（例如）於包含金屬催化劑及含碳氣體之反應器中合成碳奈米管（參見例如讥A 5643502)。碳奈米管係例如由 Bayer MaterialScienee、The dispersion of the present invention contains a carbon nanotube as a component hydrazine. Carbon nanotubes and their preparation are known to those skilled in the art and have been described, for example, in the literature of still-2005/0 1 86378 A1. The carbon nanotubes can be synthesized, for example, in a reactor comprising a metal catalyst and a carbonaceous gas (see, for example, 讥A 5643502). The carbon nanotube system is, for example, by Bayer MaterialScienee,

Hyperion Catalysis或 Applied Sciences Inc 出售。較佳之碳奈米管通常具有單壁或多壁管狀結構。單壁碳奈米管（SWCN)係由單一石墨碳層形成，且多壁碳奈米管 122438.doc -14- 200815545 (MWCN)係由複數個如此之石墨碳層形成。該等石墨層具有圍繞圓柱體軸之同心排列。碳奈米管之長度直徑比一般為至較佳至少〗00、尤其較佳至少1〇〇〇。該等奈米管之直徑通常處於O.OOMO.S㈣之範圍0，較佳處於至讀之範圍内，尤其較佳處㈣鳥至⑽叩之範圍内。碳奈米管之長度通常為_咖_、較佳㈣至⑽ '、尤其較佳，。碳奈米管具有形式上已纏繞有層之t空圓柱核心e該空腔直徑通f為0.⑽至〇1 μ幸乂 ^土 0.008至〇.〇】5 μΐΏ。在碳奈米管之一典型實施例 :’管壁係由(例如)8個圍繞空腔之石墨子層組成。此處之碳奈^管可呈由複數個奈米管組成之直徑達测卿、較佳直仫達500 μηι的聚集體形式。該等聚集體可呈巢狀形式、精梳紗形式或開放網路結構形式。 #在本發明之一實施例[碳奈米管可藉由首先使碳奈求 :併入黏合劑組份Α中而添加至本發明之分散液中；若組伤A為水合物或聚合物混合物，則該併入可發生於產生黏口，^且知八之單體聚合期間或之後。若在聚合之後添加奈米=，則較佳經由在擠壓機或捏合機中添加至聚合物炼體 =來/〗、、加不、米官。捏合機或擠壓機中之混合程序可大體上或甚至完全粉碎碳奈米管聚集體且碳奈米管被分散於=合物基質中。在將^奈米管預先併人黏合劑組份A中之-較佳實施例中：將碳奈米管計量量入黏合劑組份A中之形式可為於較 k自用作組伤A之聚合物之群的聚合物中之高濃度母膠 122438.doc 200815545 形式。碳奈米管在母膠中之濃度通常處於5至50重量％、車乂仏8至3。重量％、尤其較佳^至^重量％之範圍内。母膠之製備係描述於（例如）US_A 564通中。使用母膠可尤其改良對聚集體之粉碎作用。由於併入分散液中或預先併入組份A中，故碳奈米管之長度分布可比最初所用之長度分布短。Hyperion Catalysis or Applied Sciences Inc for sale. Preferred carbon nanotubes typically have a single or multi-wall tubular structure. Single-walled carbon nanotubes (SWCN) are formed from a single graphitic carbon layer, and multi-walled carbon nanotubes 122438.doc -14- 200815545 (MWCN) are formed from a plurality of such graphitic carbon layers. The graphite layers have a concentric arrangement around the axis of the cylinder. The carbon nanotubes have a length to diameter ratio of generally at least 00, particularly preferably at least 1 Torr. The diameter of the nanotubes is usually in the range of 0. O. OMMO. S (4), preferably in the range of reading to the reading, particularly preferably in the range of (4) birds to (10) 。. The length of the carbon nanotubes is usually _coffee_, preferably (four) to (10)', and particularly preferably. The carbon nanotube has a t-cylindrical core e which has been wound with a layer in the form. The diameter of the cavity is 0. (10) to 〇1 μ乂^^0.000.00 to 〇.〇] 5 μΐΏ. In a typical embodiment of a carbon nanotube: the wall is composed of, for example, eight graphite sublayers surrounding the cavity. Here, the carbon nanotubes may be in the form of aggregates of a diameter of up to a number of nanotubes and a diameter of up to 500 μm. The aggregates may be in the form of a nest, a combed yarn or an open network structure. #In an embodiment of the present invention [carbon nanotubes may be added to the dispersion of the present invention by first incorporating carbon into the binder component; if the group A is a hydrate or a polymer In the case of a mixture, the incorporation may occur during or after the polymerization of the monomer. If nano+ is added after the polymerization, it is preferably added to the polymer refining body = in the extruder or the kneader, and is added to the rice. The mixing procedure in the kneader or extruder can substantially or even completely comminute the carbon nanotube aggregates and the carbon nanotubes are dispersed in the = compound matrix. In the preferred embodiment of the present invention, the carbon nanotubes are metered into the binder component A in a form which can be used as a group injury A in comparison with k. A high concentration of masterbatch in the polymer of the polymer group 122438.doc 200815545. The concentration of the carbon nanotubes in the masterbatch is usually between 5 and 50% by weight and the rutting is 8 to 3. It is in the range of % by weight, particularly preferably ^ to ^% by weight. The preparation of the masterbatch is described, for example, in US-A 564. The use of a masterbatch can especially improve the comminution of the aggregates. Due to incorporation into the dispersion or pre-incorporation into component A, the length distribution of the carbon nanotubes can be shorter than the length distribution originally used.

組份C # 命適、田組伤C傣由具有任何所要幾何形狀且由任何所要導 “才料組成或由各種導電材料之混合物組成或由導電材料與料電材料之混合物組成的導電顆粒中之任一者提供， /等顆粒之平均直徑為0 001至100 _，較佳為0·⑽5至π μϊη尤其車乂佳為0·01至10 _(用Microtrac Χ100設備經由雷射繞射量測法測定)。為達成本發明之目的，”導電顆粒” f所具電阻低於1〇9歐姆之顆粒。適當導電材料之實例為 ^ (厌二石墨）、導電金屬錯合物、導電有機化合物或導肇電聚合物（例如聚嘆吩或聚吡咯）或金屬（較佳為鋅、鎳、鋼、錫、鈷、錳、鐵、鎂、鉛、鉻、鉍、銀、金、鋁、鈦、鈀、鉑、钽）以及其合金或包含該等金屬中之至少一者的金屬混合物。適當之合金之實例為CuZn、、 . CuNi、SnPb、SnBi、SnCo、NiPb、ZnFe、ZnNi、ZnC〇及Component C #命适,田组伤C傣 is composed of conductive particles having any desired geometry and consisting of any desired material or a mixture of various conductive materials or a mixture of conductive material and electrical material. Any of them provides that the average diameter of the /etc particles is from 0 001 to 100 _, preferably from 0·(10)5 to π μϊη, especially from 0·01 to 10 _ (by the Microtrac Χ100 device via laser diffraction For the purpose of the present invention, "conductive particles" f have particles having a resistance lower than 1 〇 9 ohms. Examples of suitable conductive materials are ^ (anti-graphite), conductive metal complexes, conductive organic a compound or a conductive polymer (such as polyseptene or polypyrrole) or a metal (preferably zinc, nickel, steel, tin, cobalt, manganese, iron, magnesium, lead, chromium, bismuth, silver, gold, aluminum, Titanium, palladium, platinum, rhodium) and alloys thereof or metal mixtures comprising at least one of the metals. Examples of suitable alloys are CuZn, .CuNi, SnPb, SnBi, SnCo, NiPb, ZnFe, ZnNi, ZnC And

ZnMn。尤其較佳為銘、鐵、銅、錄、銀、锡、辞及其混合物。尤其較佳為鐵粉及鋼粉。至屬，除了金屬含量以外，可具有非金屬含量。舉例而吕，盒層可存在於金屬之至少一部分表面上。適當塗層可 122438.doc 200815545 為無機（例如Si〇另-種金屬二她旨)或有機的。該金屬〜冑次孟屬氣化物塗覆。該全屬门4田然亦可矣形式存在。同樣可以部分氧价金屬粉末切具有 =實例為針*、心或二金夢助於已：顆粒。此類金屬粉末為所熟悉之汽。t‘為球已知方法製備，例如經由金屬函〜°或可易於化學逛原或經由氧现'合玫之電解沈積或肱八茂 ^末之遏原（例如藉助於&严 /屬炫體噴霧或霧化’特別係在、:广)或經由 ^在鐵之情況下，較佳為使用二或：之冷卻劑氧化物還原。亦有 — 〃豆5進仃霧化且使鐵佳粒度之全屬μ Γ 磨粗趟金屬粉末來製造具較又之“初末。舉例而言，球磨係適合於匕其較佳係使用具有球中、二’ 粉。孟屬知末’尤其羰基鐵係：：=五幾基鐵之熱分解來製備幾基鐵粉且其(例如） 'lmann S Encycl°P^ia of Industrial Chemistry > ^版，第AM卷，第別頁中。舉例而言，可在高溫下於可加熱分解容器中使五幾基鐵分解，該分解容器包含一由耐熱材料（諸如石英玻璃或似鋼）組成之管，該管較佳處於垂直4立罟日+ 置且由加熱設備（例如由加熱帶、電熱絲或加熱套（經熱流體流過）組成）所圍繞。取基鐵粉在沈積時之平均粒徑可經由分解反應之製程參數及進订而控制在較寬範圍内且一般為0·01至1 00 μηι，較佺為0·1至50 μιτι，尤其較佳為0.5至10 μπι。 I22438.doc 200815545 若意欲使用兩種不同金屬彤+ , 全屬之…“ 份C’則此可經由兩種 “物來達成。尤其較佳為，兩種金屬為選“ 紹、鐵、銅、銀、鋅及敎成m 自由然而，組份（：亦可包含第—金入口土屬及弟一金屬，苴Φ筮- 至屬呈合金（與第一金屬或與— ’、一次夕種其他金屬开彡士、人金）形式，或組份C可包含兩種 y " 情況下，金屬組份中之每一者又门在為寺兩種母者不同於另一者且其金愿賴私之形狀因此可彼此獨立地經選為相同或不同。 /、不僅金屬之選擇而且金屬之金屬顆粒於明之分散液在塗覆後之转杻4 曰耆本發土偎傻之特性。就形狀而言，孰者已知之許多變I#係玎认. …、自匕員技術可為針狀、圓杠拟u 〃屬顆粒之形狀 p 4片狀或球形。該等顆粒形狀為㈣化形狀，作實）!汉你；此叮& 為理想仁Λ IV、形狀可與此隨製備方法度上之不同。Α 士血为罕乂大或較小程、' ，舉例而言，液滴狀顆粒士目的而理相化之為基於本發明里心化之球形形狀的實際偏差物。 I面上可購得具有各種顆粒形狀之金屬。右至屬組份在其金屬顆粒形狀方面屬為球形且第-全屬貝丨較佳第一金乐一孟屬為薄片狀或針狀。在不同顆教形壯+ A、之h況下，較佳之金屬同槐鋼、銀、辞及錫。 J樣為鋁、鐵、ZnMn. Particularly preferred are Ming, iron, copper, recorded, silver, tin, and their mixtures. Particularly preferred are iron powder and steel powder. The genus, in addition to the metal content, may have a non-metallic content. For example, the layer may be present on at least a portion of the surface of the metal. A suitable coating can be 122438.doc 200815545 is inorganic (such as Si〇 another kind of metal) or organic. The metal ~ 胄次孟属 is coated with a vapor. This is all in the form of the door 4 Tianran can also exist. The same can be part of the oxygen price of the metal powder cut = example for the needle *, heart or two gold dreams have been: particles. Such metal powders are familiar steam. t' is prepared by a known method for the ball, for example, via a metal letter ~ ° or can be easily chemically browsed or electrolyzed via oxygen, or deposited in the end of the dynasty (for example, by means of & strict / genus The body spray or atomization is carried out in particular, or in the case of iron, preferably using two or a coolant oxide. There are also - 〃 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 In the ball, the two 'powder. Menggenzhizhi', especially the carbonyl iron system:: = thermal decomposition of pentadyl iron to prepare a few base iron powder and its (for example) 'lmann S Encycl ° P ^ ia of Industrial Chemistry > ^ Edition, vol. AM, page. For example, the pentadyl iron can be decomposed in a heat-decomposable container at a high temperature, the decomposition vessel comprising a heat-resistant material (such as quartz glass or steel) The tube is preferably placed in a vertical vertical position and surrounded by a heating device (for example, consisting of a heating belt, a heating wire or a heating jacket (flowing through a hot fluid)). The average particle diameter can be controlled within a wide range by the process parameters of the decomposition reaction and the ordering, and is generally from 0. 01 to 100 μm, more preferably from 0.1 to 50 μm, particularly preferably from 0.5 to 10 μm. I22438.doc 200815545 If you want to use two different metals 彤+, all belong to..." C' can be achieved by two kinds of substances. Especially preferably, the two metals are selected as "sho, iron, copper, silver, zinc and bismuth. However, the composition (: can also contain the first gold The entrance soil and the younger brother, the metal, 苴Φ筮- to the genus is in the form of an alloy (with the first metal or with - ', one other night metal other gentleman, human gold), or the component C can contain two y &quot In the case of the metal component, each of the two members of the temple is different from the other, and the shape of the golden parent is chosen to be the same or different independently of each other. The choice and the metal metal particles in the bright dispersion in the coating after the transfer of 4 曰耆发发发。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。 The technique can be a needle shape or a round bar. The shape of the particle is p 4 or spherical. The shape of the particle is (4) shape, and it is true! Han You; This 叮 & is ideal for Λ IV, shape This can be different from the preparation method. The blood of the scorpion is a rare or small process, 'for example, the droplet-like particle is rationalized as a practical deviation based on the spherical shape of the present invention. Metals having various particle shapes are commercially available on the I side. The right-to-belong component is spherical in shape of its metal particle shape, and the first-to-all-beauty-like genus is preferably flaky or needle-like. In the case of different shapes and strong + A, the best metal is the same steel, silver, remarks and tin. J-like aluminum, iron,

