TWI578099B - Photocurable resin composition containing metal particle and use thereof - Google Patents
Photocurable resin composition containing metal particle and use thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/08—Metals
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L101/00—Compositions of unspecified macromolecular compounds
- C08L101/12—Compositions of unspecified macromolecular compounds characterised by physical features, e.g. anisotropy, viscosity or electrical conductivity
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/0047—Photosensitive materials characterised by additives for obtaining a metallic or ceramic pattern, e.g. by firing
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
- G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
- G03F7/031—Organic compounds not covered by group G03F7/029
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/20—Conductive material dispersed in non-conductive organic material
- H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/09—Use of materials for the conductive, e.g. metallic pattern
- H05K1/092—Dispersed materials, e.g. conductive pastes or inks
- H05K1/095—Dispersed materials, e.g. conductive pastes or inks for polymer thick films, i.e. having a permanent organic polymeric binder
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/08—Metals
- C08K2003/0806—Silver
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/001—Conductive additives
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/003—Additives being defined by their diameter
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/006—Additives being defined by their surface area
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
- H05K2201/02—Fillers; Particles; Fibers; Reinforcement materials
- H05K2201/0203—Fillers and particles
- H05K2201/0206—Materials
- H05K2201/0215—Metallic fillers
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
- H05K2201/02—Fillers; Particles; Fibers; Reinforcement materials
- H05K2201/0203—Fillers and particles
- H05K2201/0242—Shape of an individual particle
- H05K2201/026—Nanotubes or nanowires
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
- H05K2201/03—Conductive materials
- H05K2201/032—Materials
- H05K2201/0326—Inorganic, non-metallic conductor, e.g. indium-tin oxide [ITO]
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
- H05K2201/10—Details of components or other objects attached to or integrated in a printed circuit board
- H05K2201/10007—Types of components
- H05K2201/10083—Electromechanical or electro-acoustic component, e.g. microphone
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K2203/00—Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
- H05K2203/05—Patterning and lithography; Masks; Details of resist
- H05K2203/0502—Patterning and lithography
- H05K2203/0514—Photodevelopable thick film, e.g. conductive or insulating paste
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- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Microelectronics & Electronic Packaging (AREA)
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- Conductive Materials (AREA)
- Parts Printed On Printed Circuit Boards (AREA)
- Materials For Photolithography (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Manufacturing Of Printed Circuit Boards (AREA)
- Manufacturing Of Printed Wiring (AREA)
Description
本發明係有關一種含有金屬微粒子之光硬化性樹脂組成物。以及有關使用上述含有金屬微粒子之光硬化性樹脂組成物的電氣佈線電路圖案之製造方法,以及經由該製造方法而得之觸控面板用基板、顯示裝置用基板、資訊處理終端裝置用基板等之電氣佈線電路形成基板者。 The present invention relates to a photocurable resin composition containing metal fine particles. And a method for producing an electrical wiring circuit pattern using the photocurable resin composition containing the metal fine particles, a substrate for a touch panel, a substrate for a display device, a substrate for an information processing terminal device, and the like. The electrical wiring circuit forms a substrate.
近年來,在電路材料及顯示器中,對小型化、高密度化、高精密化、高信賴性的要求提高,對此而期望圖案加工技術的改善。特別是,導電電路圖案之微細化在小型化及高密度化為不可或缺之要求,因而提議各種方法。 In recent years, in terms of circuit materials and displays, demands for miniaturization, high density, high precision, and high reliability have been increasing, and improvement in pattern processing technology has been desired. In particular, the miniaturization of the conductive circuit pattern is indispensable for miniaturization and high density, and various methods have been proposed.
基板上形成電氣佈線電路圖案之方法已知有印刷法以及光微影法。 A method of forming an electrical wiring circuit pattern on a substrate is known as a printing method and a photolithography method.
為了以印刷法形成高精密電路圖案,且為了抑制印刷時在電路的滲透而必須提高導電膏的黏度。然而,如提高導電膏的黏度,例如在網版印刷法中,因版眼阻塞而引起生產性降低之問題,故難以施行高精密化 。並且,一般,可對應量產步驟之列間距(line & space)的極限在200μm。 In order to form a high-precision circuit pattern by a printing method, it is necessary to increase the viscosity of the conductive paste in order to suppress penetration of the circuit at the time of printing. However, if the viscosity of the conductive paste is increased, for example, in the screen printing method, the productivity is lowered due to clogging of the stencil, so that it is difficult to perform high precision. . Moreover, in general, the limit of the line & space corresponding to the mass production step is 200 μm.
並且,光微影法雖可對應高精密之電路圖案,然為改善電路與基板的密接性,必須在基板整面進行金屬濺鍍。更且,必須有抗蝕膜、圖案曝光、顯影、蝕刻以及光阻剝離等多數步驟,相較於印刷法,生產性低劣。並且,濺鍍步驟所產生之針孔會有使產率降低之問題。 Further, although the photolithography method can correspond to a high-precision circuit pattern, in order to improve the adhesion between the circuit and the substrate, it is necessary to perform metal sputtering on the entire surface of the substrate. Further, it is necessary to have a plurality of steps such as a resist film, pattern exposure, development, etching, and photoresist peeling, and the productivity is inferior to the printing method. Moreover, the pinholes generated by the sputtering step have a problem of lowering the yield.
為改善上述問題,而盛行含有金屬微粒子之光硬化性樹脂組成物的開發。 In order to improve the above problems, development of a photocurable resin composition containing metal fine particles has been prevailing.
專利文獻1中記載:將包含有金屬膠體粒子與使其分散用之高分子分散劑與光自由基起始劑與溶媒之組成物塗布在基板上,將此藉由光微影法進行圖案化,再經加熱使顯出導電性之方法。然而,上述方法係為得到導電性而必須在200℃以上進行燒成處理,故電路圖案形成所用之基板則僅限於玻璃及陶瓷等之耐熱性者。 Patent Document 1 discloses that a metal colloidal particle and a polymer dispersing agent for dispersing it and a composition of a photoradical initiator and a solvent are coated on a substrate, and patterned by photolithography. And heating to show the conductivity. However, since the above method is required to perform baking treatment at 200 ° C or higher in order to obtain conductivity, the substrate used for circuit pattern formation is limited to heat resistance such as glass and ceramics.
近來已開發一種塑膠基板用之低溫燒成型之導電膏,開發出以120℃左右之較為低溫的熱處理而得到導電性者(專利文獻2)。然而,熱處理時間須要60分鐘等,為了以工業規格進行大量生產,就生產性觀點而言並無法滿足。 Recently, a conductive paste for low-temperature firing of a plastic substrate has been developed, and a heat treatment at a relatively low temperature of about 120 ° C has been developed to obtain conductivity (Patent Document 2). However, the heat treatment time takes 60 minutes, etc., and in order to mass-produce with industrial specifications, it cannot be satisfied from the viewpoint of productivity.
[專利文獻1]日本特開2003-140330號公報 [Patent Document 1] Japanese Patent Laid-Open Publication No. 2003-140330
[專利文獻2]日本專利第3218767號公報 [Patent Document 2] Japanese Patent No. 3218767
本發明之目的係提供一種可在薄膜基板上形成高精密之電路圖案,且為得到低電阻之電路圖案的理想之含有金屬微粒子之光硬化性樹脂組成物。更且,本發明之目的係提供一種薄膜基板上之高精密且低電阻之電氣佈線電路圖案之製造方法、及由該方法而得之電氣佈線電路基板。 An object of the present invention is to provide a photocurable resin composition containing metal fine particles which can form a high-precision circuit pattern on a film substrate and which is a circuit pattern having a low electric resistance. Furthermore, an object of the present invention is to provide a method of manufacturing a high-precision and low-resistance electrical wiring circuit pattern on a film substrate, and an electrical wiring circuit board obtained by the method.
本發明者等為解決上述課題而反覆研究之結果,發現一種含有金屬微粒子之光硬化性樹脂組成物,係含有具導電性之微粒子(A)與光硬化性樹脂組成物(B)之含有金屬微粒子之光硬化性樹脂組成物,該樹脂組成物中,具導電性的金屬微粒子(A)之含量係在62至86重量%之範圍,且具導電性之微粒子(A)係具有:(i)50%平均粒徑係0.1至5μm、(ii)敲緊密度在2.5g/cm3以下且(iii)BET比表面積在1.5m2/g以下之物性,藉由使用具有上述物性之該樹脂組成物,即不會使生產性降低,且在不具有高耐熱性之PET薄膜等薄膜基板上可形成具有高導電性,密接性以及解析度優異之高精密的電氣佈線電路圖案。 In order to solve the above problems, the inventors of the present invention have found that a photocurable resin composition containing metal fine particles contains a metal containing conductive particles (A) and a photocurable resin composition (B). The photocurable resin composition of the microparticles, wherein the content of the conductive metal microparticles (A) in the resin composition is in the range of 62 to 86% by weight, and the conductive microparticles (A) have: (i) a resin having a 50% average particle diameter of 0.1 to 5 μm, (ii) a knocking degree of 2.5 g/cm 3 or less, and (iii) a BET specific surface area of 1.5 m 2 /g or less, by using the resin having the above physical properties The composition, that is, the high-precision electrical wiring circuit pattern having high conductivity, excellent adhesion, and excellent resolution can be formed on a film substrate such as a PET film which does not have high heat resistance without lowering productivity.
本發明係依據該等見解而完成者,係提供下述含有金屬微粒子之光硬化性樹脂組成物、使用此之電氣佈線電路圖案的製造方法、及由此方法所製造之電氣佈線電 路基板。 According to the present invention, the present invention provides a photocurable resin composition containing metal fine particles, a method for producing an electrical wiring circuit pattern using the same, and an electric wiring manufactured by the method. Road substrate.
(1)一種含有金屬微粒子之光硬化性樹脂組成物,其係含有具導電性之微粒子(A)與光硬化性樹脂組成物(B)之含有金屬微粒子之光硬化性樹脂組成物,該含有金屬微粒子之光硬化性樹脂組成物中,相對於組成物之總量,具導電性的微粒子(A)之含量係在62至86重量%之範圍,且具導電性之微粒子(A)係具有下述物性:(i)50%平均粒徑係0.1至5μm、(ii)敲緊密度在2.5g/cm3以下、(iii)BET比表面積在1.5m2/g以下。 (1) A photocurable resin composition containing metal fine particles, which comprises a photocurable resin composition containing fine particles (A) and a photocurable resin composition (B) containing metal fine particles, and the composition In the photocurable resin composition of the metal fine particles, the content of the conductive fine particles (A) is in the range of 62 to 86% by weight with respect to the total amount of the composition, and the conductive fine particles (A) have The following physical properties: (i) 50% average particle diameter is 0.1 to 5 μm, (ii) knocking degree is 2.5 g/cm 3 or less, and (iii) BET specific surface area is 1.5 m 2 /g or less.
(2)如(1)之含有金屬微粒子之光硬化性樹脂組成物,其中,相對於具導電性之微粒子(A)100重量份,光硬化性樹脂組成物(B)之含量在15至60重量份之範圍。 (2) The photocurable resin composition containing metal fine particles according to (1), wherein the photocurable resin composition (B) is contained in an amount of 15 to 60 with respect to 100 parts by weight of the conductive fine particles (A). The range of parts by weight.
(3)如(1)或(2)之含有金屬微粒子之光硬化性樹脂組成物,其中,具導電性之微粒子(A)係銀或含銀之合金。 (3) The photocurable resin composition containing metal fine particles according to (1) or (2), wherein the conductive fine particles (A) are silver or an alloy containing silver.
(4)如(1)至(3)中任一項之含有金屬微粒子之光硬化性樹脂組成物,其中,光硬化性樹脂組成物(B)係包含鹼可溶性樹脂者。 (4) The photocurable resin composition containing metal fine particles according to any one of (1) to (3), wherein the photocurable resin composition (B) contains an alkali-soluble resin.
(5)如(1)至(4)中任一項之含有金屬微粒子之光硬化性樹脂組成物,其中,光硬化性樹脂組成物(B)係含有具O-醯基肟構造之光聚合起始劑者。 (5) The photocurable resin composition containing metal fine particles according to any one of (1) to (4), wherein the photocurable resin composition (B) contains photopolymerization having an O-fluorenyl fluorene structure Starter.