組份D 此外，本發明$八Λ °其由溶劑或溶 (例如正辛烷、In addition, the present invention is in the form of a solvent or a solvent (e.g., n-octane,

乃 < 刀散液包含溶劑組份D 劑混合物組成。適當溶劑之管·々丨& 】為脂族烴類及芳族烴類 122438.doc -18- 200815545 環己烷、甲苯、二甲苯）、醇類（例如甲醇、乙醇、丙醇、2-丙醇、1-丁醇、2_ 丁醇、戊醇）、多元醇類（諸如甘油乙一醇、丙二醇、新戊二醇）' 烷基酯類（例如乙酸曱酉曰乙S欠乙酯、乙酸丙酯、乙酸丁酯、乙酸異丁酯、乙酸異丙酯、3-甲基丁醇）、烷氧基醇類（例如甲氧基丙醇、甲氧基丁醇、乙氧基丙醇）、烷基苯類（例如乙基苯、異丙基苯）丁基乙一醇、丁基二乙二醇、烷基乙二醇乙酸酯類 (例如丁基乙二醇乙酸酯、丁基二乙二醇乙酸酯）、碳酸酯類（例如碳酸乙二酯及碳酸丙二酯）、氨仿、二丙酮醇、二乙二醇二烷基醚類、二乙二醇單烷基醚類、二丙二醇二烷基趟類、二丙二醇單烧基醚類、二乙二醇烧基醚乙酸醋類、二丙二醇烧基醚乙酸_、H二丙二醇及二丙一醇醚類、二乙二醇及二乙二醇醚類、DB坷二元酸酯類）、醚類（例如***、四氫呋喃）、氯化乙烯、乙二醇、乙二醇乙酸_、乙二醇二曱醚、甲紛、内g旨類（例如丁内酯）、酮類(丙酮、2-丁酮、環己酮、甲基乙基酮(ΜΕκ)、曱基異丁基酮（MIBK)、二乙二醇甲醚、二氯甲烷、曱二醇、甲基乙二醇乙酸酯、甲基苯酚(鄰甲酚、間甲酚、對 :酚）、吡嘻啶酮類（例如N-甲基_2_吡咯啶酮）、丙二醇、石反§夂丙一、四氣化碳、甲笨、三經曱基丙烧（丁明、芳 =烴類及混合物、脂族烴類及混合物、醇單莊類（例如松月曰％ )水以及由該等〉谷劑中之兩種或兩種以上溶劑組成之混合物。較佳之溶劑為醇類（例如乙醇、丙醇、2_丙醇、丁 122438.doc 200815545 醇）、烷氧基醇類（例如甲氧基丙醇、乙氧基丙醇、丁基乙二醇、丁基二乙二醇)、丁内醋、二乙二醇二烷基醚類、二乙二醇單烷基醚類、二丙二醇二烷基醚類、二丙二醇單烷基醚類、酯類（例如乙酸乙酯、乙酸丁酯、丁基乙二醇 :酸_、丁基二乙二醇乙酸醋、二乙二醇燒基：讓 '員、-丙二醇醚乙酸酯、DBE)、醚類(例如四氫呋喃）、多元醇類（諸如甘油）、乙二醇、丙二醇、新戊二醇）、酉同類 (例如丙酮、甲基乙基酮、甲基、丞” 丁基酮、裱己酮）' 烴類 (例如％己烷、乙基苯、甲苯、二 Τ本）甲基-2-吡咯啶明、水以及該等溶劑之混合物。若分散液係藉由喷墨法而塗佈 #J Λ ^ ^ ^ , 土筛至襯底，則特別較佳之溶〜基醉類(例如乙氧基丙醇、丁基乙二醇、丁基二乙-酵)及多元醇類(諸如甘油)、：乙酸酷、丁基乙二醇乙酸_、二丙1甲其&-乙-知水、環一丙一知甲基醚乙酸酯）.、 t " 5、丁内酯、N-曱基吡咯烷酮、DBE以及$ # 劑之混合物。以及忒寻溶The < knife dispersion comprises a solvent component D mixture mixture. Tubes of suitable solvents · 々丨 & amps are aliphatic hydrocarbons and aromatic hydrocarbons 122438.doc -18- 200815545 cyclohexane, toluene, xylene), alcohols (eg methanol, ethanol, propanol, 2- Propyl alcohol, 1-butanol, 2-butanol, pentanol), polyols (such as glycerol glycol, propylene glycol, neopentyl glycol) 'alkyl esters (such as ethyl acetate S ethyl ester, acetic acid Propyl ester, butyl acetate, isobutyl acetate, isopropyl acetate, 3-methylbutanol, alkoxy alcohols (eg methoxypropanol, methoxybutanol, ethoxypropanol) , alkylbenzenes (such as ethylbenzene, cumene) butyl ethyl alcohol, butyl diethylene glycol, alkyl glycol acetates (such as butyl glycol acetate, butyl two Ethylene glycol acetate), carbonates (such as ethylene carbonate and propylene carbonate), ammonia, diacetone, diethylene glycol dialkyl ether, diethylene glycol monoalkyl ether , dipropylene glycol dialkyl hydrazine, dipropylene glycol monoalkyl ether, diethylene glycol alkyl ether acetate vinegar, dipropylene glycol alkyl ether acetic acid _, H dipropylene glycol and dipropylene ether ether , diethylene glycol and diethylene glycol ethers, DB坷 dibasic acid esters), ethers (such as diethyl ether, tetrahydrofuran), ethylene chloride, ethylene glycol, ethylene glycol acetic acid, ethylene glycol Ether, A, G (such as butyrolactone), ketones (acetone, 2-butanone, cyclohexanone, methyl ethyl ketone (ΜΕκ), decyl isobutyl ketone (MIBK), two Ethylene glycol methyl ether, dichloromethane, decanediol, methyl glycol acetate, methyl phenol (o-cresol, m-cresol, p-phenol), pyridone (for example, N-A) Base 2_pyrrolidone), propylene glycol, stone anti-cyanate, tetra-carbonized carbon, methyl stupid, tri-propyl mercapto-propene (Ding Ming, aromatic = hydrocarbons and mixtures, aliphatic hydrocarbons and mixtures, a mixture of alcohol and a mixture of two or more solvents of the granules. Preferred solvents are alcohols (eg, ethanol, propanol, 2-propanol, butyl). 122438.doc 200815545 Alcohol), alkoxy alcohols (such as methoxypropanol, ethoxypropanol, butyl glycol, butyl diethylene glycol), butane vinegar, diethylene glycol dioxane Ethers, two Glycol monoalkyl ethers, dipropylene glycol dialkyl ethers, dipropylene glycol monoalkyl ethers, esters (eg ethyl acetate, butyl acetate, butyl glycol: acid _, butyl diethylene) Alcoholic acid vinegar, diethylene glycol alkyl: let 'member, - propylene glycol ether acetate, DBE), ethers (such as tetrahydrofuran), polyols (such as glycerol), ethylene glycol, propylene glycol, neopentyl glycol ), 酉 similar (eg acetone, methyl ethyl ketone, methyl, hydrazine butyl ketone, hexanone) 'hydrocarbons (eg % hexane, ethyl benzene, toluene, diterpenoid) methyl-2 - pyrrolidine, water and a mixture of such solvents. If the dispersion is coated with #J Λ ^ ^ ^ by an ink jet method, and the soil is sieved to the substrate, it is particularly preferably dissolved in the base (for example, B Oxypropanol, butyl glycol, butyl di-ethyl) and polyols (such as glycerol), : acetic acid, butyl glycol acetic acid _, dipropyl 1 ace & A mixture of water, cyclomethicone, methyl ether acetate, t " 5, butyrolactone, N-mercaptopyrrolidone, DBE, and $#. And 忒溶

組份E 分=:分散液亦可包含分一。其由…種述二者已知適用於分散液且在先前技術中已描散劑為界：―種分散劑原則上係適合的。較佳之分陽離子、力⑷或界面⑦性劑混合物’例如為陰離子、兩性或非離子界面活性劑。較佳為熟習此項員技術者已知之市面上可購得的寡 122438.doc -20. 200815545 聚分散劑及聚合分散劑，該等分散劑係描述於CD R5mpp Chemie Lexikon-3,0版 ’ Stuttgart/New York: Georg Thieme Verlag 2006，關鍵詞"Dispergierhilfsmitter [Dispersing agent]中 ° 實例為聚羧酸、多元胺、由長鏈多元胺組成之鹽及由聚羧酸組成之鹽、胺/醯胺官能性聚酯及聚丙烯酸酯、大豆卵鱗脂、聚翁酸鹽、改質酿蛋白。該等聚合分散劑可呈嵌段共聚物、梳形聚合物或無規共聚物之形式。陽離子及陰離子界面活性劑係（例如）描述於 "Encyclopedia of Polymer Science and Technology% J.Component E == The dispersion may also contain one part. It is known that both are suitable for use in dispersions and have been delineated in the prior art: "dispersants are in principle suitable. Preferably, the cation, force (4) or interfacial 7 mixture is, for example, an anionic, amphoteric or nonionic surfactant. Preferably, the commercially available oligo 122438.doc -20. 200815545 polydispersant and polymeric dispersant are known to those skilled in the art and are described in CD R5mpp Chemie Lexikon-3, version 0' Stuttgart/New York: Georg Thieme Verlag 2006, keyword "Dispergierhilfsmitter [Dispersing agent]° Examples are polycarboxylic acids, polyamines, salts consisting of long-chain polyamines and salts consisting of polycarboxylic acids, amines/醯Amine functional polyester and polyacrylate, soybean egg yolk, polyuronate, modified brewing protein. The polymeric dispersants may be in the form of block copolymers, comb polymers or random copolymers. Cationic and anionic surfactants are described, for example, in "Encyclopedia of Polymer Science and Technology% J.