(6)一種電氣佈線電路圖案之製造方法,係包含下述步驟:聚對苯二甲酸乙二酯(PET)膜上披覆有氧化銦錫(ITO)、氧化鋅(ZnO)或銀奈米線而成之透明導電膜基板 上,塗布如(1)至(5)中任一項之含有金屬微粒子之光硬化性樹脂組成物的塗布步驟;隔著應形成之電氣佈線電路圖案所對應的薄膜或遮罩,對含有金屬微粒子之光硬化性樹脂組成物的塗膜照射活化能射線使塗膜硬化之曝光步驟;將塗膜之未曝光部分以顯影液溶解、去除並乾燥之顯影步驟。 (6) A method of manufacturing an electrical wiring circuit pattern comprising the steps of: coating a polyethylene terephthalate (PET) film with indium tin oxide (ITO), zinc oxide (ZnO) or silver nanoparticles Transparent conductive film substrate The coating step of coating the photocurable resin composition containing the metal fine particles according to any one of (1) to (5); and containing the metal via a film or a mask corresponding to the electric wiring circuit pattern to be formed The coating film of the photocurable resin composition of the microparticles is irradiated with an activation energy ray to cure the coating film; the developing step of dissolving, removing and drying the unexposed portion of the coating film with a developing solution.
(7)一種電氣佈線電路基板,係使用如(6)之電氣佈線電路圖案之製造方法所製造者。 (7) An electric wiring circuit board manufactured by using the method of manufacturing an electric wiring circuit pattern of (6).
如依本發明之含有金屬微粒子之光硬化性樹脂組成物,其係含有具導電性之微粒子(A)與光硬化性樹脂組成物(B)之含有金屬微粒子之光硬化性樹脂組成物,該樹脂組成物中,具導電性的微粒子(A)之含量係在62至86重量%之範圍,且具導電性之微粒子(A)係具有:(i)50%平均粒徑係0.1至5μm、(ii)敲緊密度在2.5g/cm3以下且(iii)BET比表面積在1.5m2/g以下之物性,藉由使用該樹脂組成物,可在耐熱性低的薄膜基板上形成導電性優異且密接性優異之電氣電路圖案。並且,即使如以往之含有金屬微粒子之光硬化性樹脂組成物不進行加熱處理,亦可呈現導電性。並且,藉由使用本發明之樹脂組成物,即可製造高精密之電氣佈線電路圖案,可得到高精密之電氣佈線電路基板。 A photocurable resin composition containing metal fine particles according to the present invention, which comprises a photocurable resin composition containing fine particles (A) and a photocurable resin composition (B) containing metal fine particles, In the resin composition, the content of the conductive fine particles (A) is in the range of 62 to 86% by weight, and the conductive fine particles (A) have: (i) 50% average particle diameter of 0.1 to 5 μm, (ii) physical properties of knocking tightness of 2.5 g/cm 3 or less and (iii) BET specific surface area of 1.5 m 2 /g or less, and formation of conductivity on a film substrate having low heat resistance by using the resin composition An electrical circuit pattern that is excellent in adhesion and excellent in adhesion. Further, even if the photocurable resin composition containing metal fine particles as in the prior art is not subjected to heat treatment, conductivity can be exhibited. Further, by using the resin composition of the present invention, a high-precision electrical wiring circuit pattern can be manufactured, and a highly precise electrical wiring circuit board can be obtained.
以下,詳細說明本發明。 Hereinafter, the present invention will be described in detail.
本發明之含有金屬微粒子之光硬化性樹脂組成物係含有具導電性之微粒子(A)與光硬化性樹脂組成物(B)之組成物。較佳者係使具導電性之微粒子(A)均一地分散在光硬化性樹脂組成物(B)中者。並且,可在基板上形成塗膜,且經活化能射線照射之部分(曝光部分)經聚合而不溶於顯影液,不被光照射之部分(未曝光部分)只要溶於顯影液者即可。 The photocurable resin composition containing metal fine particles of the present invention contains a composition of conductive fine particles (A) and photocurable resin composition (B). Preferably, the conductive fine particles (A) are uniformly dispersed in the photocurable resin composition (B). Further, a coating film can be formed on the substrate, and the portion irradiated with the active energy ray (exposed portion) is polymerized and insoluble in the developer, and the portion (unexposed portion) not irradiated with light can be dissolved in the developer.
本發明之含有金屬微粒子之光硬化性樹脂組成物中,相對於含有金屬微粒子之光硬化性樹脂組成物之總量,具導電性之金屬微粒子(A)之含量如為62重量%以上即可,以64重量%以上為佳,以65重量%以上更佳,以66重量%以上又更佳。如在上述範圍,電氣佈線電路圖案之電阻值在實用上充分變低,不會妨礙信號(訊號)的傳達。 In the photocurable resin composition containing metal fine particles of the present invention, the content of the conductive metal fine particles (A) is 62% by weight or more based on the total amount of the photocurable resin composition containing the metal fine particles. More preferably, it is 64% by weight or more, more preferably 65% by weight or more, and still more preferably 66% by weight or more. As in the above range, the resistance value of the electrical wiring circuit pattern is sufficiently low in practical use, and does not hinder the transmission of signals (signals).
相對於含有金屬微粒子之光硬化性樹脂組成物之總量,具導電性之金屬微粒子(A)之含量,如為86重量%以下即可,以84重量%以下為佳,以83重量%以下更佳,以82重量%以下又更佳。如在上述範圍,不會有因感光性樹脂量的降低而使感度下降,電路圖案的形成良率顯著降低,或與基板之密接性降低、解析度下降等之問題產生。 The content of the conductive metal fine particles (A) may be 86% by weight or less based on the total amount of the photocurable resin composition containing the metal fine particles, preferably 84% by weight or less, and 83% by weight or less. More preferably, it is more preferably 82% by weight or less. In the above range, the sensitivity is lowered by the decrease in the amount of the photosensitive resin, the formation yield of the circuit pattern is remarkably lowered, or the adhesion to the substrate is lowered, and the resolution is lowered.
具導電性之金屬微粒子(A)之含量,相對於含有金屬微粒子之光硬化性樹脂組成物之總量,可列舉如下述範圍:約62至86重量%,以約64至84重量%為佳,以約65至83重量%更佳,以約66至82重量%又更佳。 The content of the conductive metal fine particles (A) is preferably in the range of about 62 to 86% by weight, preferably about 64 to 84% by weight, based on the total amount of the photocurable resin composition containing the metal fine particles. More preferably, it is about 65 to 83% by weight, more preferably about 66 to 82% by weight.
光聚合起始劑,在使用具O-醯基肟構造者時,本發明之含有金屬微粒子之光硬化性樹脂組成物中,具導電性之金屬微粒子(A)之含量,相對於含有金屬微粒子之光硬化性樹脂組成物之總量,係以70重量%以上為佳,以75重量%以上更佳。並以83重量%以下為佳。 When the photopolymerization initiator is used, the content of the conductive metal microparticles (A) in the photocurable resin composition containing the metal microparticles of the present invention is relative to the metal microparticles containing the metal microparticles. The total amount of the photocurable resin composition is preferably 70% by weight or more, more preferably 75% by weight or more. It is preferably 83% by weight or less.
光聚合起始劑,在使用具O-醯基肟構造者時,具導電性之金屬微粒子(A)之含量,相對於含有金屬微粒子之光硬化性樹脂組成物之總量,可列舉如下述範圍:以70至83重量%為佳,以75至83重量%更佳。 When the photopolymerization initiator is used, the content of the conductive metal microparticles (A) in the case of using the O-indenyl ruthenium structure is as follows, and the total amount of the photocurable resin composition containing the metal microparticles is as follows. Range: preferably from 70 to 83% by weight, more preferably from 75 to 83% by weight.
含有金屬微粒子之光硬化性樹脂組成物中,光硬化性樹脂組成物(B)的含量,相對於具導電性之微粒子(A)100重量份,係以15重量份以上(例如:20.5重量份以上)為佳,以18重量份以上更佳。並且,以60重量份以下(例如:53.9重量份以下)為佳,以50重量份以下更佳,尤以45重量份以下又更佳。 In the photocurable resin composition containing metal fine particles, the content of the photocurable resin composition (B) is 15 parts by weight or more based on 100 parts by weight of the conductive fine particles (A) (for example, 20.5 parts by weight). The above) is preferably more preferably 18 parts by weight or more. Further, it is preferably 60 parts by weight or less (e.g., 53.9 parts by weight or less), more preferably 50 parts by weight or less, still more preferably 45 parts by weight or less.
含有金屬微粒子之光硬化性樹脂組成物中,光硬化性樹脂組成物(B)的含量,相對於具導電性之微粒子(A)100重量份,可列舉如下述範圍:以15至60重量份(例如:20.5至53.9重量份)為佳,以18至50重量份更佳,尤以18至45重量份又更佳。 In the photocurable resin composition containing metal fine particles, the content of the photocurable resin composition (B) is, for example, in the following range: from 15 to 60 parts by weight based on 100 parts by weight of the conductive fine particles (A). (e.g., 20.5 to 53.9 parts by weight) is preferably 18 to 50 parts by weight, more preferably 18 to 45 parts by weight.
本發明之含有金屬微粒子之光硬化性樹脂組 成物,除了具導電性之微粒子(A)與光硬化性樹脂組成物(B)以外,亦可含有調平劑、增黏劑、抗沉澱劑、提升密接性用之偶合劑以及消泡劑等之含有金屬微粒子之光硬化性樹脂組成物用的添加劑。 Photocurable resin group containing metal microparticles of the present invention The product may contain, in addition to the conductive fine particles (A) and the photocurable resin composition (B), a leveling agent, a tackifier, an anti-precipitating agent, a coupling agent for improving adhesion, and an antifoaming agent. An additive for a photocurable resin composition containing metal fine particles.
調平劑之例可列舉如:聚醚改質聚二甲基矽氧烷、聚酯改質聚二甲基矽氧烷、聚酯改質甲基烷基聚矽氧烷、聚醚改質聚甲基烷基矽氧烷、芳烷基改質聚甲基烷基矽氧烷、聚酯改質含羥基之聚二甲基矽氧烷、聚醚酯改質含羥基之聚二甲基矽氧烷、丙烯酸系共聚物、甲基丙烯酸系共聚物、聚醚改質聚甲基烷基矽氧烷、丙烯酸烷酯共聚物、甲基丙烯酸烷酯共聚物、丙烯酸、丙烯酸烷基酯共聚物、聚氧伸烷基單烷基或烯基醚之接枝化共聚物、卵磷脂等之習知物。 Examples of the leveling agent include, for example, a polyether modified polydimethyl siloxane, a polyester modified polydimethyl siloxane, a polyester modified methyl alkyl polyoxy siloxane, a polyether modified product. Polymethylalkyl sulfoxane, aralkyl modified polymethyl alkyl decane, polyester modified hydroxyl-containing polydimethyl siloxane, polyether ester modified hydroxyl-containing polydimethyl a siloxane, an acrylic copolymer, a methacrylic copolymer, a polyether modified polymethylalkyl siloxane, an alkyl acrylate copolymer, an alkyl methacrylate copolymer, an acrylic acid, an alkyl acrylate copolymer A conventionally grafted copolymer of polyalkylene monoalkyl or alkenyl ether, lecithin or the like.
調平劑之添加量,相對於含有金屬微粒子之光硬化性樹脂組成物之總量,係以0.1重量%以上為佳。如在此範圍內,可充分地獲得調平劑之效果。並且,調平劑之添加量,相對於含有金屬微粒子之光硬化性樹脂組成物係以3重量%以下為佳。如在此範圍內,不會引發密接性下降、印刷性惡化等。並且,即使增至該範圍以上,亦不會使調平劑效果更加提升。 The amount of the leveling agent to be added is preferably 0.1% by weight or more based on the total amount of the photocurable resin composition containing the metal fine particles. As in this range, the effect of the leveling agent can be sufficiently obtained. Further, the amount of the leveling agent to be added is preferably 3% by weight or less based on the photocurable resin composition containing the metal fine particles. If it is this range, the fall of adhesiveness, the deterioration of printability, etc. are not caused. Moreover, even if it is increased above this range, the effect of the leveling agent is not improved.
增黏劑在需要高黏度化時,係可使用氯乙烯-乙酸乙烯酯共聚樹脂、聚酯樹脂、丙烯酸樹脂、聚胺基甲酸酯樹脂等之各種聚合物;羧甲基纖維素等之多糖類;糊精棕櫚酸酯等之糖脂肪酸酯;辛酸鋅等之金屬皂;膨潤石等之膨潤性黏土礦物;薰衣草油、石油經蒸餾之 礦物性揮發油等。 When the tackifier requires high viscosity, various polymers such as vinyl chloride-vinyl acetate copolymer resin, polyester resin, acrylic resin, and polyurethane resin can be used; Sugar; fatty acid esters such as dextrin palmitate; metal soaps such as zinc octoate; swelling clay minerals such as bentonite; lavender oil, petroleum by distillation Mineral volatile oil, etc.
增黏劑之添加量,相對於含有金屬微粒子之光硬化性樹脂組成物之總量,係以0.1重量%以上為佳。如在此範圍內,可充分地獲得增黏劑之效果。並且,增黏劑之添加量,相對於含有金屬微粒子之光硬化性樹脂組成物之總量,係以5重量%以下為佳。如在此範圍內,不會引發印刷性的惡化等。 The amount of the tackifier added is preferably 0.1% by weight or more based on the total amount of the photocurable resin composition containing the metal fine particles. As in this range, the effect of the tackifier can be sufficiently obtained. Further, the amount of the tackifier added is preferably 5% by weight or less based on the total amount of the photocurable resin composition containing the metal fine particles. If it is within this range, deterioration of printability or the like is not caused.
抗沉澱劑係可使用例如:長鏈聚醯胺系、長鏈聚醯胺系之磷酸鹽、聚醯胺系、不飽和多元羧酸、含三級胺基之聚合物等之市售品。 As the anti-precipitation agent, for example, a commercially available product such as a long-chain polyamine-based, a long-chain polyamine-based phosphate, a polyamine-based, an unsaturated polycarboxylic acid, or a tertiary amino group-containing polymer can be used.
抗沉澱劑之添加量,相對於含有金屬微粒子之光硬化性樹脂組成物之總量,係以0.1重量%以上為佳。如在此範圍內,可充分地獲得抗沉澱劑之效果。並且,抗沉澱劑之添加量,相對於含有金屬微粒子之光硬化性樹脂組成物之總量,係以3重量%以下為佳。如在此範圍內,不會因多餘的增黏效果而引發印刷性的惡化等。並且,即使增至該範圍以上,亦不會使抗沉澱劑效果更加提升。 The amount of the anti-precipitating agent to be added is preferably 0.1% by weight or more based on the total amount of the photocurable resin composition containing the metal fine particles. As in this range, the effect of the anti-precipitating agent can be sufficiently obtained. Further, the amount of the anti-precipitating agent to be added is preferably 3% by weight or less based on the total amount of the photocurable resin composition containing the metal fine particles. Within this range, deterioration of printability or the like is not caused by an excessive viscosity-increasing effect. Moreover, even if it is increased above this range, the effect of the anti-precipitant is not improved.
提升密接性用之偶合劑係以具反應性官能基之烷氧基矽烷化合物為佳,例如可列舉:乙烯基三氯矽烷、乙烯基三甲氧基矽烷及乙烯基三乙氧基矽烷等具有乙烯基之烷氧基矽烷化合物;2-(3,4-環氧環己基)乙基三甲氧基矽烷、3-環氧丙氧基丙基三甲氧基矽烷、3-環氧丙氧基丙基甲基二乙氧基矽烷以及3-環氧丙氧基丙基三乙氧基矽烷等含有環氧基之烷氧基矽烷化合物;對苯乙 烯基三甲氧基矽烷等具有苯乙烯基之烷氧基矽烷化合物;3-甲基丙烯醯氧基丙基甲基二甲氧基矽烷、3-甲基丙烯醯氧基丙基三甲氧基矽烷、3-甲基丙烯醯氧基丙基甲基二乙氧基矽烷以及3-甲基丙烯醯氧基丙基三乙氧基矽烷等具有甲基丙烯醯氧基之烷氧基矽烷化合物;3-丙烯醯氧基丙基三甲氧基矽烷等具有丙烯醯氧基之烷氧基矽烷化合物;N-2-(胺基乙基)-3-胺基丙基甲基二甲氧基矽烷、N-2-(胺基乙基)-3-胺基丙基三甲氧基矽烷、N-2-(胺基乙基)-3-胺基丙基三乙氧基矽烷、3-胺基丙基三甲氧基矽烷、3-胺基丙基三乙氧基矽烷、3-三乙氧基矽基-N-(1,3-二甲基亞丁基)丙基胺、N-苯基-3-胺基丙基三甲氧基矽烷以及N-(乙烯基苄基)-2-胺基乙基-3-胺基丙基三甲氧基矽烷之鹽酸鹽等具有胺基之烷氧基矽烷化合物;3-脲基丙基三乙氧基矽烷等具有脲基之烷氧基矽烷化合物;3-氯丙基三甲氧基矽烷等具有氯丙基之烷氧基矽烷化合物;3-巰基丙基甲基二甲氧基矽烷以及3-巰基丙基三甲氧基矽烷等具有巰基之烷氧基矽烷化合物;雙(三乙氧基矽基丙基)四硫化物等具有硫基之烷氧基矽烷化合物;3-異氰酸酯丙基三乙氧基矽烷等具有異氰酸酯基之烷氧基矽烷化合物;咪唑矽烷等具有咪唑基之烷氧基矽烷化合物等。 The coupling agent for improving the adhesion is preferably an alkoxydecane compound having a reactive functional group, and examples thereof include ethylene having trivinyl decane, vinyl trimethoxy decane, and vinyl triethoxy decane. Alkoxy decane compound; 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, 3-glycidoxypropyltrimethoxydecane, 3-glycidoxypropyl An alkoxy decane compound containing an epoxy group such as methyl diethoxy decane or 3-glycidoxy propyl triethoxy decane; a styryl alkoxydecane compound such as an alkenyltrimethoxydecane; 3-methacryloxypropylmethyldimethoxydecane, 3-methylpropenyloxypropyltrimethoxydecane An alkoxydecane compound having a methacryloxycarbonyl group such as 3-methacryloxypropylmethyldiethoxydecane or 3-methylpropenyloxypropyltriethoxydecane; An alkoxydecane compound having an acryloxy group such as acryloxypropyltrimethoxydecane; N-2-(aminoethyl)-3-aminopropylmethyldimethoxydecane, N -2-(Aminoethyl)-3-aminopropyltrimethoxydecane, N-2-(aminoethyl)-3-aminopropyltriethoxydecane, 3-aminopropyl Trimethoxydecane, 3-aminopropyltriethoxydecane, 3-triethoxyindolyl-N-(1,3-dimethylbutylidene)propylamine, N-phenyl-3- An alkoxydecane compound having an amine group such as an aminopropyltrimethoxydecane and a hydrochloride salt of N-(vinylbenzyl)-2-aminoethyl-3-aminopropyltrimethoxydecane; a ureido-based alkoxydecane compound such as 3-ureidopropyltriethoxydecane; 3-chloropropyl Alkoxydecane compound having a chloropropyl group such as methoxy decane; alkoxy decane compound having a mercapto group such as 3-mercaptopropylmethyldimethoxydecane and 3-mercaptopropyltrimethoxydecane; Alkoxydecane compound having a sulfur group such as triethoxymercaptopropyl)tetrasulfide; an alkoxydecane compound having an isocyanate group such as 3-isocyanatepropyltriethoxydecane; imidazolium or the like having an imidazolyl group Alkoxydecane compounds and the like.
偶合劑之添加量,相對於含有金屬微粒子之光硬化性樹脂組成物之總量,係以0.1重量%以上為佳。如在此範圍內,可充分地獲得偶合劑之效果。並且,偶合劑之添加量,相對於含有金屬微粒子之光硬化性樹脂組成物 之總量,係以5重量%以下為佳。如在此範圍內,不會引發解析性降低。並且,即使增至該範圍以上,亦不會使偶合劑效果更加提升。 The amount of the coupling agent added is preferably 0.1% by weight or more based on the total amount of the photocurable resin composition containing the metal fine particles. As in this range, the effect of the coupling agent can be sufficiently obtained. Further, the amount of the coupling agent added is relative to the photocurable resin composition containing the metal fine particles. The total amount is preferably 5% by weight or less. As far as this range is concerned, no decrease in resolution is caused. Moreover, even if it is increased above this range, the effect of the coupling agent is not improved.
消泡劑之例可列舉如:聚矽氧樹脂、聚矽氧溶液、不含聚矽氧之特殊消泡劑、丙烯酸烷基酯共聚物、甲基丙烯酸烷基酯共聚物、烷基乙烯基醚、丙烯酸系共聚物、消泡性聚合物、聚矽氧烷、消泡性聚矽氧烷、聚甲基烷基矽氧烷、聚醚改質聚矽氧烷、烷烴系礦物油等之習知物。 Examples of the antifoaming agent include polyfluorene oxide resin, polyfluorene oxide solution, special antifoaming agent without polyoxymethylene, alkyl acrylate copolymer, alkyl methacrylate copolymer, and alkyl vinyl group. Ether, acrylic copolymer, antifoaming polymer, polyoxyalkylene oxide, antifoaming polyoxyalkylene oxide, polymethylalkyl siloxane, polyether modified polyoxy siloxane, alkane mineral oil, etc. Traditional things.
消泡劑之添加量,相對於含有金屬微粒子之光硬化性樹脂組成物之總量,係以0.01重量%以上為佳。如在此範圍內,可充分地獲得消泡劑之效果。並且,消泡劑之添加量,相對於含有金屬微粒子之光硬化性樹脂組成物之總量,係以1重量%以下為佳。如在此範圍內,不會引發密接性降低、組成物之分散性惡化等。並且,即使增至該範圍以上,亦不會使消泡劑效果更加提升。 The amount of the antifoaming agent added is preferably 0.01% by weight or more based on the total amount of the photocurable resin composition containing the metal fine particles. As is within this range, the effect of the antifoaming agent can be sufficiently obtained. Further, the amount of the antifoaming agent added is preferably 1% by weight or less based on the total amount of the photocurable resin composition containing the metal fine particles. Within this range, the adhesion is not lowered, the dispersibility of the composition is deteriorated, and the like. Moreover, even if it is increased above this range, the effect of the antifoaming agent will not be improved.
對於形成電氣佈線電路圖案,係將本發明之含有金屬微粒子之光硬化性樹脂組成物均一地塗布在基板上,使該塗膜密接遮罩圖案,並照射活化能射線,使含有金屬微粒子之光硬化性樹脂組成物硬化。並且,藉由使用顯影液去除未曝光部分,可得到電氣佈線電路圖案。上述電氣佈線電路圖案係可使用作為可撓性電路基板、觸控面板用基板、顯示裝置用基板等之電路圖案。 In the formation of the electric wiring circuit pattern, the photocurable resin composition containing the metal fine particles of the present invention is uniformly applied onto the substrate, and the coating film is adhered to the mask pattern, and the active energy ray is irradiated to cause the light containing the metal microparticles. The curable resin composition is hardened. Further, an electric wiring circuit pattern can be obtained by removing the unexposed portion by using a developing solution. As the electrical wiring circuit pattern, a circuit pattern such as a flexible circuit board, a touch panel substrate, or a display device substrate can be used.
本發明之含有金屬微粒子之光硬化性樹脂組成物中 所使用之具導電性之金屬微粒子(A)係具有:(i)50%平均粒徑係0.1至5μm、(ii)敲緊密度在2.5g/cm3以下且(iii)BET比表面積在1.5m2/g以下之物性,如為具導電性者,並無特別限制而可使用。 The conductive metal fine particles (A) used in the photohardenable resin composition containing metal fine particles of the present invention have: (i) 50% average particle diameter of 0.1 to 5 μm, and (ii) knocking degree of 2.5. The physical properties of g/cm 3 or less and (iii) BET specific surface area of 1.5 m 2 /g or less are not particularly limited as long as they are electrically conductive.
(i)50%平均粒徑如為0.1μm以上(例如:大於0.1μm)即可,以0.3μm以上為佳。如在此範圍內,不會有粒子間之接觸面積過小而使導電性降低之問題。並且,小於0.1μm之奈米金屬因電漿子吸收而吸收光,因此,如此之含有金屬微粒子之光硬化性樹脂組成物無法進行利用曝光之電路形成。 (i) The 50% average particle diameter may be 0.1 μm or more (for example, more than 0.1 μm), and preferably 0.3 μm or more. If it is within this range, there is no problem that the contact area between the particles is too small to lower the conductivity. Further, since the nano metal of less than 0.1 μm absorbs light by absorption by the plasmonic material, the photocurable resin composition containing the metal fine particles cannot be formed by a circuit using exposure.