Wiley & Sons (1966)，第 5 卷，第 816至 818 頁及"Emulsion Polymerisation and Emulsion Polymers”，編者Ρ· Lovell及 Μ· El’Asser，Verlag Wiley & Sons (1997)，第 224-226 頁中ο 陰離子界面活性劑之實例為具有8至30個碳原子、較佳 1 2至1 8個碳原子之鏈長之有機羧酸的鹼金屬鹽。該等鹼金屬鹽一般被稱為皂類。通常所用之鹽為鈉鹽、鉀鹽或銨盖其他可使用之陰離子界面活性劑為具有8至3 0個碳原子、較佳12至18個碳原子之烷基硫酸鹽及烷基磺酸鹽或烷基方基％酸鹽。特別適合之化合物為十二烷基硫酸鹼金屬例如十_烷基硫酸鈉或十二烷基硫酸鉀）及石蠟 ’、1之I至屬鹽。其他適合之化合物為十二烷基苯磺酸鈉及二辛基磺基琥珀酸鈉。適當之陽離子界面活性劑之實例為胺鹽或二胺鹽、四級 122438.doc 21 200815545 叙鹽（例如溴化十六基三曱基銨）以及經長鏈取代之環胺（諸如°比°定、嗎啉、哌啶）之鹽。尤其使用三烷基胺之四級銨鹽’例如漠化十六基三曱基銨。此處之烷基較佳具有1至 20個碳原子。根據本發明，非離子界面活性劑尤其可用於組份E中。子”面活性劑係（例如）描述於CD R5mpp Chemie η 1·〇版，Stuttgart/New York: Georg Thieme VerlagWiley & Sons (1966), Vol. 5, pp. 816-818 and "Emulsion Polymerisation and Emulsion Polymers," Editors Love Lovell and Μ El'Asser, Verlag Wiley & Sons (1997), pp. 224- An example of an anionic surfactant is an alkali metal salt of an organic carboxylic acid having a chain length of 8 to 30 carbon atoms, preferably 12 to 18 carbon atoms. These alkali metal salts are generally referred to as Soaps. The commonly used salts are sodium, potassium or ammonium. Other anionic surfactants which can be used are alkyl sulfates and alkyl groups having 8 to 30 carbon atoms, preferably 12 to 18 carbon atoms. A sulfonate or an alkyl square based acid salt. A particularly suitable compound is an alkali metal lauryl sulfate such as sodium lauryl sulfate or potassium lauryl sulfate, and a paraffin wax, a salt of I. Other suitable compounds are sodium dodecylbenzene sulfonate and sodium dioctyl sulfosuccinate. Examples of suitable cationic surfactants are amine or diamine salts, Grade IV 122438.doc 21 200815545 Salts (eg Cetyltrimethylammonium bromide) and long chain substituted cyclic amines a salt such as a phage, a morpholine or a piperidine. In particular, a quaternary ammonium salt of a trialkylamine such as desertified hexadecanyltrimethylammonium is used. The alkyl group here preferably has from 1 to 20 Carbon Atoms According to the present invention, nonionic surfactants are especially useful in component E. The sub-active surfactant system (for example) is described in CD R5mpp Chemie η 1·〇, Stuttgart/New York: Georg Thieme Verlag

1 995 ’ 關鍵詞 ’’Nichtionische Tenside，，[Nonionic surfactants]中。適合之非離子界面活性劑之實例為基於聚氧化乙烯或聚氧化丙烯之物質，諸如來自BASF AktiengeseUsch⑽之1 995 ‘ Keywords ’’Nichtionische Tenside, [Nonionic surfactants]. Examples of suitable nonionic surfactants are those based on polyethylene oxide or polypropylene oxide, such as from BASF Aktiengese Usch (10).

Pl_i’或Tetronic@。適用作非離子界面活性劑之聚伸烷二醇一般具有處於1000至15000 g/m〇1、較佳2〇〇〇至13〇⑽ 卜尤其較佳4000至110⑽之範圍内的數均莫耳貝里Μη。較佳之非離子界面活性劑為聚乙二醇。聚伸烷二醇本身為已知的或可藉由本身已知之方法備，例如稭由使用諸如氯氧化納錢氧化卸之驗金、里：催或使用諸如甲氧化納、乙氡化鈉、乙氧化鉀或 /、丙乳化鉀之鹼金屬醇鹽催化劑且同時添加至少— 2至8個反應性氫原子、較佳_個反應性氯原 ^含子進仃陰離子聚合，或藉由使用諸如五氯化銻、⑪刀硼或漂白土之路层渐龄,τ · …、峻合氟化路易4 MLewls acid)催化劑、為— 伸烧基上具有2至4個碳原子之氧化婦的起始=種於子聚合。、違行陽離 I22438.doc -22- 200815545 氡化丁烯、氧化苯乙烯且較佳丁烯或2,3- 千乂1土為虱化乙烯及/ 烯。氡化烯可單獨地、相繼，1化丙 u人旁地或以混合物形可使用之起動分子之實例為物化式使用。 -辦 ^ K，有機二羧酸類，諸如丁己二酸、鄰苯二甲酸或對笨二甲酸；脂…丁經取代或經N-單烧基或N，m，象二烧、次方族未上具有1至4個碳原子的二胺類，諸如未：：代：：貌基或二烷基取代之乙二胺、 3 I早烷基 π丙二胺、…-丁、三伸乙基四胺、】，6-己二胺。胺或1，2·、1，3·、^^-或其他可使用之起動分子為：甲基乙醇胺及队乙基 '、歹，如乙醇胺、N- 胺、N-甲基二乙醇胺❹·乙1㈣如二乙醇例如三乙醇胺n 醇恥；及三烷醇胺類，㈡“女’及氰。較佳使用多元醇或具有多於三個官能Α ^、―凡醇或三此暴之酉子類，例如二醉、I丙二醇、二乙二醇、二丙二醇、ΐ4% α丙 1，6-己二醇、甘油、三羥，丁一醇、梨糖醇。土、兀、異戊四醇、薦糖及山其他適當之組份丘為酯化聚伸烷二醇，^张植伸烷二醇之單醋、-— 冶如所提及之聚 ' —知、三酯或聚酯，J:可驻士丄Α 知之方式，使所提及之聚 /、 e由以本身已 (較佳為己二酸或對笨A : ^ 0Η基圓與有機酸飞對本二f酸）反應來製備。非離子界面活性m藉由氧基化而製傷之物質，_ 性岛原子之化合物炫貝例如乳化婦於腊肪醇、含氧醇或烷 122438.doc -23 - 200815545 基紛上之加合物。舉例而言，可將氧化乙烯或i，2_氧化丙烯用於該烷氧基化反應。其他可處之非離子界面活性劑為烧氧基化或非烧氧基化糖酯或糖&|。耱鱗為藉由使脂肪醇與糖反應而獲得之烷基糖薈，且糖醋係藉由使糖與脂肪酸反應而獲得。製備所提及之物質所需的糖、脂肪醇及脂肪酸為熟習此項技術者所知。適當之糖係（例如）描述於Beyer/Walter，Lehrbuch der organischen Chemie，S，Hirzel Verlag Stuttgart，第 19版， 1981，第392至425頁中。可能之糖為D-山梨糖醇及藉由使 D-山梨糖醇脫水所獲之脫水山梨糖醇。適Ϊ之脂肪酸為具有6至26個碳原子、較佳8至22個碳原子、尤其較佳10至20個碳原子之飽和或單不飽和或多不飽和未分支或分支羧酸，舉例而言如CD R5mpp Chemie Lexikon-1.0版，Stuttgart/New Y〇rk: Ge〇rg Thieme 1995 ’ 關鍵一 FettsSuren”[Fatty acids]中所提及。可想到之脂肪酸為月桂酸、棕櫚酸、硬脂酸及油酸。適S之脂肪醇之碳骨架與如適當之脂肪酸所描述之化合物的碳骨架相同。糖醚、糖酯及其製備方法為熟習此項技術者所知。較佳之糖醚係藉由已知方法經由使所提及之糖與所提及之脂肪醇反應而氣備。較佳之糖酯係藉由已知方法經由使所提及之糖與所提及之脂肪酸反應而製備。適當之糖酯為脫水山梨糖醇與脂肪酸形成之單酯、二酯及三酯，尤其脫水山梨 122438.doc •24- 200815545 糖醇早月桂酸妒醇三月桂酸二Γ山梨糖醇二月桂酸sl、脫水山梨糖酉旨、脫水山¥詩1—錢§9、脫水山梨糖醇單棕櫚酸糸糖％二核櫚酸酯、脫水酯、脫水山半糖萨w s t & 木+ ’二彳示櫚酸 st η %早硬脂酸醋、脫水山梨糖醇二硬脂酸酉日、脫水山梨糖醇二 ffit ^ , 予—硬知I S曰及脫水山梨糖醇倍半油酸脱水山梨糖醇單油酸_及二油酸酿之混合物。Pl_i’ or Tetronic@. The polyalkylene glycol useful as a nonionic surfactant generally has a number average molar in the range of 1000 to 15000 g/m 〇 1, preferably 2 〇〇〇 to 13 〇 (10) 卜, particularly preferably 4000 to 110 (10). Berry Μη. A preferred nonionic surfactant is polyethylene glycol. The polyalkylene glycol itself is known or can be prepared by a method known per se, for example, the straw is subjected to a gold test such as chlorination, a nucleus, or a sodium sulfonate, such as sodium methoxide or sodium hydride. An alkali metal alkoxide catalyst of potassium ethoxide or /, propylene emulsified potassium and simultaneously adding at least - 2 to 8 reactive hydrogen atoms, preferably - reactive chlorine precursors, an anion polymerization, or by using, for example, The ruthenium pentachloride, the 11-knife boron or the bleaching earth road layer is gradually aged, the τ · ..., the fluorinated Lewis 4 MLewls acid catalyst, and the oxidized woman having 2 to 4 carbon atoms on the extended base Start = seed in the sub-aggregation. I. 违丁烯、 I I 22 22 22 22 22 22 22 22 22 22 22 22 22 22 22 22 22 22 22 22 22 22 22 22 22 22 22 22 22 22 22 22 22 22 22 22 22 22 22 I The decene oxide can be used in a physicochemical manner, either individually or sequentially, as an example of a starting molecule which can be used in the form of a mixture. - do ^ K, organic dicarboxylic acids, such as butadipic acid, phthalic acid or p-dicarboxylic acid; fat ... but substituted by N-monoalkyl or N, m, like two burning, sub-family There are no diamines having 1 to 4 carbon atoms, such as:::: amorphine or dialkyl substituted ethylenediamine, 3 I early alkyl pipropane diamine, ... - butyl, s Tetraamine, 】, 6-hexanediamine. Amine or 1,2·, 1,3·, ^^- or other starter molecules that can be used are: methylethanolamine and group ethyl', hydrazine, such as ethanolamine, N-amine, N-methyldiethanolamine ❹ B 1 (4) such as diethanol such as triethanolamine n smear; and trialkanolamines, (2) "female" and cyanide. It is preferred to use polyol or have more than three functional Α ^, "alcohol or three storms" Subclasses, such as di-drug, I-propanediol, diethylene glycol, dipropylene glycol, ΐ4% α-propyl 1,6-hexanediol, glycerol, trihydroxyl, butanol, sorbitol. Earth, strontium, isoprene Alcohol, sucrose and other suitable components of the mountain are esterified polyalkylene glycols, mono- vinegars of alkane diols, and lignins, triesters or polyesters as mentioned. : can be settled in a way that allows the mentioned poly /, e to be prepared by reacting itself (preferably adipic acid or a stupid A: ^ 0 Η circle with an organic acid fly to the di-f acid) A substance that is inactivated by oxylation of a nonionic interfacial activity, a compound of a stagnation atom, such as an emulsified emulsifier, an oxo alcohol or an alkane 122438.doc -23 - 200815545 For example, ethylene oxide or i,2-propylene oxide can be used for the alkoxylation reaction. Other nonionic surfactants which can be used are alkoxylated or non-oxyalkylated sugar esters. Or sugar &| The scale is an alkyl glycoside obtained by reacting a fatty alcohol with a sugar, and the sweet and sour is obtained by reacting a sugar with a fatty acid. The sugar required for preparing the substance mentioned, Fatty alcohols and fatty acids are known to those skilled in the art. Suitable sugar systems are described, for example, in Beyer/Walter, Lehrbuch der organischen Chemie, S, Hirzel Verlag Stuttgart, 19th edition, 1981, pp. 392-425. Possible sugars are D-sorbitol and sorbitan obtained by dehydrating D-sorbitol. Suitable fatty acids have 6 to 26 carbon atoms, preferably 8 to 22 carbon atoms, especially Preferred are saturated or monounsaturated or polyunsaturated unbranched or branched carboxylic acids of 10 to 20 carbon atoms, for example as CD R5mpp Chemie Lexikon-1.0, Stuttgart/New Y〇rk: Ge〇rg Thieme 1995 ' Key one is mentioned in FettsSuren" [Fatty Acid]. Fatty acids which are conceivable are lauric acid, palmitic acid, stearic acid and oleic acid. The carbon skeleton of the fatty alcohol suitable for S is the same as the carbon skeleton of the compound as described for the appropriate fatty acid. Sugar ethers, sugar esters and methods for their preparation are known to those skilled in the art. Preferred sugar ethers are prepared by reacting the mentioned sugars with the mentioned fatty alcohols by known methods. Preferred sugar esters are prepared by reacting the mentioned sugars with the fatty acids mentioned by known methods. Suitable sugar esters are monoesters, diesters and triesters formed by sorbitan and fatty acids, especially dehydrated sorbus 122438.doc •24- 200815545 Sugar alcohol early lauric acid sterol trilaurate sorbitan dilaurate Sl, sorbitan sugar, dehydrated mountain ¥ poetry 1 - money § 9, sorbitan monopalmitate 糸 sugar % dinuclear palmitic acid ester, dehydrated ester, dehydrated mountain half sugar sawst & wood + 'two 彳Show palmitic acid st η % early stearate, sorbitan distearate bismuth, sorbitan di ffit ^, pre-hard knowing IS曰 and sorbitan sesquioleate sorbitan A mixture of monooleic acid and dioleic acid.

此可此之組份E為藉由使上述糖喊及糖g旨烧氧基化而獲得之烧氧基化糖料糖較佳之炫氧基化劑為氧化乙細及1，2_氧化丙烯。院氧基化度一般為⑴。，較佳為2 至1〇’尤其較佳為2至6。此等之實例^經由上述脫水山梨糖醇醋之乙氧基化而獲得之聚山梨醇_，其（例如）描述於 CD R_pp Chemie 〇版，⑽响賴，％士The component E which is obtained by the alkoxylation of the sugar and the sugar is preferably an alkoxylated sugar which is oxidized ethylene and 1,2-propylene oxide. . The degree of hospitalization is generally (1). It is preferably 2 to 1 〇', particularly preferably 2 to 6. Examples of such ^ Polysorbate obtained by ethoxylation of the above sorbitan vinegar, which is, for example, described in CD R_pp Chemie 〇, (10) 响, %士

Georg Thieme VerIag 1995 ’ 關鍵詞 [Polysorbates]中。適當之聚山梨醇醋為聚乙氧基脫水山梨糖醇月桂酸酯及相應硬脂酸酯、棕櫚酸酯、三硬酯酸酯、油酸酯及三油酸酯，尤其聚乙氧基脫水山梨糖醇硬脂酸酉旨’其可例如作為來自ICI America Inc.之Tween® 60獲得 (例如描述於 CD Rdmpp Chemie Lexik〇n-l.〇版，Georg Thieme VerIag 1995 ‘Keywords [Polysorbates]. Suitable polysorbate vinegar is polyethoxylated sorbitan laurate and corresponding stearates, palmitates, tristearate, oleate and trioleate, especially polyethoxylated Sorbitol stearate can be obtained, for example, as Tween® 60 from ICI America Inc. (for example, as described in CD Rdmpp Chemie Lexik〇nl.

Stuttgart/New Yoik. Georg Thieme Verlag 1995，關鍵詞 nTweer^n 中）。亦有可能使用聚合物作為分散劑。Stuttgart/New Yoik. Georg Thieme Verlag 1995, keyword nTweer^n). It is also possible to use a polymer as a dispersing agent.

組份F 本發明之分散液亦可包含至少一種不同於組份A、B、 122438.doc -25- 200815545 C、D及E之其他添加劑F。其可由一或多種添加劑組成。舉例而言，組份F可包含可溶性、纖維性或微粒添加此等之混合物。&處較佳為市面上可購得之產&。” 亦有可能使用填充劑或增強材料，例如玻璃粉、破物、玻璃非編織物、礦物纖維、鬚晶、氣化銘纖維、、: 母、粉狀石英或石夕灰石。亦可能使用石夕石、石夕酸鹽（例^ 八⑽仙或頁錢鹽）、染料、脂肪酸、脂㈣胺、W 劑、濕潤劑、乾燥劑、錯合劑、碳酸鈣、碳酸鋇、二‘化鈦、蠟、矽灰石、顏料或芳族聚醯胺纖維。亦有可能使用其他添加劑，例如具有搖變效應之試劑，例如石夕石；石夕酸鹽，仏丨丄Λ 例如Aerosils或膨潤土；或具有搖變效應之有機試劑及辋# _ y t 捫化剑，例如聚丙烯酸、聚胺基甲酸酉曰氫化萬麻油、染料、脂肪酸、脂肪醯月安、增塑劑、濕润劑、消泡劑、潤滑劑、乾燥劑、交聯劑、光引發劑、錯合劑、壤、顏料。卜本&月之$散液可包含（例如）加工助劑及穩定劑 (例如UV穩定劑、潤滑劑、防腐劑及阻燃劑）作為組份F。本^月亦提卩f重用於製備本發明之分散液的方法，其中其步驟包含·· a )使組伤A至C與至少一部分組份〇以及（若適當時）e、f 及其他組份混合；及 b!) 使該混合物分散； C )右"適田日守’添加步驟a,)中未使用之比例之組份D以便調節黏度而適於特定塗佈法。 122438.doc -26- 200815545 該分散液可使用熟習此項技術者已知之組件經由強烈混合及分散而製備。其包括在提供強烈分散之組件（例如: 合γ球研磨機、玻珠研磨機、溶解機、三李昆研磨機㈣子-定子混合機）中混合該等組份。八有可能在方法之一個步驟中混合分散液之所有所要組 '、而亦可旎預先混合兩種或兩種以上組份（例如如上所述之組份A與B)，且稍後推混其餘組份直至達至法之後續獨立步驟。 Μ 本發明進—步提供—種用於在―不導電基板之至少分表面上fit —金屬層的方法，其巾其步驟包含： a) 至少部分地塗佈本發明之分散液於該基板上； b) 至少部分乾燥且/或部分硬化塗佈於該基板上散液層；及茨刀 c) 精由無電流法及/或電鑛法沈積_金屬於該經至分乾燥且/或固化之分散液層上，且形成一金屬層/ 在塗佈該分散液期間且為調節步驟a)中之黏度，較該分散液進行攪拌且控制其溫度。土、 =當：在步驟b)與。之間’亦可能引入活。其包含經由至少部人ϋ ^ @ i 地化學破碎及/或機械破碎該經乾文品及:或固化之分散液層而至少部分地釋放導電顆粒。^ 一=導電顆粒包含易於能夠氧化之材料，則可在該方法之一變體中’在結構化或非結構化乾燥及/或固化之層上形成金屬岸之·‘ 政'夜除。此處之氧二二二粒之氧化層至少部分地移曰的私除可（例如）以化學方式及/或機械方 122438.doc -27- 200815545 式進行。可用於處理經龄烽，、二卑L /本及/或固化之分散液層以便以化學方式自導電顆粒移除氧化&的、# ^ 牙虱化層的適當物質之實例為酸，諸如濃硫酸或稀硫酸，式、、歲豳次/辰鹽酸或稀鹽酸、檸檬酸、硭Component F The dispersion of the present invention may also comprise at least one other additive F different from components A, B, 122438.doc - 25 - 200815545 C, D and E. It may consist of one or more additives. For example, component F can comprise a mixture of soluble, fibrous or particulate additives. The & is preferably commercially available & It is also possible to use fillers or reinforcing materials such as glass powder, broken materials, glass non-woven fabrics, mineral fibers, whiskers, gasification fibers,: mother, powdered quartz or Shishi limestone. It is also possible to use Shi Xishi, Shi Xi acid salt (example ^ eight (10) sen or yam salt), dyes, fatty acids, lipids (tetra) amines, W agents, wetting agents, desiccants, complexing agents, calcium carbonate, barium carbonate, titanium , wax, ash stone, pigment or aromatic polyamide fiber. It is also possible to use other additives, such as agents with a rocking effect, such as Shi Xishi; shi shi salt, 仏丨丄Λ such as Aerosils or bentonite; Or an organic reagent with a shake effect and 辋# _ yt 扪化剑, such as polyacrylic acid, urethane hydrogenated cannabis oil, dyes, fatty acids, fat 醯月安, plasticizer, wetting agent, defoaming Agents, lubricants, desiccants, cross-linking agents, photoinitiators, complexing agents, soils, pigments. Buben & Month's dispersion can contain, for example, processing aids and stabilizers (eg UV stabilizers, lubricants) Agent, preservative and flame retardant) as component F. This ^ Also described is a method for reconstituting a dispersion of the present invention, wherein the steps comprise: a) mixing the group A to C with at least a portion of the component mash and, if appropriate, e, f and other components; And b!) Disperse the mixture; C) Right " Optima's addition of component D in unused proportions in step a, to adjust viscosity for a particular coating method. 122438.doc -26- 200815545 The dispersion can be prepared by intensive mixing and dispersion using components known to those skilled in the art, including components that provide strong dispersion (eg, gamma ball mill, bead mill, dissolver, San Like) Mixing the components in a grinder (4) sub-stator mixer. 8. It is possible to mix all the desired groups of the dispersion in one step of the method, or to mix two or more components in advance (for example) Components A and B) as described above, and later the remaining components are pushed up until the subsequent independent steps of the method are reached. Μ The present invention provides a step-by-step method for fitting at least the surface of the non-conductive substrate. a method of metal layer, the step of which comprises: a) at least partially coating the dispersion of the present invention on the substrate; b) at least partially drying and/or partially hardening the dispersion layer applied to the substrate; and c) c) precision by currentless method and/or Electrodeposition deposition _ metal on the dried and/or solidified dispersion layer and forming a metal layer / during the coating of the dispersion and adjusting the viscosity in step a), compared to the dispersion Stir and control the temperature. Soil, = when: between step b) and . may also be introduced. It involves chemically breaking and/or mechanically breaking the dried text through at least part of the body: Or curing the layer of the dispersion to at least partially release the conductive particles. ^ A conductive particle comprising a material that is susceptible to oxidation can be 'in structured or unstructured drying and/or curing in a variant of the method The formation of the metal shore on the layer of 'political' night. The private removal of the oxygen dioxide layer at least partially by oxidation can be carried out, for example, by chemical and/or mechanical means 122438.doc -27-200815545. An example of a suitable material that can be used to treat age-old bismuth, bismuth L/n and/or solidified dispersion layers to chemically remove oxide & oxidized & gingivalized layers is acid, such as Concentrated sulfuric acid or dilute sulfuric acid, formula, 豳豳 / Chen hydrochloric acid or dilute hydrochloric acid, citric acid, cesium