並且,50%平均粒徑如為5μm以下(例如:小於5μm)即可,以3μm以下為佳。如在上述範圍內,即不會導致解析性降低。 Further, the 50% average particle diameter may be 5 μm or less (for example, less than 5 μm), and preferably 3 μm or less. If it is within the above range, it does not cause a decrease in resolution.
50%平均粒徑方面,較佳者係大於0.1μm且小於5μm,或約為0.3至5μm,以約0.3至3μm更佳。 In terms of 50% average particle diameter, it is preferably more than 0.1 μm and less than 5 μm, or about 0.3 to 5 μm, more preferably about 0.3 to 3 μm.
本發明中之50%平均粒徑係指,組成物之整體或部分所包含之具導電性的微粒子全部以粒徑大小排列時之中間值(中央值)。本發明中之50%平均粒徑係經微型追蹤(micro track)法(雷射繞射/散射法)所測定之值。 The 50% average particle diameter in the present invention means an intermediate value (central value) when all of the conductive fine particles contained in the whole or a part of the composition are arranged in a particle size. The 50% average particle diameter in the present invention is a value measured by a micro track method (laser diffraction/scattering method).
(ii)敲緊密度如為2.5g/cm3以下(例如:小於2.5g/cm3)即可。如在上述範圍內,光的透過性不會變差,光硬化性樹脂組成物(B)成分之硬化變得充分,其結果,使含有金屬微粒子之光硬化性樹脂組成物與基板間之密接性,以及解析度變得充分者。 (ii) The knocking degree may be 2.5 g/cm 3 or less (for example, less than 2.5 g/cm 3 ). When the light transmittance is not deteriorated, the curing of the photocurable resin composition (B) component is sufficient, and as a result, the photocurable resin composition containing the metal fine particles is adhered to the substrate. Sex, and the resolution becomes sufficient.
本發明中之敲緊密度係指,將導電粉充填至容器中 後,進行輕敲(將容器移至上方後,使容器自由落下),破壞導電粉間之空隙,並將導電粉緊密充填時之表觀密度,敲緊密度之測定方法係例如:將導電粉投入並填滿30mL量筒,設在輕敲傳感器後輕敲100次,然後測定導電粉的體積。敲緊密度D[g/cm3]可由量筒內之質量W[g]、輕敲後之體積V[cm3],以下述式(1)求取。 The knocking degree in the present invention means that after the conductive powder is filled into the container, tapping (moving the container to the top and allowing the container to fall freely), breaking the gap between the conductive powders, and filling the conductive powder tightly The apparent density and the knocking degree are measured by, for example, charging a conductive powder and filling a 30 mL measuring cylinder, tapping the sensor 100 times after tapping the sensor, and then measuring the volume of the conductive powder. The knocking degree D [g/cm 3 ] can be obtained by the following formula (1) from the mass W [g] in the measuring cylinder and the volume V [cm 3 ] after tapping.
D=W/V (1) D=W/V (1)
(iii)BET比表面積在1.5m2/g以下(例如:小於1.5m2/g)者即可,以1.3m2/g以下為佳。金屬微粒子之比表面積大時,黏合劑樹脂滲入細孔,此部分即減少密接性賦予作用、感光性改善作用之所謂黏合劑樹脂的作用。本發明中,由於BET比表面積在上述範圍內,將使光硬化性樹脂組成物(B)中無須大量的黏合劑樹脂,其結果,不會使電氣佈線電路圖案的電阻值上升。 (iii) The BET specific surface area is 1.5 m 2 /g or less (for example, less than 1.5 m 2 /g), preferably 1.3 m 2 /g or less. When the specific surface area of the metal fine particles is large, the binder resin penetrates into the pores, and this portion serves as a so-called binder resin which reduces the adhesion imparting action and the photosensitivity improving effect. In the present invention, the BET specific surface area is in the above range, so that a large amount of the binder resin is not required in the photocurable resin composition (B), and as a result, the electric resistance value of the electric wiring circuit pattern is not increased.
BET法係指利用惰性氣體之低溫低濕物理吸附之方法。本發明中之BET比表面積係,在粉體粒子表面使吸附佔有面積之已知分子以液體氮之溫度吸附,由其量以求取試料之比表面積之方法所測定之值。 The BET method refers to a method of low temperature and low humidity physical adsorption using an inert gas. The BET specific surface area in the present invention is a value measured by a method in which a known molecule having an adsorption-occupying area is adsorbed at a temperature of liquid nitrogen on the surface of the powder particle, and the specific surface area of the sample is determined.
具導電性之微粒子(A)的形狀,如為得到目的之導電性者,則無特別限定,惟可列舉如:球狀、碎片狀、粒狀、棒狀、線狀等。其中,在含有金屬微粒子之光硬化性樹脂組成物中之分散性良好之點上,係以粒狀者為佳。 The shape of the conductive fine particles (A) is not particularly limited as long as it is a conductive property for the purpose, and examples thereof include a spherical shape, a chip shape, a granular shape, a rod shape, and a linear shape. Among them, in the case where the dispersibility in the photocurable resin composition containing metal fine particles is good, it is preferred that the particles are in a granular form.
具導電性之微粒子(A)之例可列舉如:金、銀、銅、鉑族金屬等貴金屬,或是鎳、鋁等導電性高的金 屬等單體金屬,或者包含該等單體金屬之合金的微粒子等。並且,單體之金屬微粒子或該等合金的金屬微粒子可組合2種以上使用。其中,因導電性良好,故以金、銀、銅或包含該等之合金的金屬微粒子為佳,以銀或包含銀之合金的金屬微粒子更佳。 Examples of the conductive fine particles (A) include noble metals such as gold, silver, copper, and platinum group metals, and gold having high conductivity such as nickel and aluminum. A monomeric metal such as a genus or a fine particle containing an alloy of the monomeric metals. Further, the metal fine particles of the monomer or the metal fine particles of the alloy may be used in combination of two or more kinds. Among them, since the conductivity is good, it is preferable to use gold, silver, copper or metal fine particles containing the alloy, and metal fine particles of silver or an alloy containing silver are more preferable.
具導電性之微粒子(A)可使用市售者,亦可使用以氣相法或液相化學還原法所製造者。具導電性之微粒子(A)的具體之製造方法可例示如:日本特公昭63-31522號公報所記載之噴霧熱分解法;日本特開2011-12290所記載之金屬氧化物、或金屬氫氧化物照射微波進行加熱、還原之方法;日本特開2010-265543所記載之金屬錯體化合物經熱分解而得還原體之方法;日本特開2010-77472所記載之金屬離子以多元醇還原之方法;日本特開2002-20809號公報所記載之製造方法;以及日本特開2004-99992號公報所記載之製造方法等。 The conductive fine particles (A) can be used commercially, and those produced by a vapor phase method or a liquid phase chemical reduction method can also be used. Specific examples of the production method of the conductive fine particles (A) include a spray pyrolysis method described in Japanese Patent Publication No. Sho 63-31522, and a metal oxide or metal hydroxide described in JP-A-2011-12290. A method of heating and reducing by irradiating a microwave with a microwave; a method of obtaining a reduced body by thermal decomposition of a metal complex compound described in JP-A-2010-265543; and a method for reducing metal ions described in JP-A-2010-77472 The production method described in Japanese Laid-Open Patent Publication No. 2002-20809, and the production method described in JP-A-2004-99992.
本發明中使用之光硬化性樹脂組成物(B)如為經電子束、紫外線、可見光等活化能射線照射而顯現光硬化性者即可使用,並無特別限制。 The photocurable resin composition (B) used in the present invention can be used as long as it exhibits photocurability by irradiation with an active energy ray such as an electron beam, ultraviolet light or visible light, and is not particularly limited.
光硬化性樹脂組成物(B)一般係吸收活化能射線之化合物(例如:下述之黏合劑聚合物(b-1)或聚合性化合物(b-2))如為以單體引起反應而硬化者即可。並且,吸收活化能射線之化合物本身雖不硬化,然光硬化性樹脂組成物中所含的其他化合物(例如:下述之光硬化性起始劑(b-3))如為與吸收活化能射線之化合物作用而硬化者即 可。並且,此時所參與之化合物的種類可為2種以上。可例示例如:如包含聚合性化合物與光聚合起始劑之組成物。 The photocurable resin composition (B) is generally a compound that absorbs an active energy ray (for example, a binder polymer (b-1) or a polymerizable compound (b-2) described below), for example, to cause a reaction by a monomer. Hardened. Further, although the compound which absorbs the active energy ray itself is not hardened, the other compound contained in the photocurable resin composition (for example, the photocurable initiator (b-3) described below) is an absorption activation energy. The compound of the ray acts and hardens can. Further, the types of the compounds involved at this time may be two or more. For example, a composition comprising a polymerizable compound and a photopolymerization initiator may be exemplified.
光硬化性樹脂組成物(B)之較佳者可為包含黏合劑聚合物(b-1)、聚合性化合物(b-2)以及光聚合起始劑(b-3)者。更且,在光硬化性樹脂組成物(B)中,可因應所需而調配溶媒、光聚合起始劑以外之光硬化性樹脂用之添加劑。 The photocurable resin composition (B) may preferably be a binder polymer (b-1), a polymerizable compound (b-2), and a photopolymerization initiator (b-3). In addition, in the photocurable resin composition (B), an additive for a photocurable resin other than a solvent or a photopolymerization initiator may be blended as needed.
黏合劑聚合物(b-1)即使與光硬化性樹脂組成物(B)之其他成分混合,如為不引起分離、沉降、析出等者,並無特別限制而可使用,可維持與基板之密接性者即可適用。例如:基板係使用聚對苯二甲酸乙二酯(PET)膜時,黏合劑聚合物(b-1)如為PET膜之溶解度參數(SP值)具有接近11.3之值者即可,具體上可例示如:(甲基)丙烯酸酯樹脂、環氧樹脂、酚樹脂、聚胺基甲酸酯、聚苯乙烯、乙酸乙烯酯聚合物、聚醯胺、氯乙烯-乙酸乙烯酯共聚物、纖維素二乙酸酯、聚氯乙烯、硝基纖維素以及具有特多龍(tetoron)等之構造的聚合物。其中,以(甲基)丙烯酸酯樹脂、環氧樹脂、纖維素二乙酸酯、聚苯乙烯為佳,以(甲基)丙烯酸酯樹脂、聚苯乙烯更佳。 When the binder polymer (b-1) is mixed with other components of the photocurable resin composition (B), it is not particularly limited and can be used without causing separation, sedimentation, precipitation, etc., and can be maintained with the substrate. Adhesives are available. For example, when the substrate is a polyethylene terephthalate (PET) film, the binder polymer (b-1) may have a solubility parameter (SP value) of the PET film of approximately 11.3, specifically For example, (meth) acrylate resin, epoxy resin, phenol resin, polyurethane, polystyrene, vinyl acetate polymer, polyamine, vinyl chloride-vinyl acetate copolymer, fiber Diacetate, polyvinyl chloride, nitrocellulose, and a polymer having a structure such as tetoron. Among them, (meth) acrylate resin, epoxy resin, cellulose diacetate, and polystyrene are preferred, and (meth) acrylate resin and polystyrene are more preferable.
並且,作為使用光硬化性樹脂組成物(B)之光微影法之顯影液,一般係使用金屬鹼水溶液及有機鹼水溶液等鹼性之溶液。因此,經活化能射線而硬化後之顯影處理中的解析度優異之黏合劑聚合物(b-1)係以鹼可溶 性樹脂為佳,例如可使用分子中具有羧基或磺基等之鹼可溶性之黏合劑聚合物。鹼可溶性之黏合劑聚合物可例示如:具有1個以上之羧基的乙烯性不飽和單體經聚合而成之均聚物或共聚物,或具有1個以上之羧基的乙烯性不飽和單體及可與其共聚之乙烯性不飽和單體經聚合而成之共聚物等。 In addition, as a developing solution of the photolithography method using the photocurable resin composition (B), an alkaline solution such as a metal alkali aqueous solution or an organic alkali aqueous solution is generally used. Therefore, the binder polymer (b-1) excellent in resolution in the development treatment after hardening by activation of energy rays is soluble in alkali The resin is preferably used, and for example, an alkali-soluble binder polymer having a carboxyl group or a sulfo group in the molecule can be used. The alkali-soluble binder polymer may, for example, be a homopolymer or a copolymer obtained by polymerizing an ethylenically unsaturated monomer having one or more carboxyl groups, or an ethylenically unsaturated monomer having one or more carboxyl groups. And a copolymer obtained by polymerizing an ethylenically unsaturated monomer copolymerizable therewith.
具有1個以上之羧基的乙烯性不飽和單體可例示如:(甲基)丙烯酸、桂皮酸、富馬酸、伊康酸、巴豆酸、乙烯乙酸以及馬來酸等,其中以(甲基)丙烯酸為佳。黏合劑聚合物(b-1)可使用該等單體之1種或2種以上經聚合之聚合物。 The ethylenically unsaturated monomer having one or more carboxyl groups may, for example, be (meth)acrylic acid, cinnamic acid, fumaric acid, itaconic acid, crotonic acid, ethylene acetic acid, maleic acid, etc., wherein (methyl) ) Acrylic is preferred. As the binder polymer (b-1), one type or two or more types of polymerized polymers of these monomers can be used.
可與具有1個以上之羧基的乙烯性不飽和單體共聚之乙烯性不飽和單體可例示如:(甲基)丙烯酸酯系不飽和單體、乙二醇酯系(甲基)丙烯酸酯、丙二醇系(甲基)丙烯酸酯、丁二醇系單(甲基)丙烯酸酯、甘油單(甲基)丙烯酸酯、(甲基)丙烯醯胺不飽和單體、N-取代馬來醯亞胺等。 The ethylenically unsaturated monomer copolymerizable with the ethylenically unsaturated monomer having one or more carboxy groups may, for example, be a (meth) acrylate-based unsaturated monomer or a glycol ester-based (meth) acrylate. , propylene glycol (meth) acrylate, butane diol mono (meth) acrylate, glycerol mono (meth) acrylate, (meth) acrylamide unsaturated monomer, N-substituted Malayan Amines, etc.
可與具有1個以上之羧基的乙烯性不飽和單體共聚之乙烯性不飽和單體之具體例可例示如:(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸異丁酯、(甲基)丙烯酸環己酯、(甲基)丙烯酸羥基乙酯、(甲基)丙烯酸甲氧基乙酯、(甲基)丙烯酸乙氧基乙酯、(甲基)丙烯醯胺、N-甲基(甲基)丙烯醯胺、N-環己基馬來醯亞胺等。並且,可例示如:苯乙烯、α-甲基苯乙烯、乙烯基醚、乙烯基吡咯啶酮、(甲基)丙烯腈等。 Specific examples of the ethylenically unsaturated monomer copolymerizable with the ethylenically unsaturated monomer having one or more carboxyl groups may, for example, be methyl (meth)acrylate, ethyl (meth)acrylate, or (methyl). Isobutyl acrylate, cyclohexyl (meth) acrylate, hydroxyethyl (meth) acrylate, methoxyethyl (meth) acrylate, ethoxyethyl (meth) acrylate, (meth) propylene Indoleamine, N-methyl(meth)acrylamide, N-cyclohexylmaleimide, and the like. Further, examples thereof include styrene, α-methylstyrene, vinyl ether, vinylpyrrolidone, and (meth)acrylonitrile.
又,黏合劑聚合物(b-1)係可使用:藉由將1種或2種以上之具有1個以上之羧基的乙烯性不飽和單體、及可與其共聚的1種或2種以上之乙烯性不飽和單體組合後使共聚而得之共聚物。 In addition, one or two or more kinds of ethylenically unsaturated monomers having one or more carboxyl groups and one or more types copolymerizable therewith can be used as the binder polymer (b-1). The copolymer obtained by copolymerizing the ethylenically unsaturated monomers.
在得到共聚物時之反應條件及各單體成分之組成比,可依目的之黏合劑聚合物(b-1)的物性(數量平均分子量、玻璃轉移溫度等)而適當地選擇。 The reaction conditions and the composition ratio of each monomer component in the case of obtaining a copolymer can be appropriately selected depending on the physical properties (number average molecular weight, glass transition temperature, and the like) of the binder polymer (b-1).
黏合劑聚合物(b-1)亦可使用經活化能射線照射使光二聚化反應等而交聯之聚合物。如此聚合物之例可例示如:具有桂皮酸骨架、馬來醯亞胺骨架、苯乙烯骨架、蒽骨架或吡骨架等之聚合物,具體上可例示如:聚桂皮酸乙烯酯、具有馬來醯亞胺骨架之聚合物的Aronix UVT-302(東亞合成)等。 The binder polymer (b-1) may also be a polymer which is crosslinked by photodimerization reaction or the like by irradiation with an active energy ray. Examples of such a polymer can be exemplified by having a cinnamic acid skeleton, a maleimine skeleton, a styrene skeleton, an anthracene skeleton or a pyridyl group. Specific examples of the polymer such as a skeleton include Aronix UVT-302 (East Asia Synthetic) having a polymer of a polyethyl cinnamate and a polymer having a maleic imine skeleton.
本發明之光硬化性樹脂組成物(B)中使用的黏合劑聚合物(b-1),由於顯影性、及所形成之電路圖案與基板間之密接性等的性能之平衡良好,因此,數量平均分子量以約2,000至500,000之範圍者為佳,以約4,000至100,000之範圍者為特佳。 The binder polymer (b-1) used in the photocurable resin composition (B) of the present invention has a good balance between developability and adhesion between the formed circuit pattern and the substrate. The number average molecular weight is preferably in the range of about 2,000 to 500,000, and particularly preferably in the range of about 4,000 to 100,000.
光硬化性樹脂組成物(B)中之黏合劑聚合物(b-1)的使用量,相對於光硬化性樹脂組成物(B)之總量,例如約為20至65重量%之範圍即可。 The amount of the binder polymer (b-1) used in the photocurable resin composition (B) is, for example, about 20 to 65 wt%, based on the total amount of the photocurable resin composition (B). can.
聚合性化合物(b-2)係可例示自由基聚合性化合物,其中,由反應性高、可提高樹脂組成物對光的感度之點上,以多官能(甲基)丙烯酸酯化合物為佳。具體上可例 示如:聚乙二醇二(甲基)丙烯酸酯(伸乙基之數為2至14者)、三羥甲基丙烷二(甲基)丙烯酸酯、三羥甲基丙烷三(甲基)丙烯酸酯、二-三羥甲基丙烷四(甲基)丙烯酸酯、三羥甲基丙烷乙氧基三(甲基)丙烯酸酯、三羥甲基丙烷丙氧基三(甲基)丙烯酸酯、三羥甲基丙烷乙二醇加成物三丙烯酸酯、四羥甲基甲烷三(甲基)丙烯酸酯、四羥甲基甲烷四(甲基)丙烯酸酯、聚丙二醇二(甲基)丙烯酸酯(伸丙基之數為2至14者)、新戊四醇三(甲基)丙烯酸酯、新戊四醇四(甲基)丙烯酸酯、二新戊四醇五(甲基)丙烯酸酯、二新戊四醇六(甲基)丙烯酸酯等,其中,以聚乙二醇二(甲基)丙烯酸酯(伸乙基之數為2至14者)、三羥甲基丙烷三(甲基)丙烯酸酯、三羥甲基丙烷乙二醇加成物三丙烯酸酯、新戊四醇三(甲基)丙烯酸酯為佳。 The polymerizable compound (b-2) is exemplified by a radical polymerizable compound, and a polyfunctional (meth) acrylate compound is preferred because it has high reactivity and can improve the sensitivity of the resin composition to light. Specific examples Such as: polyethylene glycol di (meth) acrylate (extension of the number of 2 to 14), trimethylolpropane di (meth) acrylate, trimethylolpropane tri (methyl) Acrylate, di-trimethylolpropane tetra(meth)acrylate, trimethylolpropane ethoxy tris(meth)acrylate, trimethylolpropane propoxytri(meth)acrylate, Trimethylolpropane ethylene glycol adduct triacrylate, tetramethylol methane tri(meth)acrylate, tetramethylol methane tetra(meth)acrylate, polypropylene glycol di(meth)acrylate (the number of propyl groups is 2 to 14), neopentyl alcohol tri (meth) acrylate, neopentyl alcohol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, Dipentaerythritol hexa(meth) acrylate, etc., wherein polyethylene glycol di(meth)acrylate (the number of ethyl groups is 2 to 14), trimethylolpropane tris(methyl) Acrylate, trimethylolpropane ethylene glycol adduct triacrylate, and neopentyl alcohol tri(meth)acrylate are preferred.
聚合性化合物(b-2)可單獨使用,或將2種以上適當地組合使用。 The polymerizable compound (b-2) may be used singly or in combination of two or more kinds as appropriate.
並且,光硬化性樹脂組成物(B)中之聚合性化合物(b-2)的使用量,相對於光硬化性樹脂組成物(B)中所含的黏合劑聚合物(b-1)100重量份,如在約10至150重量份之範圍即可,以約15至65重量份之範圍更佳。 In addition, the amount of the polymerizable compound (b-2) used in the photocurable resin composition (B) is 100% with respect to the binder polymer (b-1) contained in the photocurable resin composition (B). The parts by weight may be in the range of about 10 to 150 parts by weight, more preferably in the range of about 15 to 65 parts by weight.
光聚合起始劑(b-3)如為在活化能射線之波長具有吸收帶,且生成硬化(聚合)反應之起始種者,即可使用而無特別限制。通常,硬化反應中使用之活化能射線方面,從成本面而言,以紫外線為適用。因此,光聚合起始劑之種類豐富,以與單體之反應性優異的光自由基聚合 起始劑為佳。 The photopolymerization initiator (b-3) is used as it is an initiator having an absorption band at the wavelength of the active energy ray and generates a hardening (polymerization) reaction, and is not particularly limited. Generally, in terms of the active energy ray used in the hardening reaction, ultraviolet rays are suitable from the viewpoint of cost. Therefore, the photopolymerization initiator is abundant in kind, and photo-radical polymerization excellent in reactivity with a monomer is obtained. The initiator is preferred.