酸、醯胺基磺酸、甲酸、乙酸。 H 表面處氧化層之至少部分移除及導電顆粒之至少部分釋放亦可在同一操作中進行。本發明之分散液所塗佈之適當不導電基板的實例為剛性或可撓性襯底。適當之襯底之實例為增強型或非增強型聚合物。適當之$合物為環氧樹脂或&質環氧樹月旨，例如雙官能或多官能雙酚A或雙酚F樹脂、環氧酚醛清漆樹脂、^ 化％氧樹脂、芳族聚醯胺增強型或玻璃纖維增強型或紙增強型環氧樹脂（例如FR4)、玻璃纖維增強型塑料、液晶聚合物（LCP)、聚苯硫醚（PPS)、聚曱醛（p〇M) '聚芳基醚酮 (PAEK)、聚 _ _ 酮（PEEK)、聚醯胺（pA)、聚碳酸 _ (pc)、聚對苯二曱酸丁二酯（PBT)、聚對苯二甲酸乙二酯（ρΕτ)、 I fe亞胺（PI)、聚醯亞胺樹脂、氰酸酯、雙馬來醯亞胺-三嗪樹脂、耐綸（nylon)、乙烯基酯樹脂、聚酯、聚酯樹脂、聚醯胺、聚苯胺、酚系樹脂、聚吡咯、聚萘對苯二曱酸酯 (PEN)、聚曱基丙烯酸甲酯、磷改質環氧樹脂、聚伸乙二氧基σ塞吩、經酚系樹脂塗覆之芳族聚醯胺紙、聚四氟乙烯 (PTFE)、二聚氰胺樹脂、聚;5夕氧樹脂、氟樹脂、介電質、 ΑΡΡΕ、聚醚醯亞胺（ΡΕΙ)、聚苯醚（ρρο)、聚丙烯（ρρ)、聚乙烯（ΡΕ)、聚砜（PSU)、聚醚颯（pES)、聚芳基醯胺 (ΡΑΑ)、聚氣乙烯（PVC)、聚苯乙烯（ps)、丙稀腈_ 丁二烯· 122438.doc -28- 200815545 苯乙稀（)、丙稀腈_苯乙稀·丙稀酸酿（asa)、苯乙雄一丙烤腈（SAN)以及兩種或兩種以上上述聚合物之混合物淡合物）’其可呈極其廣泛多樣之形式。該等基板可包含熟習此項技術者已知之添加劑’例如阻燃劑。原則上’亦可能使用列於組似下之聚合物中的任一種聚合物。其他適當之基板為複合材料、泡沫型聚合物、 styr〇P，、St_ur@、Mw_(pu)、^wi 織品:硬紙板、紙板 '、紙、經聚合物塗覆之紙、木材、礦物材料石夕、玻璃、植物組織或動物組織，或經樹脂浸透之紡織品’該等基板已受壓以得到薄片或卷形物。為達成本發明之目的，”不導電基板”較佳意謂基板之表面電阻大於1〇9歐姆/公分。刀政液可4由力習此項技術者已知之方法塗佈。可於基板表面之一或多個側面上進行塗佈且該塗佈可為一維、二、隹或一 ’准的。基板_般可具有適於所欲目的之任何所要幾何形狀。 :分散液可藉由習知之塗覆法(洗鑄、展塗、到塗、刷塗、印刷（凹版印刷、網印、彈性凸版印刷、移印、喷墨、平版印刷、如DE1005 1850中所述之LaserSonic⑧法或其他印刷方法）、冑塗、浸塗、滾軋、撒粉、流體化床或員似方法）塗佈。層厚較佳為自〇·〇!至100 μπι、更佳自至5〇啤、尤其較佳自1至25 μη不等。該等層可以非結構化或結構化方式塗佈。 122438.doc -29- 200815545 使用習知方法你以社m ^ 使以 '“冓化或非結構化形式塗佈之八乾燥或硬化。舉例而言，刀散液 _ A 』稭由化學途徑，例如細士封人劑之聚合、聚加成或聚縮入，廡、'二由黏合束輻射'微波輻射、汛輻 t黾子 4丄，仏、 #射或加熱）而使分散液硬介，$ 精由純物理途徑經由墓發，或由物理及化學途徑之組合進行乾燥。了此知在分散液塗佈且、鹿g / ―、乾4及/或硬化後所獲得之無電流法及/或電鍍法後_ 凡4精由忒俊、、負沈積金屬於至少部分硬化之分散液層上。f l杯及/或本發明之分散液於步驟3)中可以結構化或非結構塗佈°較佳以連續程序進行塗佈步驟[步驟a)]、 ^ 硬化步驟[步驟b)]及另一金屬之沈積步驟二小匕⑷）之簡單實施使此成為可能n = 續過程當然亦有可能。牛連步驟C)中藉由無電流法及/或電錄法所進行之金屬沈積可藉由熟習此項技術者已知且文獻中已描述之方法來進行。有可犯藉由無電流法及/或電鍍法（亦即應用外加電壓及電 :流動)塗佈一或多個金屬層。原則上，比分散液之組份C 貴重之金屬中的任一種金屬皆可用於此處之無電流法沈積。對於電鍍法沈積而言，原則上有可能使用任何金屬。較佳使用電鍍法來沈積銅層、鉻層、銀層、金層及/或鎳層。此處所用之電解質溶液可包含（例如）酸性硫酸鋼鍍液。步驟c)中所沈積之一或多個層的厚度係在熟習此項技術者已知之習知範圍内且對於本發明並不重要。 122438.doc •30- 200815545 儘官不需要在藉由無電流法及/或電嫉法進前對可金屬化之基板之夺而、隹—壯w老孟屬化之 > <丞販之表面進打特別處理，但有沾習此項技術者已知之方此曰由以受押方★栋本品』，表面活化可藉工方式使表面粗糙化或使用受控方法之碳奈米管及（例如）全屬群』木擇放表面上严并）’屬顆粒而用於改良黏著性或加速金 “積。碳奈米管及金屬顆粒之釋放亦有下列好人物基質中需要較小比例以實現金屬化。 Λ 梯Γ而言’可經由機械磨，(詳言之經由刷光、研磨或使用研磨劑進行之拋光 ^ 以趙…… 水流屋力下之衝擊、喷砂或起N 一氧化石反（乾冰）進石貧/ )或I曰由物理方法（例如經由加熱、雷射、冰帝s i 先、電軍或電漿放電）及/或化學磨蝕（砰吕之經由蝕刻及/或氧飾…“ 乂乳化)進仃表面活化。進行機械磨钱及/或化學磨餘之方法兔於先前技術中。為^白此項技術者所知且已描述用於抛光之研磨劑可為熟習此項技術者已知之研磨劑中的任-種研磨劑。適當之研磨劑之實例為浮石粉。為在壓，下使用貪射水机時腐飿掉經硬化分散液層的頂層，喷射水流較佳包含小固體顆4 ^ 耻顆粒，诸如平均粒徑分布範圍為40至 120 μηι、較佳 60至 8〇少、办 γ lw μ之，于石粉（A12〇3)或粒徑大於3 μΓη 之粉狀石英（Si02)。在化學磨飯之情況下，較佳使用適於聚合物之化學製劑或化學製劑混合物。在興在化干磨餘之情況下，聚合物可（例如）在表面處至少部；士良、〜刀地為 >谷劑所溶解掉，或基質材料之化學結構可至少在某種程产又上‘助於適當試劑而被破壞， 122438.doc 200815545 仗而釋放喊奈米管。可使基質材料膨脹之試劑亦適用於釋放碳奈米管、。該膨脹作用產彻，待沈積之金屬離子可自1解貝各液滲人該等空腔，為此允許較多數目之碳奈米吕的孟屬化。較多數目之所釋放的碳奈米管使金屬化過程之速率升高。 “若基質材料為(例如)環氧樹脂、改質環氧樹脂、環氧酚 :清漆樹脂、聚丙烯酸醋、ABS、苯乙烯_丁二烯共聚物或 :醚，則碳奈米管及（例如）金屬顆粒之釋放較佳藉由氧化劑而發生。該氧化劑破壞基質材料之結合，為此使黏合劑脫離且隨之釋放顆粒。適t之氧化劑之實例為鍾酸鹽^ 士:過錳酸鉀、錳酸鉀、過錳酸鈉、錳酸鈉）、過氧化氫、氧氣、在例如錳鹽、鉬鹽、鉍鹽、鎢鹽及鈷鹽之催化劑存在下的氧氣、臭氧、五氧化二飢、二氧化石西、多硫化錄溶液、在氨或胺存在下之硫、二氧化鐘、高鐵酸卸、重絡酸鹽/硫酸、於硫酸或乙酸或乙酸肝中之鉻酸、硝酸、氫碘酸、氫溴酸、重鉻酸吡錠、鉻酸_吡啶錯合物、鉻酸酐、氧化鉻（VI)、過碘酸、四乙酸鉛、醌、曱基醌、蒽醌、溴、氣'氟、鐵鹽溶液、硫酸氫鹽溶液、過碳酸鈉、含氧 il酸鹽（oxohalic acid)(例如氣酸鹽或溴酸鹽或碘酸鹽）、過自酸鹽（例如過碘酸鈉或過氯酸鈉）、過硼酸鈉、重鉻酸鹽 (例如重鉻酸鈉）、過硫酸鹽（諸如過氧化二硫酸鉀、過氧: 單硫酸鉀）、氣鉻酸吼錠、次齒酸鹽（例如次氯化鈉）、在親電子試劑存在下之二甲亞砜、氫過氧化第三丁基、3•氣過笨甲酸、2,2-二甲基丙链、戴斯_馬丁（Des_Manin)過碘 122438.doc -32- 200815545 凡二酿氯、尿素-過氧化氫加合物、過氧化尿素、2-二氧碟基笨甲酸、過氧化單硫酸鉀、間氯過苯甲酸、N_甲基 j啉小氧化物、氫過氧化2-甲基丙-2-基、過乙酸、新戊醛、四氧化餓、過硫酸氫鉀、釕（ΙΠ)鹽及釕（IV)鹽、在 2,2,6,6_四甲基哌啶基N•氧化物存在下之氧氣、三乙醯氧基過碘蜿 '二氟過乙酸、三甲基乙醛、硝酸銨。在該過程 /、月間可視情況提高溫度以便改良釋放過程。車乂佳為錳酸鹽（諸如過錳酸鉀、錳酸鉀、過錳酸鈉、錳酉欠鈉）過氧化氫、N-甲基嗎啉N-氧化物、過碳酸鹽（例如過^酸鈉或過碳酸鉀）、過硼酸鹽（例如過硼酸鈉或過硼酸鉀）、過硫酸鹽（諸如過硫酸鈉或過硫酸鉀）、鈉、鉀及銨之過氧：二碲酸鹽及過氧化單硫酸鹽、次氣化鈉、尿素·過 ^ 氫力5物、含氧鹵酸鹽（諸如氯酸鹽或溴酸鹽或破酸鹽）、過鹵酸鹽（諸如過碘酸鈉或過氯酸鈉）、過氧二硫酸四土鉍、鐵鹽溶液、五氧化二釩、重鉻酸吡錠、鹽酸、溴、氯、重鉻酸鹽。斤尤其权佳為過錳酸鉀、錳酸鉀、過錳酸鈉、錳酸鈉、過，化氫及其加合物、過删酸鹽、過碳酸鹽、過硫酸鹽、過氧二硫酸鹽、次氯化鈉及過氯酸鹽。為釋放包含（例如）1 结構之基質材料（例如聚醋樹脂、聚酷丙稀酸酿、聚_丙缚酸_、聚醋胺基甲酸_)中的碳奈米管及(例如)金屬顆粒’較佳使用(例如)酸性或驗性化學製劑及/或化學製劑混人物。， j 口物較佳之酸性化學製劑及/或化學製劑混合物為（例如）澧酴& )辰戍稀酸，諸如鹽酸、硫酸、磷 122438.doc *33- 200815545 酸或硝酸。視基質材料而定，有機酸亦可為適用的，例如曱酸或乙酸。適當之㈣化學製劑及/或化學製劑混合物為（例如）鹼，諸如氫氧化鈉溶液、氫氧化鉀溶液、氫氧化銨或碳酸鹽（諸如碳酸鈉或碳酸鉀）。在該過程期間可視情況提高溫度以便改良釋放過程。Acid, decyl sulfonic acid, formic acid, acetic acid. At least partial removal of the oxide layer at the surface of H and at least partial release of the conductive particles can also be performed in the same operation. An example of a suitable non-conductive substrate to which the dispersion of the present invention is applied is a rigid or flexible substrate. Examples of suitable substrates are reinforced or unreinforced polymers. Suitable compounds are epoxy resins or & epoxy resins, such as difunctional or polyfunctional bisphenol A or bisphenol F resins, epoxy novolac resins, % oxygen resins, aromatic polyfluorenes. Amine-enhanced or glass-reinforced or paper-reinforced epoxy (eg FR4), glass-reinforced plastic, liquid crystal polymer (LCP), polyphenylene sulfide (PPS), polyfurfural (p〇M) ' Polyaryletherketone (PAEK), poly-ketone (PEEK), polydecylamine (pA), polycarbonate_(pc), polybutylene terephthalate (PBT), polyethylene terephthalate Diester (ρΕτ), Ifeimine (PI), Polyimide Resin, Cyanate, Bismaleimide-Triazine Resin, Nylon, Vinyl Ester Resin, Polyester, Poly Ester resin, polyamide, polyaniline, phenolic resin, polypyrrole, polynaphthalene terephthalate (PEN), polymethyl methacrylate, phosphorus modified epoxy resin, poly(ethylene dioxy) σ Phenol, phenolic resin coated aromatic polyamide paper, polytetrafluoroethylene (PTFE), melamine resin, poly; 5 oxirane resin, fluororesin, dielectric, bismuth, polyether oxime Imine ), polyphenylene ether (ρρο), polypropylene (ρρ), polyethylene (ΡΕ), polysulfone (PSU), polyether oxime (pES), polyaryl decylamine (ΡΑΑ), polyethylene (PVC), Polystyrene (ps), acrylonitrile - butadiene · 122438.doc -28- 200815545 styrene (), acrylonitrile - styrene - acrylic acid (asa), phenylethyl male-acrylonitrile (SAN) and a mixture of two or more of the above polymers, a mixture thereof, which can be in an extremely wide variety of forms. The substrates may comprise additives known to those skilled in the art, such as flame retardants. It is also possible in principle to use any of the polymers listed in the group of polymers. Other suitable substrates are composites, foam polymers, styr〇P, St_ur@, Mw_(pu), ^wi fabrics: cardboard, cardboard', paper, polymer coated paper, wood, mineral materials Stone, glass, plant tissue or animal tissue, or resin impregnated textiles' such substrates have been pressed to obtain flakes or rolls. For the purposes of the present invention, "non-conductive substrate" preferably means that the surface resistance of the substrate is greater than 1 〇 9 ohms / cm. Knife Liquid 4 can be applied by methods known to those skilled in the art. Coating can be performed on one or more sides of the substrate surface and the coating can be one dimensional, two, 隹 or one. The substrate may generally have any desired geometric shape suitable for the intended purpose. The dispersion can be applied by conventional coating methods (washing, spreading, coating, brushing, printing (gravure printing, screen printing, flexographic printing, pad printing, inkjet, lithography, as in DE 1005 1850). Coating by the LaserSonic 8 method or other printing method), smear coating, dip coating, rolling, dusting, fluidized bed or similar method. The layer thickness is preferably from 〇·〇! to 100 μπι, more preferably from 5 〇 beer, especially preferably from 1 to 25 μη. The layers can be applied in a non-structural or structured manner. 122438.doc -29- 200815545 Using the conventional method, you can make the eight drying or hardening of the coating in the form of 'deuterated or unstructured form. For example, the knife dispersion _ A 』 straw is chemically routed, For example, the polymerization, polyaddition or polycondensation of the scorpion sealant, 庑, 'two by the adhesive beam radiation 'microwave radiation, 汛黾 t黾 4丄, 仏, #射或加热) to make the dispersion hard , refined by a purely physical route through the tomb, or by a combination of physical and chemical routes. This is known as the currentless method obtained after dispersion coating, deer g / ―, dry 4 and / or hardened And/or after the electroplating method _ _ 4 fine 忒 Jun, negatively deposited metal on the at least partially hardened dispersion layer. The fl cup and / or the dispersion of the invention can be structured or unstructured in step 3) The simple implementation of the coating step [step a)], the ^ hardening step [step b)] and the deposition step of another metal (2)) is made possible. It is possible that the metal deposition in the step C) by the no-current method and/or the electro-recording method can be borrowed. It is known to those skilled in the art and which have been described in the literature. It is possible to apply one or more metal layers by means of a currentless method and/or an electroplating method (i.e., application of applied voltage and electricity: flow). In principle, any of the metals which are more valuable than component C of the dispersion can be used for the currentless deposition here. For electroplating deposition, it is in principle possible to use any metal. Depositing a copper layer, a chromium layer, a silver layer, a gold layer and/or a nickel layer. The electrolyte solution used herein may comprise, for example, an acid sulfuric acid steel plating bath. The thickness of one or more layers deposited in step c) It is within the conventional knowledge known to those skilled in the art and is not critical to the invention. 122438.doc • 30- 200815545 It is not necessary to be metallized by the currentless method and/or the electric enthalpy method. The substrate is captured, and the 隹壮壮老老老老 & & & & & & 特别特别特别特别特别特别特别特别特别特别特别特别特别特别特别特别特别特别特别特别特别特别特别特别特别特别特别特别特别特别特别特别特别特别特别Surface activation can be used to roughen or control the surface Carbon nanotubes and methods of (e.g.) the whole population genus "Optional wood and put strict upper surface) 'for improving the adhesion of metallic particles or accelerate gold" plot. The release of carbon nanotubes and metal particles also requires a small proportion of the following good human matrix to achieve metallization. Λ Γ Γ ' ' can be mechanically milled, (in detail, by brushing, grinding or polishing with abrasives ^ to Zhao ... under the impact of water flow, sandblasting or N-oxidized stone (dry ice) ) into the stone poor /) or I 曰 by physical methods (such as via heating, laser, ice emperor first, electric or plasma discharge) and / or chemical abrasion (砰之 etching and / or oxygen decoration ... "乂Emulsifying) 仃 surface activation. Methods for mechanical grinding and/or chemical grinding. Rabbits are known in the prior art. It is known to the skilled person and the abrasives described for polishing may be familiar to the art. Any of the abrasives known in the abrasives. An example of a suitable abrasive is pumice powder. The top layer of the hardened dispersion layer is rotted when the water is used under pressure, and the jet stream preferably contains small Solid particles 4 ^ shame particles, such as an average particle size distribution ranging from 40 to 120 μηι, preferably 60 to 8 〇 less, γ lw μ, in stone powder (A12〇3) or powdered quartz with a particle size greater than 3 μΓη (Si02). In the case of chemical milling, it is preferred to use a polymer. a chemical or chemical mixture. In the case of a dry grinding, the polymer can be, for example, at least at the surface; the sap, the stalk is dissolved, or the chemistry of the matrix material. The structure can be destroyed at least in some process and by the help of appropriate reagents, and the reagents that can expand the matrix material are also suitable for releasing the carbon nanotubes. The effect is that the metal ions to be deposited can infiltrate the cavities from the solution of the shellfish, and a larger number of carbon nanotubes are allowed for this purpose. A larger number of carbon nanotubes are released. Increasing the rate of the metallization process. "If the matrix material is, for example, epoxy resin, modified epoxy resin, epoxy phenol: varnish resin, polyacrylic acid vinegar, ABS, styrene-butadiene copolymer or: The ether, then the release of the carbon nanotubes and, for example, metal particles, preferably occurs by the oxidant. The oxidant destroys the bond of the matrix material, for which the binder is detached and the particles are subsequently released. Examples of suitable oxidizing agents are sulphuric acid salts: potassium permanganate, potassium manganate, sodium permanganate, sodium manganate, hydrogen peroxide, oxygen, in, for example, manganese, molybdenum, strontium, tungsten Oxygen, ozone, pentoxide, sulphur dioxide, multi-sulfurization solution, sulfur in the presence of ammonia or amine, oxidization clock, ferric acid unloading, heavy complexes in the presence of catalysts of salt and cobalt salts Chromic acid, citric acid, nitric acid, hydroiodic acid, hydrobromic acid, pyridinium dichromate, chromic acid pyridine complex, chromic anhydride, chromium oxide (VI), periodic acid in sulfuric acid or acetic acid or acetic acid liver , lead tetraacetate, hydrazine, hydrazine, hydrazine, bromine, gas 'fluorine, iron salt solution, hydrogen sulfate solution, sodium percarbonate, oxohalic acid (such as gas or bromate Salt or iodate), persalt (such as sodium periodate or sodium perchlorate), sodium perborate, dichromate (such as sodium dichromate), persulfate (such as potassium peroxodisulfate) , peroxy: potassium monosulfate), bismuth chromite ingot, hypodentite (such as sodium hypochlorite), dimethyl sulfoxide, hydrogen in the presence of electrophile Oxidized tert-butyl, 3 • gas over-formified formic acid, 2,2-dimethylpropyl chain, Des_Manin iodine 122438.doc -32- 200815545 where two chlorine, urea-hydrogen peroxide plus Compound, urea peroxide, 2-dioxos, acid, potassium monooxysulfate, m-chloroperbenzoic acid, N-methyl-p-sized small oxide, 2-methylpropan-2-yl hydroperoxide , peracetic acid, pivalaldehyde, tetraoxide, potassium hydrogen persulfate, barium (ΙΠ) salt and cerium (IV) salt, in the presence of 2,2,6,6-tetramethylpiperidinyl N•oxide Oxygen, triethoxy methoxy iodine 蜿 'difluoroperacetic acid, trimethyl acetaldehyde, ammonium nitrate. During the process, the temperature may be increased during the month to improve the release process. Car 乂 is a manganate (such as potassium permanganate, potassium manganate, sodium permanganate, manganese bismuth) hydrogen peroxide, N-methylmorpholine N-oxide, percarbonate (for example, ^ Sodium or potassium percarbonate), perborate (such as sodium perborate or potassium perborate), persulfate (such as sodium persulfate or potassium persulfate), sodium, potassium and ammonium peroxy: dicaprate and Peroxymonosulfate, sodium sub-sodium, urea, hydrogen, oxyhalide (such as chlorate or bromate or acid salt), perhalogenate (such as sodium periodate) Or sodium perchlorate), tetramethane peroxodisulfate, iron salt solution, vanadium pentoxide, pyridinium dichromate, hydrochloric acid, bromine, chlorine, dichromate. In particular, jin is potassium permanganate, potassium manganate, sodium permanganate, sodium manganate, hydrogen peroxide, its adduct, chlorate, percarbonate, persulfate, peroxodisulfate Salt, sodium hypochlorite and perchlorate. To release carbon nanotubes and, for example, metal particles in a matrix material comprising, for example, a structure (eg, polyester resin, polyacrylic acid, poly-acrylic acid, polyacetamide) 'It is preferred to use, for example, an acidic or anatory chemical and/or chemical compound. Preferably, the acidic chemical formulation and/or chemical formulation mixture is, for example, 澧酴& 戍戍戍, such as hydrochloric acid, sulfuric acid, phosphorus 122438.doc *33- 200815545 acid or nitric acid. Depending on the matrix material, organic acids may also be suitable, such as citric acid or acetic acid. Suitable (iv) chemical and/or chemical mixture is, for example, a base such as a sodium hydroxide solution, a potassium hydroxide solution, ammonium hydroxide or a carbonate such as sodium carbonate or potassium carbonate. The temperature may be increased during the process to improve the release process.