光自由基聚合起始劑之具體例可例示如:苯偶姻、苯乙酮、2-甲基蒽醌、2,4-二甲基硫雜蒽酮、2,4-二乙基硫雜蒽酮、2-異丙基硫雜蒽酮、4-異丙基硫雜蒽酮、2,4-二異丙基硫雜蒽酮、二苯基酮、4-苄醯基-4’-甲基二苯基硫醚、2,4-二異丙基氧蔥酮、2-羥基-2-甲基-1-苯基-丙烷-1-酮、2,2-二甲氧基-1,2-二苯基乙烷-1-酮、1-羥基-環己基-苯基-酮、2-羥基-2-甲基-1-苯基-丙烷-1-酮、1-[4-(2-羥基乙氧基)-苯基]-2-羥基-2-甲基-1-丙烷-1-酮、2-羥基-1-[4-[4-(2-羥基-2-甲基-丙醯基)-苄基]苯基]-2-甲基-丙烷-1-酮、2-甲基-1-(4-甲基硫苯基)-2-啉基丙烷-1-酮、2-苄基-2-二甲基胺基-1-(4-啉基苯基)-丁酮-1,2-(二甲基胺基)-2-[(4-甲基苯基)甲基]-1-[4-(4-啉基)苯基]-1-丁酮、2,4,6-三甲基苄醯基-二苯基膦氧化物、雙(2,4,6-三甲基苄醯基)-苯基膦氧化物、1,2-辛烷二酮,1-[4-(苯硫基)-,2-(O-苄醯基肟)、乙酮,1-[9-乙基-6-(2-甲基苄醯基)-9H-咔唑-3-基]-,1-(O-乙醯基肟)等。其中在對光之感度優異之點上,係以2,4,6-三甲基苄醯基-二苯基膦氧化物、雙(2,4,6-三甲基苄醯基)-苯基膦氧化物、1,2-辛烷二酮,1-[4-(苯硫基)-,2-(O-苄醯基肟)、乙酮,1-[9-乙基-6-(2-甲基苄醯基)-9H-咔唑-3-基]-,1-(O-乙醯基肟)為佳,以1,2-辛烷二酮,1-[4-(苯硫基)-,2-(O-苄醯基肟)、乙酮,1-[9-乙基-6-(2-甲基苄醯基)-9H-咔唑-3-基]-,1-(O-乙醯基肟)更佳。 Specific examples of the photoradical polymerization initiator may, for example, be benzoin, acetophenone, 2-methylhydrazine, 2,4-dimethylthiaxanone, 2,4-diethylthiazepine Anthrone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diisopropylthiaxanone, diphenylketone, 4-benzylindolyl-4'- Methyl diphenyl sulfide, 2,4-diisopropyloxene, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 2,2-dimethoxy-1 , 2-diphenylethane-1-one, 1-hydroxy-cyclohexyl-phenyl-one, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 1-[4- (2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1-[4-[4-(2-hydroxy-2-methyl) -Benzyl)-benzyl]phenyl]-2-methyl-propan-1-one, 2-methyl-1-(4-methylthiophenyl)-2- Lolinylpropan-1-one, 2-benzyl-2-dimethylamino-1-(4- Phenylphenyl)-butanone-1,2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4- Phenyl)phenyl]-1-butanone, 2,4,6-trimethylbenzylidene-diphenylphosphine oxide, bis(2,4,6-trimethylbenzylidene)-phenyl Phosphonium oxide, 1,2-octanedione, 1-[4-(phenylthio)-, 2-(O-benzylindenyl), ethyl ketone, 1-[9-ethyl-6-( 2-methylbenzylindenyl)-9H-indazol-3-yl]-, 1-(O-ethenylhydrazine) and the like. Among them, in the point of sensitivity to light, 2,4,6-trimethylbenzylidene-diphenylphosphine oxide, bis(2,4,6-trimethylbenzylidene)-benzene Phosphine oxide, 1,2-octanedione, 1-[4-(phenylthio)-, 2-(O-benzylindenyl), ethyl ketone, 1-[9-ethyl-6- (2-methylbenzylindenyl)-9H-indazol-3-yl]-, 1-(O-ethylindenyl) is preferred as 1,2-octanedione, 1-[4-( Phenylthio)-, 2-(O-benzylindolyl), ethyl ketone, 1-[9-ethyl-6-(2-methylbenzyl)-9H-indazol-3-yl]- , 1-(O-ethinyl) is more preferred.
並且,黏合劑聚合物(b-1)在使用鹼可溶性樹 脂時,作為光聚合起始劑(b-3)係以使用具有O-醯基肟構造之光聚合起始劑者為佳。 Also, the binder polymer (b-1) is using an alkali soluble tree In the case of a fat, the photopolymerization initiator (b-3) is preferably a photopolymerization initiator having an O-fluorenylfluorene structure.
光硬化性樹脂組成物(B)中之光聚合起始劑(b-3)的使用量,相對於光硬化性樹脂組成物(B)中所含的黏合劑聚合物(b-1)100重量份,如在約1至20重量份之範圍即可,以約2至15重量份之範圍更佳。 The photopolymerization initiator (b-3) used in the photocurable resin composition (B) is used in an amount relative to the binder polymer (b-1) 100 contained in the photocurable resin composition (B). The parts by weight may be in the range of about 1 to 20 parts by weight, more preferably in the range of about 2 to 15 parts by weight.
本發明之光硬化性樹脂組成物(B)中,因應所需,在不影響本發明之效果的範圍內,可添加溶劑、阻聚劑、光聚合促進劑、增敏劑等之光硬化性樹脂組成物用的添加劑。 In the photocurable resin composition (B) of the present invention, photocuring properties such as a solvent, a polymerization inhibitor, a photopolymerization accelerator, and a sensitizer can be added as long as the effects of the present invention are not affected. An additive for a resin composition.
本發明之光硬化性樹脂組成物(B)可因應所需而含有溶媒。溶媒如為可溶解光硬化性樹脂組成物(B)中之黏合劑聚合物(b-1)、聚合性化合物(b-2)、光聚合起始劑(b-3)之液體介質即可使用而無特別限制。而且,光硬化性樹脂組成物(B)中之各成分,不一定必需完全溶解於溶媒中,以本發明之光硬化性樹脂組成物(B)為整體,如為可均一地分散或可維持溶解的狀態之溶媒即可,不一定須有使上述全部成分溶解之能力。 The photocurable resin composition (B) of the present invention may contain a solvent as needed. The solvent is, for example, a liquid medium of the binder polymer (b-1), the polymerizable compound (b-2), and the photopolymerization initiator (b-3) in the photocurable resin composition (B). Use without special restrictions. Further, each component in the photocurable resin composition (B) does not necessarily have to be completely dissolved in the solvent, and the photocurable resin composition (B) of the present invention as a whole may be uniformly dispersed or maintained. The solvent in a dissolved state may not necessarily have the ability to dissolve all of the above components.
本發明中使用之溶媒之例可例示如:乙醇、丙醇、異丙醇、丁醇、異丁醇、2-丁醇、己醇、乙二醇等之直鏈、分支、二級或多元醇類;甲基乙基酮、環己酮、異佛酮等之酮類;甲苯、二甲苯等芳香族烴類;Swasol系列(丸善石油化學公司製造)、Solvesso系列(Exxon化學 公司製造)等石油系芳香族系混合溶劑、溶纖素、丁基溶纖素等溶纖素類;卡必醇、乙基卡必醇、丁基卡必醇等卡必醇類;丙二醇單甲醚、丙二醇二甲醚等丙二醇烷基醚類;二丙二醇單甲醚、二丙二醇二甲醚等聚丙二醇烷基醚類;乙酸乙酯、乙酸丁酯、溶纖素乙酸酯、丁基溶纖素乙酸酯、丁基卡必醇乙酸酯、丙二醇單甲醚乙酸酯等乙酸酯類;N-甲基吡咯啶酮以及二烷二醇醚類等。 The solvent used in the present invention may, for example, be linear, branched, secondary or plural such as ethanol, propanol, isopropanol, butanol, isobutanol, 2-butanol, hexanol or ethylene glycol. Alcohols; ketones such as methyl ethyl ketone, cyclohexanone, isophorone; aromatic hydrocarbons such as toluene and xylene; Swasol series (made by Maruzen Petrochemical Co., Ltd.), Solvesso series (Exxon chemistry) Company-made) petroleum-based aromatic mixed solvents, cellosolve such as cellosolve and butyl cellosolve; carbitol such as carbitol, ethyl carbitol, butyl carbitol, propylene glycol monomethyl ether Propylene glycol alkyl ethers such as propylene glycol dimethyl ether; polypropylene glycol alkyl ethers such as dipropylene glycol monomethyl ether and dipropylene glycol dimethyl ether; ethyl acetate, butyl acetate, fibrin acetate, butyl cellulolytic B Acetate such as acid ester, butyl carbitol acetate or propylene glycol monomethyl ether acetate; N-methylpyrrolidone and dialkyl glycol ether.
溶媒可單獨使用,亦可將2種以上適當地組合使用。 The solvent may be used singly or in combination of two or more kinds as appropriate.
光硬化性樹脂組成物(B)中之溶媒的使用量,可適當地調製使含有金屬微粒子之光硬化性樹脂組成物的黏度成為約10至1000dpa.S之範圍即可,以調製成為約100至500dpa.S之範圍為佳。 The amount of the solvent used in the photocurable resin composition (B) can be appropriately adjusted so that the viscosity of the photocurable resin composition containing the metal fine particles is about 10 to 1000 dpa. The range of S can be adjusted to be about 100 to 500 dpa. The range of S is better.
本發明之電氣佈線電路圖案之製造方法係包含:使用上述說明的本發明之含有金屬微粒子之光硬化性樹脂組成物,在基板上形成電氣電路圖案之步驟的方法,係可例示包含下述步驟之方法:上述說明的本發明之含有金屬微粒子之光硬化性樹脂組成物的調製方法;基板上塗布上述含有金屬微粒子之光硬化性樹脂組成物之步驟(塗布步驟);隔著應形成之電氣佈線電路圖案所對應的膜或遮罩,對塗布在基板上之含有金屬微粒子之光硬化性樹脂組成物的塗膜照射活化能射線使塗膜硬化之步驟(曝光步驟);將上述基板上之未曝光部分以顯影液溶解、去除並乾燥之步驟(顯影步驟)。 The method for producing an electric wiring circuit pattern according to the present invention includes the step of forming an electric circuit pattern on a substrate by using the photocurable resin composition containing metal fine particles of the present invention described above, and the method includes the following steps Method for preparing a photocurable resin composition containing metal fine particles of the present invention described above; a step of applying the photocurable resin composition containing metal fine particles on a substrate (coating step); a film or a mask corresponding to the wiring circuit pattern, a step of irradiating the coating film of the photocurable resin composition containing the metal fine particles coated on the substrate with an active energy ray to cure the coating film (exposure step); The unexposed portion is a step of dissolving, removing, and drying the developing solution (developing step).
本發明之含有金屬微粒子之光硬化性樹脂組 成物的調製步驟中,具導電性之微粒子(A)、光硬化性樹脂組成物(B)以及因應所需而添加之其他成分的混合或混練方法,係以將各成分在含有金屬微粒子之光硬化性樹脂組成物中均一分散並混合之方法即可進行,而無特別限定。如此之方法,可例示使用如:機械攪拌器、磁攪拌器、超音波分散機、行星式軋機、球磨機或三輥研磨機等之方法。由操作容易之點,以使用行星式軋機之方法為佳,由可均一分散之點,以使用三輥研磨機之方法為佳,亦可組合2種以上之方法。 Photocurable resin group containing metal microparticles of the present invention In the preparation step of the product, the method of mixing or kneading the conductive fine particles (A), the photocurable resin composition (B), and other components added as needed is to contain the respective components in the metal microparticles. The method of uniformly dispersing and mixing the photocurable resin composition can be carried out without particular limitation. In such a method, a method such as a mechanical stirrer, a magnetic stirrer, an ultrasonic disperser, a planetary mill, a ball mill or a three-roll mill can be exemplified. It is preferable to use a planetary rolling mill from the point of easy operation, and it is preferable to use a three-roll mill by a point which can be uniformly dispersed, or a combination of two or more methods.
並且,亦可將光硬化性樹脂組成物(B)另行調製者、與具導電性之微粒子(A)以及其他成分混合而調製含有金屬微粒子之光硬化性樹脂組成物,亦可將具導電性之微粒子(A)、光硬化性樹脂組成物(B)及其他成分同時混合而調製含有金屬微粒子之光硬化性樹脂組成物。 In addition, the photocurable resin composition (B) may be separately prepared, mixed with the conductive fine particles (A) and other components to prepare a photocurable resin composition containing metal fine particles, or may be electrically conductive. The fine particles (A), the photocurable resin composition (B), and other components are simultaneously mixed to prepare a photocurable resin composition containing metal fine particles.
塗布步驟係將上述調製步驟中所調製之含有金屬微粒子之光硬化性樹脂組成物以網版印刷法、棒塗布或刮刀塗布等之塗布方法,塗布在玻璃基板、陶瓷基板或膜狀樹脂基板等並使之乾燥。 In the coating step, the photocurable resin composition containing the metal fine particles prepared in the above-described preparation step is applied to a glass substrate, a ceramic substrate, a film-like resin substrate, or the like by a coating method such as screen printing, bar coating or blade coating. And let it dry.
本發明之方法係,即使使用耐熱性低的膜狀樹脂基板,亦可形成高導電性、高密接性以及高精密之電路圖案,因此可適用膜狀樹脂基板。膜狀樹脂基板之例可例示如:聚對苯二甲酸乙二酯(PET)、聚碳酸酯(PC)、聚苯乙烯(PS)、聚二氯乙烯(PVDC)等之耐熱性低的基板,以電路圖案之密接性良好之觀點,可適用基板表面易於接著處理者。並且,亦可使用薄膜上披覆有ITO(氧化銦錫) 、ZnO(氧化鋅)或銀奈米線而成之透明導電膜。 In the method of the present invention, even if a film-like resin substrate having low heat resistance is used, a circuit pattern having high conductivity, high adhesion, and high precision can be formed. Therefore, a film-shaped resin substrate can be applied. Examples of the film-like resin substrate include a substrate having low heat resistance such as polyethylene terephthalate (PET), polycarbonate (PC), polystyrene (PS), or polyvinylidene chloride (PVDC). From the viewpoint of good adhesion of circuit patterns, it is possible to apply a substrate surface to facilitate handling. Also, the film may be coated with ITO (indium tin oxide) A transparent conductive film made of ZnO (zinc oxide) or silver nanowire.