亦可使用溶劑來釋放基質材料中之碳奈米管及（例如）金屬顆粒。因為基質材料必須經受溶劑之溶解或溶劑之溶劑化作用，所以溶劑必須恰當地與基質材料相匹配。若使用可溶解基質材料之溶劑，則使底層與溶劑接觸僅較短時間’為此使基質材料之上層溶劑化且因此分離。原則上，可使用上述溶劑中之任一種溶劑。較佳 (mibk)、—乙二醇單丁基醚。為改良溶劑特性，在溶解程序期間可視情況提高溫度。本發明亦提供-種基板表面，其具有可藉由上述用於製造金屬層之本發明方法獲得的具至少部分導電性之層。此類基板表面可用於傳導電流或熱量、屏蔽電磁輻射或用於磁化。本發明亦提供本發明之分散液用於塗佈金屬層的用途。本發明之基板表面以及本發明之方法詳言之可各種應用。；本發明之基板表面及/或本發明之方法（例如）適用於梦造印刷電路板上之導電帶。該等印刷電路板之實例為彼等具 U2438.doc -34 - 200815545 有夕層内外子層、微通道、板載晶片之印刷電路板、可挽性及硬性印刷電路板，該等印刷電路板(例如)被安裝於諸如以下之產口口中：電腦、電話、電視機、電動汽車組件' 鍵盤、無線電、視訊播放機、⑽放機、cd_r〇m播放機 j DVD播放機、遊戲控制台、量測裝置及控制裝置、感應為、電氣廚用機 '電動玩具等。、… 本發明之方法亦可用以於可撓性電路襯底 :。該等可繞性電路概底(例如)為由已在上面印刷導電:: 構之上述襯底材料組成的塑料箱 : 製造HFID天線、輕„。w U之方法亦適用於狀電魔、座椅加戈；線1吉構、晶片卡模組、帶幕或電漿顯示幕；二:二體、太％能電池或LCD顯示阻或對流器或電熔，.二或其他電容器、電電鑛法塗覆之產二適用於製造呈任何所要形式的由定之；。"例如經早側或雙側金屬塗覆(具有確 f Μ用予;合物基板或瓜模製互連裝置；或適用於二:之裝錦性或功能性表面，其例如用於屏蔽輻射或用於導熱或於產品上用作封裝。導具有有機電子組件之觸點的天線或製造由不亦了之表面上用於電磁屏蔽(咖)目的之塗層。料組成内部塗層以用於製造具有由不導電材亦可為二：支樓的高頻信號波導。基板表面中另—可能用途為用於燃料電池應用之雙極板的流場區 122438.doc -35- 200815545 亦可能使用上述不導電基板來製造非結構化或結構化電層以用於模製物之後續裝飾性金屬化。藉助於本發明之分散液用於製造金屬層以及本發明之基 =面：本發明方法之應用範圍允許金屬化基板(其中：寻基板本身不導電）之低成本製造，該等金屬化基板詳+ ==及感應器、電磁輕射吸收體或氣體屏障或裝： :件(:；之用於機動車輛領域、衛生設施領域、玩具 ΐ域太Γ領域及辦公領域之裝純部件）及封褒以及二㉝明亦可用於紙f、***、個人身份證件等之安王P刷的領域。本發明之方法可用於纺織品 =能化(傳輸器、_天線、詢答器天線及其他：: 感應益、加熱元件、抗靜電系統 ' ^ ^ ^ ,, x 、匕枯嵌專用於塑料之技月尹电糸統）、屏蔽系統等）。 At十之抗雨該等應用之實例為外殼，.諸如電腦外殼；顯电活、音訊設備、視訊設備、订力電子組件、軍事及非置…攝影機之外殼；以及配件、淋浴器噴頭、淋浴扶手及淋浴牛:：洗-把柄及門捏手、衛生間紙輥固持哭、；缸寺：、-屬化門子上之金屬化裝…生條帶及❹ ^巴、体具及鏡殼。同孝木及封裝材料之外亦可提及’汽車領域中之金屬化塑料表面條帶、車外後視鏡、散熱器格拇、^^面，例如裝飾性面、外部車身部件及内部部件正-化、翼型表飾性輪罩。 ^、踏腳板替代物及裝 122438.doc -36 - 200815545 洋a之，h今已在某種程度上或完全由金屬製得之部件可由非導電材料製得。舉例而言，此處可提及落水管、槽、門以及窗框。亦可能製造積體電氣模組上之接觸點或接觸墊或導線。亦可能製造薄金屬箔或經單側或雙側層壓之聚合物襯底材料或金屬化塑料表面，例如裝飾性條帶或車外後視鏡。Solvents can also be used to release the carbon nanotubes and, for example, metal particles in the matrix material. Since the matrix material must be subjected to solvent dissolution or solvent solvation, the solvent must be properly matched to the matrix material. If a solvent which dissolves the matrix material is used, the underlayer is contacted with the solvent for only a short period of time. For this purpose, the upper layer of the matrix material is solvated and thus separated. In principle, any of the above solvents can be used. Preferred (mibk), ethylene glycol monobutyl ether. To improve solvent properties, the temperature can be increased as appropriate during the dissolution procedure. The invention also provides a substrate surface having a layer of at least partial conductivity obtainable by the method of the invention described above for the manufacture of a metal layer. Such substrate surfaces can be used to conduct current or heat, shield electromagnetic radiation, or be used for magnetization. The invention also provides the use of the dispersion of the invention for coating a metal layer. The substrate surface of the present invention, as well as the method of the present invention, can be applied in various applications. The substrate surface of the present invention and/or the method of the present invention, for example, is suitable for use in a conductive tape on a dream printed circuit board. Examples of such printed circuit boards are those having U2438.doc -34 - 200815545 inner and outer sub-layers, micro-channels, printed circuit boards for on-board wafers, pullability and rigid printed circuit boards, such printed circuit boards (for example) installed in a production port such as: computer, telephone, television, electric car component 'keyboard, radio, video player, (10) player, cd_r〇m player j DVD player, game console, Measuring device and control device, induction, electric kitchen machine, electric toy, etc. The method of the present invention can also be applied to a flexible circuit substrate: The flexible circuit basics are, for example, plastic boxes consisting of the above-mentioned substrate materials which have been printed on the following:: HFID antennas are manufactured, and the method of light „.w U is also applicable to the electric magic and seat. Chair Gago; line 1 ji, wafer card module, with curtain or plasma display screen; 2: two-body, too% energy battery or LCD display resistance or convector or fused, two or other capacitors, electric mine The method of coating is suitable for the manufacture of any desired form; for example, by early-side or double-sided metal coating (with or without a composite substrate or a melon molded interconnect device; or Applicable to two: a cosmetic or functional surface, for example for shielding radiation or for heat conduction or for use as a package on a product. Conducting an antenna with contacts for organic electronic components or manufacturing on a surface A coating for the purpose of electromagnetic shielding (coffee). The composition is composed of an internal coating for the manufacture of a high-frequency signal waveguide having a non-conductive material or a second: a branch. Another possible use of the substrate is for fuel. Flow field of battery application bipolar plate 122438.doc -35- 200815545 Using the above non-conductive substrate to fabricate an unstructured or structured electrical layer for subsequent decorative metallization of the molded article. Use of the dispersion of the present invention for the manufacture of a metal layer and the base = face of the present invention: the present invention The scope of application of the method allows low-cost fabrication of metallized substrates (where: the substrate itself is not electrically conductive), such metallized substrates are detailed + == and sensors, electromagnetic light absorbers or gas barriers or devices: : (: ; used in the field of motor vehicles, sanitary facilities, toys, equipment, and office equipment, and the packaging and packaging, as well as the paper, credit card, personal identification, etc. The field of the invention can be used for textiles = energy (transmitters, antennas, antennas and other antennas:: induction, heating elements, antistatic systems ' ^ ^ ^ ,, x , In the plastic technology month Yindian system, shielding system, etc.. At ten anti-rain examples of such applications are the outer casing, such as computer casing; display live, audio equipment, video equipment, power components, military And non-set... The outer casing of the camera; and the accessories, the shower head, the shower handrail and the shower cow:: wash-handle and door handle, bathroom paper roll hold crying; cylinder temple:, - metalized on the door of the door... And ❹ ^巴, body and mirror shell. In addition to filial wood and packaging materials can also be mentioned in the automotive field of metallized plastic surface strips, exterior mirrors, radiator grid thumb, ^^ surface, for example Decorative surface, exterior body parts and internal components, positive-wing, airfoil-shaped wheel cover. ^, stepping board substitute and equipment 122438.doc -36 - 200815545 Ocean a, h is now to some extent or Parts made entirely of metal may be made of a non-conductive material. For example, downpipes, tanks, doors, and window frames may be mentioned herein. It is also possible to make contact points or contact pads or wires on an integrated electrical module. It is also possible to manufacture thin metal foil or polymer substrate materials or metallized plastic surfaces which are laminated on one or both sides, such as decorative strips or exterior mirrors.