塗布步驟中,可將乾燥溫度約設在60至120℃,乾燥時間約設在5至60分鐘左右。 In the coating step, the drying temperature can be set to about 60 to 120 ° C, and the drying time is set to about 5 to 60 minutes.
基板上之塗膜的厚度並無特別限制,以約1至30μm(例如:大於1μm且小於30μm)為佳,以約5至15μm(例如:大於5μm且小於15μm)更佳。 The thickness of the coating film on the substrate is not particularly limited, and is preferably about 1 to 30 μm (for example, more than 1 μm and less than 30 μm), more preferably about 5 to 15 μm (for example, more than 5 μm and less than 15 μm).
曝光步驟中,隔著應形成之電氣佈線電路圖案所對應的膜或遮罩,對塗布在基板上之塗膜照射活化能射線使照射部硬化。所照射之活化能射線可例示如:紫外線、電子束以及X射線等,其中以紫外線為佳。光源係可使用:低壓汞燈、高壓汞燈、超高壓汞燈、鹵素燈以及黑光燈等。並且,曝光方式可例示如:與遮罩之密接曝光、接近式曝光以及投影曝光等。 In the exposure step, the coating film coated on the substrate is irradiated with an active energy ray to cure the irradiated portion via a film or a mask corresponding to the electrical wiring circuit pattern to be formed. The active energy ray to be irradiated can be exemplified by ultraviolet rays, electron beams, and X-rays, and among them, ultraviolet rays are preferred. The light source can be used: low-pressure mercury lamps, high-pressure mercury lamps, ultra-high pressure mercury lamps, halogen lamps, and black lamps. Further, the exposure method can be exemplified by adhesion exposure to a mask, proximity exposure, projection exposure, or the like.
顯影步驟係在使用顯影液,使未硬化之未曝光部分溶解、去除,即可得到目的之電氣佈線電路圖案。 The development step is to obtain a desired electrical wiring circuit pattern by using a developing solution to dissolve and remove the unhardened unexposed portion.
顯影液方面,可使本發明之含有金屬微粒子之光硬化性樹脂組成物的未曝光部分溶化者即可使用,並無特別限制。所使用之顯影液可為水性或油性之任一者,無關液體的pH。例如:光硬化性樹脂組成物(B)中存在具酸性基之化合物時,除了氫氧化鈉及碳酸鈉等金屬鹼水溶液以外,亦可使用單乙醇胺以及二乙醇胺等之有機鹼水溶液等。並且,「顯影」之原本目的係將含有金屬微粒子之光硬化性樹脂組成物的未曝光部分從基板上去除,因此,此處所謂之可溶非指使含有金屬微粒子之光硬化 性樹脂組成物全部溶解為止之意,可去除未曝光部分之程度而溶化構成含有金屬微粒子之光硬化性樹脂組成物之至少1個成分者即可。 In the case of the developer, the unexposed portion of the photocurable resin composition containing the metal fine particles of the present invention can be used without being particularly limited. The developer used may be either aqueous or oily, regardless of the pH of the liquid. For example, when a compound having an acidic group is present in the photocurable resin composition (B), an aqueous solution of an organic alkali such as monoethanolamine or diethanolamine may be used in addition to a metal alkali aqueous solution such as sodium hydroxide or sodium carbonate. Further, the original purpose of "development" is to remove the unexposed portion of the photocurable resin composition containing the metal fine particles from the substrate. Therefore, the so-called soluble non-finishing means hardening the light containing the metal fine particles. It is sufficient that all of the resin composition is dissolved, and at least one component constituting the photocurable resin composition containing the metal fine particles can be melted to the extent that the unexposed portion is removed.
顯影步驟中之顯影方式,如為一般光微影法所使用之顯影方式即可使用,並無特別限制。具體上可例示如:將形成有硬化塗膜之基板浸漬在顯影液之浸泡方式、在該基板全面噴上顯影液之噴霧方式、在容器內裝入顯影液與該基板進行處理之轉筒方式等。顯影方式可因應所使用之含有金屬微粒子之光硬化性樹脂組成物的性質而適當地決定。並且,顯影方式雖依形成電路之基板的形狀等而異,惟在去除基板上不必要的塗膜(未曝光部分)時,以噴霧方式將塗膜附著面以均一壓力流洗之方法,因可提升解析度而佳。 The developing method in the developing step can be used as the developing method used in the general photolithography method, and is not particularly limited. Specifically, for example, a method of immersing a substrate on which a cured coating film is formed in a developing solution, a spraying method in which a developing solution is sprayed on the substrate, a developing solution in which a developing solution is filled in the container, and a rotating method in which the substrate is processed can be exemplified. Wait. The development method can be appropriately determined depending on the properties of the photocurable resin composition containing metal fine particles used. Further, the development method differs depending on the shape of the substrate on which the circuit is formed, etc., but when the unnecessary coating film (unexposed portion) on the substrate is removed, the coating film adhesion surface is sprayed at a uniform pressure by spraying. Can improve the resolution and better.
為了去除不必要之顯影液而進行水洗或酸中和後,將電氣佈線電路圖案進行乾燥。乾燥溫度可設在約40至70℃,乾燥時間可設在約5至30分鐘。並且,為了進一步提高電氣佈線電路圖案與基板間之密接力,可依所需在顯影步驟後進行後烘。此時之溫度可設在約100至150℃,時間可設在約5至100分鐘。 The electric wiring circuit pattern is dried after water washing or acid neutralization in order to remove unnecessary developing solution. The drying temperature can be set at about 40 to 70 ° C, and the drying time can be set at about 5 to 30 minutes. Further, in order to further improve the adhesion between the electrical wiring circuit pattern and the substrate, post-baking may be performed after the development step as needed. The temperature at this time may be set at about 100 to 150 ° C, and the time may be set at about 5 to 100 minutes.
經上述步驟後,使用本發明之含有金屬微粒子之光硬化性樹脂組成物,即可在各種基板上形成電氣佈線電路圖案。 After the above steps, the electrical wiring circuit pattern can be formed on various substrates by using the photocurable resin composition containing metal fine particles of the present invention.
由上述說明之本發明的電氣佈線電路圖案之製造方法,可製造觸控面板用基板、顯示裝置用基板、資訊處理終端裝置用基板等之電氣佈線電路基板。 According to the method of manufacturing the electrical wiring circuit pattern of the present invention described above, an electrical wiring circuit board such as a substrate for a touch panel, a substrate for a display device, or a substrate for an information processing terminal device can be manufactured.
以下,本發明以實施例進一步具體說明。惟本發明並不僅限於此。 Hereinafter, the present invention will be further specifically described by way of examples. However, the invention is not limited to this.
下述實施例及比較例中使用之材料說明如下。 The materials used in the following examples and comparative examples are explained below.
金屬微粒子M1:銀微粒子(粒狀;50%平均粒徑0.7μm、敲緊密度1.4g/cm3、BET比表面積1.3m2/g) Metal microparticles M1: silver microparticles (granular; 50% average particle diameter 0.7 μm, knock tightness 1.4 g/cm 3 , BET specific surface area 1.3 m 2 /g)
金屬微粒子M2:銀微粒子(粒狀;50%平均粒徑0.4μm、敲緊密度1.8g/cm3、BET比表面積0.9m2/g) Metal microparticles M2: silver microparticles (granular; 50% average particle diameter 0.4 μm, knock tightness 1.8 g/cm 3 , BET specific surface area 0.9 m 2 /g)
金屬微粒子M3:銀微粒子(碎片狀;50%平均粒徑3.0μm、敲緊密度2.9g/cm3、BET比表面積0.9m2/g) Metal microparticles M3: silver microparticles (fragmented; 50% average particle diameter 3.0 μm, knock tightness 2.9 g/cm 3 , BET specific surface area 0.9 m 2 /g)
金屬微粒子M4:銀微粒子(球狀;50%平均粒徑2.7μm、敲緊密度4.4g/cm3、BET比表面積0.4m2/g) Metal microparticles M4: silver microparticles (spherical; 50% average particle diameter 2.7 μm, knock tightness 4.4 g/cm 3 , BET specific surface area 0.4 m 2 /g)
金屬微粒子M5:銀微粒子(粒狀;50%平均粒徑0.9μm、敲緊密度1.5g/cm3、BET比表面積1.8m2/g) Metal microparticles M5: silver microparticles (granular; 50% average particle diameter 0.9 μm, knock tightness 1.5 g/cm 3 , BET specific surface area 1.8 m 2 /g)
金屬微粒子M6:銀微粒子(碎片狀;50%平均粒徑7.6μm、敲緊密度5.5g/cm3、BET比表面積0.4m2/g) Metal microparticles M6: silver microparticles (fragmented; 50% average particle diameter 7.6 μm, knock tightness 5.5 g/cm 3 , BET specific surface area 0.4 m 2 /g)
上述金屬微粒子之50%平均粒徑係以(微型追蹤法)測定之值,敲緊密度及BET比表面積係以上述方法所測定之值。 The 50% average particle diameter of the above metal fine particles is a value measured by (micro tracking method), and the knocking degree and the BET specific surface area are values measured by the above method.
黏合劑聚合物P1:丙烯酸聚合物AA-6(數量平均分子量 6,000;東亞合成股份有限公司製造) Adhesive polymer P1: acrylic polymer AA-6 (quantitative average molecular weight) 6,000; manufactured by East Asia Synthetic Co., Ltd.)
黏合劑聚合物P2:丙烯酸聚合物AS-6(數量平均分子量6,000;東亞合成股份有限公司製造) Adhesive polymer P2: Acrylic polymer AS-6 (quantitative average molecular weight 6,000; manufactured by Toagosei Co., Ltd.)
聚合性化合物R1:A-200(聚乙二醇#200二丙烯酸酯;新中村化學工業製造) Polymerizable compound R1: A-200 (polyethylene glycol #200 diacrylate; manufactured by Shin-Nakamura Chemical Industry Co., Ltd.)
聚合性化合物R2:Light Acrylate PE3A(新戊四醇三(甲基)丙烯酸酯;共榮社化學製造) Polymerizable compound R2: Light Acrylate PE3A (neopentitol tris(meth)acrylate; manufactured by Kyoeisha Chemical Co., Ltd.)
光聚合起始劑I1:雙(2,4,6-三甲基苄醯基)-苯基膦氧化物(BASF公司製造) Photopolymerization initiator I1: bis(2,4,6-trimethylbenzylidene)-phenylphosphine oxide (manufactured by BASF Corporation)
光聚合起始劑I2:乙酮,1-[9-乙基-6-(2-甲基苄醯基)-9H-咔唑-3-基]-,1-(O-乙醯基肟)(BASF公司製造) Photopolymerization initiator I2: ethyl ketone, 1-[9-ethyl-6-(2-methylbenzyl)-9H-indazol-3-yl]-, 1-(O-ethylindenyl) ) (manufactured by BASF)
溶劑S1:丙二醇單甲醚(和光純藥工業股份有限公司製造) Solvent S1: propylene glycol monomethyl ether (manufactured by Wako Pure Chemical Industries Co., Ltd.)
實施例中使用之含有金屬微粒子之光硬化性樹脂組成物的組成係如表1所示,比較例中使用之含有金屬微粒子之光硬化性樹脂組成物的組成係如表2所示。另外,表1及表2中之數值係表示相對於組成物之總量的各成分之比率(重量%)。 The composition of the photocurable resin composition containing metal fine particles used in the examples is shown in Table 1, and the composition of the photocurable resin composition containing metal fine particles used in the comparative examples is shown in Table 2. Further, the numerical values in Tables 1 and 2 indicate the ratio (% by weight) of each component with respect to the total amount of the composition.