U 本發明之分散液及/或方法同樣可用於（例如）印刷電路板、RFID天線或詢答器天線、帶狀電纜或箔導體中之電洞、通道、盲孔等的金屬化以便建立貫穿上面與下面之接觸。當使用其他基板時此亦適用。此外，本發明所製造之金屬化物品_就其包含可磁化金屬而言-可用於可磁化功能性部件之領域’例如磁性面板、磁性遊戲玩具（magnetic games)及磁性表面（例如於冰箱門中）。其亦可用於良好熱導率為有利之領域中，例如用於座椅加熱系統、地面加熱系統及絕緣材料之箔。本發明之金屬化基板表面之較佳用途為由此所製造之基板用作印刷電路板、RFID天線、詢答器天線、座椅加熱系統、帶狀電纜、無觸點晶片卡、薄金屬箔或經單側或雙側層壓之聚合物襯底材料、II導體、太陽能電池或LCD顯示幕或電漿顯示幕中之導電帶或用作裝飾性應用（例如用於封裝材料）的彼等用途。本發明《分散液及方法對於詳言《使用4電漆或導電分散液提供用於不導電基板之金屬覆層的優化系統而言係重要的，當與已知系統相比較時，該等系統具有由低重量、 122438.doc -37- 200815545 良好黏著性、分散性、流動性及高電導率組成的改良特性組合。此夕卜，本發明之分散液及方法可用以於不導電材料上製造均勻且連續之金屬層。在藉由無電流法及/或電錄法進行塗覆之後，該基板可错由熟習此項技術者已知之步驟中的任—步驟進行進^ ::。舉例而可將所存在之電解質殘餘物藉由清洗；基板移除’且/或可將基板乾燥。U The dispersions and/or methods of the present invention are equally applicable to, for example, metallization of holes, channels, blind holes, etc. in printed circuit boards, RFID antennas or interrogator antennas, ribbon cables or foil conductors to establish penetration throughout The above is in contact with the following. This also applies when other substrates are used. Furthermore, the metallized articles produced by the present invention - in the case of magnetizable metals - can be used in the field of magnetizable functional components such as magnetic panels, magnetic games and magnetic surfaces (eg in refrigerator doors) ). It can also be used in areas where good thermal conductivity is advantageous, such as foils for seat heating systems, floor heating systems, and insulating materials. A preferred use of the surface of the metallized substrate of the present invention is that the substrate thus fabricated is used as a printed circuit board, an RFID antenna, an interrogator antenna, a seat heating system, a ribbon cable, a contactless wafer card, a thin metal foil Or a polymeric substrate material laminated on one or both sides, a II conductor, a solar cell or a conductive display in an LCD display or plasma display curtain or used as a decorative application (eg for packaging materials) use. The dispersions and methods of the present invention are important for the detailed description of the use of 4 electrocoats or conductive dispersions to provide an optimized system for metal coatings of non-conducting substrates, when compared to known systems, such systems It has a combination of improved properties consisting of low weight, 122438.doc -37-200815545 good adhesion, dispersibility, flowability and high electrical conductivity. Furthermore, the dispersions and methods of the present invention can be used to produce a uniform and continuous metal layer on a non-conductive material. After coating by the currentless method and/or the electro-acoustic method, the substrate may be subjected to any of the steps known to those skilled in the art. For example, the electrolyte residue present can be removed by cleaning; the substrate is removed' and/or the substrate can be dried.

122438.doc 38-122438.doc 38-

Claims

200815545 十、申請專利範圍： 1. 一種用於塗佈一金屬層於一不導電基板上之分散液，其包含： a 以組份A、B、C及D之總重量計，0.1至99.8重量％之有機黏合劑組份A ; b 以組份A、B、C及D之總重量計，0.1至30重量％之碳奈米管作為組份B ; c 以組份A、B、C及D之總重量計，〇·1至70重量％之平均直徑為〇.〇1至10〇 μΙΏ的導電顆粒作為組份C ; d 以組份A、B、C及D之總重量計，〇至99.7重量％之溶劑組份D。 2 ·如請求項1之分散液，其此外包含以下組份中之至少一者： e 以組份A、B、C及D之總重量計，0·1至20重量％之分散劑組份Ε ;以及 f 以組份A、B、C及D之總重量計，0·1至40重量％之添加劑ρ 〇 3·如請求項1或2之分散液，其中該黏合劑組份a係由聚合物或聚合物混合物組成。 4·如請求項1或2之分散液，其中組份b係由長度處於0.5至 1000 μπι之範圍内且直徑處於0.002至〇·5 μΓΩ之範圍内的單壁或多壁碳奈米管組成。 5 .如清求項1或2之分散液’其中金屬粉末係用作組份c。 6. 一種用於製備如請求項1至5中任一項之分散液的方法， 122438.doc 200815545 其中其步驟包含： a')使組份MC與至少—部分組份D以及（若適當時）組份 E、F及其他組份混合；及 b’）使該混合物分散。 7. -種用於在一不導電基板之至少一部分表面上製造_金屬層的方法，其中其步驟包含·· Μ至乂 4分地塗佈如請求項1至5中任-項之分散液於該基板上； ' b)至少部分乾燥且/或部分硬化塗佈於該基板上之該分散液層；及 C)藉由無電流法及/或電鍍法沈積一金屬於該經至少部分乾燥且/或至少部分硬化之分散液層上，且形成_ 金屬層。月长項7之方法’其中在步驟…與c)之間活化該經至少部分乾燥且/或硬化之分散液層的表面。 9 ·如請求項7至8 $古之方法，其中在步驟a)中將該分散液以結或非結構化形式塗佈。 HZ可由如請求項7至9中任-項之方法獲得之基板表 ’、’、有具至少部分導電性之金屬層。熱求項1〇之基板表面的用途’其用於傳導電流或磁化^用作$飾性金屬表面、用於屏蔽電磁輻射或用於 12·Γ=求項11之用途’其用作印刷電路板、咖天線、詢 °、、、在或其他天線結構、座椅加熱系統、帶狀電纜、 122438.doc 200815545 箔導體、無觸點晶片卡、太陽能電池或LCD顯示幕或電漿顯示幕中之導電帶，或用於製造藉由電鍍法塗覆之產品，其中該等產品可呈任何所要形式。 1 3. —種如請求項1至5中任一項之分散液的用途，其用於塗佈一金屬層。 ·200815545 X. Patent Application Range: 1. A dispersion for coating a metal layer on a non-conductive substrate, comprising: a 0.1 to 99.8 by weight based on the total weight of components A, B, C and D % of organic binder component A; b 0.1 to 30% by weight of carbon nanotubes as component B, based on the total weight of components A, B, C and D; c with components A, B, C and The total weight of D is from 1 to 70% by weight of the conductive particles having an average diameter of 〇.〇1 to 10〇μΙΏ as component C; d is based on the total weight of components A, B, C and D, 〇 Up to 99.7% by weight of solvent component D. 2. The dispersion of claim 1 further comprising at least one of the following components: e 0.1 to 20% by weight of the dispersant component based on the total weight of components A, B, C and D And a dispersion of 0.1 to 40% by weight of the total weight of the components A, B, C and D, such as the dispersion of claim 1 or 2, wherein the binder component a is It consists of a polymer or a mixture of polymers. 4. The dispersion of claim 1 or 2, wherein component b consists of a single-walled or multi-walled carbon nanotube having a length in the range of 0.5 to 1000 μm and a diameter in the range of 0.002 to 5·5 μΓΩ. . 5. The dispersion of claim 1 or 2 wherein metal powder is used as component c. 6. A process for the preparation of a dispersion according to any one of claims 1 to 5, 122438.doc 200815545 wherein the steps thereof comprise: a') component MC and at least - part D and (if appropriate) The components E, F and other components are mixed; and b') the mixture is dispersed. 7. A method for producing a metal layer on at least a portion of a surface of a non-conductive substrate, wherein the step comprises: coating the dispersion of any one of claims 1 to 5 in a range of from Μ to 乂On the substrate; 'b) at least partially drying and/or partially hardening the dispersion layer applied to the substrate; and C) depositing a metal by the currentless method and/or electroplating at least partially dried And/or at least partially hardened on the dispersion layer and forming a _ metal layer. The method of month length item 7 wherein the surface of the at least partially dried and/or hardened dispersion layer is activated between steps ... and c). 9. The method of claim 7 to 8 wherein the dispersion is applied in a knotted or unstructured form in step a). HZ can be obtained from the substrate table ',' obtained by the method of any one of claims 7 to 9, having a metal layer having at least partial conductivity. The use of the surface of the substrate for thermal application is used for conducting current or magnetization, for use as a decorative metal surface, for shielding electromagnetic radiation or for the use of 12 Γ = item 11 Board, coffee antenna, inquiry,, or other antenna structure, seat heating system, ribbon cable, 122438.doc 200815545 foil conductor, contactless wafer card, solar cell or LCD display or plasma display Conductive strips, or used to make products coated by electroplating, wherein the products can be in any desired form. The use of a dispersion according to any one of claims 1 to 5 for coating a metal layer. ·

122438.doc 200815545 七、指定代表圖： (一) 本案指定代表圖為：（無） (二) 本代表圖之元件符號簡單說明：八、本案若有化學式時，請揭示最能顯示發明特徵的化學式： (無）122438.doc 200815545 VII. Designated representative map: (1) The representative representative of the case is: (none) (2) The symbol of the symbol of the representative figure is simple: 8. If there is a chemical formula in this case, please reveal the best indication of the characteristics of the invention. Chemical formula: (none)

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