依照表1、表2所示之組成,使含有金屬微粒子之光硬化性樹脂組成物之重量的總和成為50g之方式,分別秤取各成分,將此首先以行星式軋機(Thinky製造之Awatorinentaro AR-100),共進行5分鐘之混練。此時,每隔1分鐘停止混練,使含有金屬微粒子之光硬化性樹脂 組成物不致過熱。接著,將此以三輥研磨機混練,製成膏狀之含有金屬微粒子之光硬化性樹脂組成物。 In the composition shown in Tables 1 and 2, the total weight of the photocurable resin composition containing the metal fine particles was 50 g, and the components were weighed separately. First, the planetary mill (Awatorinentaro AR manufactured by Thinky) was used. -100), a total of 5 minutes of mixing. At this time, the kneading is stopped every 1 minute to form a photocurable resin containing metal fine particles. The composition does not overheat. Then, this was kneaded by a three-roll mill to prepare a paste-like photocurable resin composition containing metal fine particles.
以厚度100μm之單面經易接著處理的PET膜(帝人杜邦薄膜股份有限公司製造03)作為基板,將上述含有金屬微粒子之光硬化性樹脂組成物以網版印刷法均一地塗布在該處理面側之表面,在80℃下乾燥10分鐘,得到10μm厚度的塗膜。接著,使描繪有列間距(line space)為50/50(μm)之細線圖案的光罩與塗膜密接,使用金屬鹵素燈照射紫外線,使含有金屬微粒子之光硬化性樹脂組成物硬化。 The photocurable resin composition containing the metal fine particles was uniformly coated on the treated surface by a screen printing method using a PET film (manufactured by Teijin DuPont Film Co., Ltd.) having a thickness of 100 μm on one side as a substrate. The surface of the side was dried at 80 ° C for 10 minutes to obtain a coating film having a thickness of 10 μm. Then, the photomask on which the fine line pattern having a line space of 50/50 (μm) is drawn is adhered to the coating film, and ultraviolet rays are irradiated with a metal halide lamp to cure the photocurable resin composition containing the metal fine particles.
接著,在顯影液中使用1%碳酸鈉,去除未曝光部分,經水洗去除不必要之顯影液。然後,在50℃乾燥5分鐘去除水分,得到電氣佈線電路圖案。 Next, 1% sodium carbonate was used in the developing solution to remove the unexposed portion, and the unnecessary developing solution was removed by washing with water. Then, it was dried at 50 ° C for 5 minutes to remove moisture, and an electrical wiring circuit pattern was obtained.
除了使用表1所示之調配的含有金屬微粒子之光硬化性樹脂組成物,使用聚酯薄膜經由濺鍍沉積法形成ITO膜之厚度100μm的透明導電性薄膜基板(日東電工股份有限公司製造之ELECRYSTA)以取代厚度100μm之單面經易接著處理的PET薄膜基板(帝人杜邦薄膜股份有限公司製造03),在ITO膜表面塗布膏狀之含有金屬微粒子之光硬化性樹脂組成物之外,以與實施例1之相同方法,得到電氣佈線電路圖案。 A transparent conductive film substrate having a thickness of 100 μm in which an ITO film is formed by a sputtering deposition method using a polyester film containing a photo-curable resin composition containing metal fine particles as shown in Table 1 (ELECRYSTA manufactured by Nitto Denko Corporation) In addition to the PET film substrate (manufactured by Teijin DuPont Film Co., Ltd.) having a thickness of 100 μm on one side, the surface of the ITO film is coated with a paste-like photocurable resin composition containing metal fine particles. In the same manner as in Example 1, an electrical wiring circuit pattern was obtained.
除了使用表1所示之調配的含有金屬微粒子之光硬化性樹脂組成物,使用銀奈米線之厚度100μm的透明導電性薄膜基板(TORAY薄膜加工股份有限公司製造)以取代厚度100μm之單面經易接著處理的PET薄膜基板(帝人杜邦薄膜股份有限公司製造03),以及在銀奈米線面塗布膏狀之含有金屬微粒子之光硬化性樹脂組成物之外,以與實施例1之相同方法,得到電氣佈線電路圖案。 In addition to the photocurable resin composition containing metal fine particles prepared as shown in Table 1, a transparent conductive film substrate (manufactured by TORAY Film Processing Co., Ltd.) having a thickness of 100 μm of a silver nanowire was used instead of a single side having a thickness of 100 μm. The PET film substrate (manufactured by Teijin DuPont Film Co., Ltd.) which is easy to be processed, and the photocurable resin composition containing metal fine particles in the form of a paste on the silver nanowire surface are the same as those of the first embodiment. The method obtains an electrical wiring circuit pattern.
除了使用表1所示之調配的含有金屬微粒子之光硬化性樹脂組成物,並在曝光時,使用描繪有列間距為30/30(μm)之細線圖案的光罩以取代描繪有列間距為50/50(μm)之細線圖案的光罩之外,以與實施例1之相同方法,得到電氣佈線電路圖案。 Instead of using the photocurable resin composition containing metal fine particles formulated as shown in Table 1, and at the time of exposure, a photomask having a fine line pattern with a column pitch of 30/30 (μm) was used instead of the column pitch. An electrical wiring circuit pattern was obtained in the same manner as in Example 1 except for a 50/50 (μm) fine line pattern mask.
使用表2所示之調配的含有金屬微粒子之光硬化性樹脂組成物,以與實施例1之相同方法,調製含有金屬微粒子之光硬化性樹脂組成物,形成電氣佈線電路圖案。 Using the photocurable resin composition containing metal fine particles prepared as shown in Table 2, a photocurable resin composition containing metal fine particles was prepared in the same manner as in Example 1 to form an electric wiring circuit pattern.
使用表2所示之調配的含有金屬微粒子之光硬化性樹脂組成物,使用聚酯薄膜經由濺鍍沉積法形成ITO膜之厚度100μm的透明導電性薄膜基板(日東電工股份有限公司製造之ELECRYSTA)以取代厚度100μm之單面經易接著處理的PET薄膜(帝人杜邦薄膜股份有限公司製造03),在ITO膜表面塗布膏狀之含有金屬微粒子之光硬化性樹脂組成物之外,以與實施例1之相同方法,得到電氣佈線 電路圖案。 A transparent conductive film substrate having a thickness of 100 μm of an ITO film formed by a sputter deposition method using a photocurable resin composition containing metal fine particles as shown in Table 2 (ELECRYSTA, manufactured by Nitto Denko Corporation) was used. In place of the photo-curable resin composition containing the metal fine particles in the form of a paste on the surface of the ITO film, instead of the PET film (manufactured by Teijin DuPont Film Co., Ltd.) having a thickness of 100 μm on one side, The same method of 1 gets electrical wiring Circuit pattern.
對於含有金屬微粒子之光硬化性樹脂組成物,評定可形成電氣佈線電路圖案之紫外線照射的最少量,對於所得到之電氣佈線電路圖案,將電阻、經顯影之解析度、與基板之密接性,以下述方法測定或評定。 The photocurable resin composition containing metal fine particles is evaluated for the minimum amount of ultraviolet radiation that can form an electrical wiring circuit pattern, and the obtained electrical wiring circuit pattern has a resolution of development, development, and adhesion to the substrate. It is measured or evaluated by the following method.
在塗有厚度10μm之含有金屬微粒子之光硬化性樹脂組成物的基板上,使描繪有細線圖案之光罩與其密接,使用鹵素燈照射100至1000mJ/cm2,顯影後,將可確認細線圖案之形成的曝光量之最少曝光量作為感度。 On a substrate coated with a photocurable resin composition containing metal fine particles having a thickness of 10 μm, a photomask having a fine line pattern is adhered thereto, and irradiated with a halogen lamp at 100 to 1000 mJ/cm 2 , and after development, a thin line pattern can be confirmed. The minimum amount of exposure of the exposure amount formed is used as the sensitivity.
比電阻之測定係使用四探針法電阻計Loresta AX(Mitsubishi Chemical Analytech股份有限公司製造),依照JIS K7149測定。比電阻在測定界限以下時係以O.L.(Over Load)表示。 The measurement of the specific resistance was carried out in accordance with JIS K7149 using a four-probe resistance meter Loresta AX (manufactured by Mitsubishi Chemical Analytech Co., Ltd.). When the specific resistance is below the measurement limit, it is represented by O.L. (Over Load).
解析度之評定係將顯影處理後之電路圖案以落射照明型之光學顯微鏡以倍率100倍觀察後,評定空間部分有無樹脂組成物的殘渣,以及線部分有無斷線。經確認無樹脂組成物的殘渣、以及線部分無斷線者以○表示;經確認有樹脂組成物的殘渣、以及線部分有斷線者以×表示。 In the evaluation of the resolution, the circuit pattern after the development treatment was observed at an magnification of 100 times by an epi-illumination type optical microscope, and the presence or absence of the residue of the resin composition in the space portion and the presence or absence of breakage of the line portion were evaluated. It is confirmed that the residue of the resin-free composition and the line portion are not broken are indicated by ○; the residue of the resin composition and the disconnection of the line portion are indicated by ×.
與基板之密接性的評定係依據JIS H8504膠帶試驗 方法施行剝離試驗。確認電路圖案有無剝離。塗膜無剝離者係以○表示;塗膜有剝離者係以×表示。 The evaluation of the adhesion to the substrate is based on the JIS H8504 tape test. Method A peel test was performed. Check if the circuit pattern is peeled off. The peeling of the coating film is indicated by ○, and the peeling of the coating film is indicated by ×.
各實施例之評定結果呈示於表3、比較例之評定結果呈示於表4。 The evaluation results of the respective examples are shown in Table 3, and the evaluation results of the comparative examples are shown in Table 4.
實施例1至8中,將具有符合50%平均粒徑在0.1μm至5μm、敲緊密度在2.5g/cm3以下、BET比表面積在1.5m2/g以下之物性的導電性之銀微粒子,相對於含有金屬微粒子之光硬化性樹脂組成物之總量,藉由在本發明之範圍內使用,形成實用上兼具充分導電性、高解析度及密接性之電氣佈線電路圖案。 In Examples 1 to 8, conductive silver particles having a physical property of 50% of an average particle diameter of 0.1 μm to 5 μm, a knocking degree of 2.5 g/cm 3 or less, and a BET specific surface area of 1.5 m 2 /g or less were obtained. By using the total amount of the photocurable resin composition containing metal fine particles, it is used within the scope of the present invention to form an electrical wiring circuit pattern which is practically excellent in electrical conductivity, high resolution, and adhesion.
並且,實施例1至8中使用之含有金屬微粒子之光硬化性樹脂組成物的感度良好,特別在實施例5中,藉由使用具有O-醯基肟構造之光聚合起始劑,相較於其他條件相同的實施例4,可提高大約2倍的感度。 Further, the photosensitivity resin composition containing the metal fine particles used in Examples 1 to 8 has a good sensitivity, and in particular, in Example 5, by using a photopolymerization initiator having an O-fluorenylfluorene structure, In Example 4, which is otherwise the same, the sensitivity is about 2 times higher.
並且,由實施例6及7之結果可知,藉由使用本發明 之含有金屬微粒子之光硬化性樹脂組成物,不論基板種類,可得到具有充分密接性之電氣佈線電路圖案。 Moreover, as can be seen from the results of Examples 6 and 7, by using the present invention The photocurable resin composition containing the metal fine particles can obtain an electrical wiring circuit pattern having sufficient adhesion regardless of the type of the substrate.
另外,在50%平均粒徑大於5μm時(比較例7)、敲緊密度大於2.5g/cm3(比較例1、2、5、7)、BET比表面積大於1.5m2/g(比較例6),以及具導電性之微粒子(A)之含量不在本發明之範圍內時(比較例3、4),在感度、比電阻、解析度、密接性之任一者出現問題。 Further, when the 50% average particle diameter is more than 5 μm (Comparative Example 7), the knock tightness is more than 2.5 g/cm 3 (Comparative Examples 1, 2, 5, and 7), and the BET specific surface area is more than 1.5 m 2 /g (Comparative Example) 6) When the content of the conductive fine particles (A) is out of the range of the present invention (Comparative Examples 3 and 4), there is a problem in any of sensitivity, specific resistance, resolution, and adhesion.
比較例2在使用銀微粒子M4時無法得到導電性。此推測係因M4為球狀金屬微粒子使粒子間之接點少而無法得到導電性。比較例3亦未得到充分的導電性。此推測係由於含有金屬微粒子之光硬化性樹脂組成物中具導電性之金屬微粒子(A)的含量超出本發明之範圍,故大量光硬化性樹脂等存在於金屬填充物之間而形成電阻,因此無法得到導電性。 In Comparative Example 2, conductivity was not obtained when silver fine particles M4 were used. This is because M4 is a spherical metal fine particle, and the contact between the particles is small, and conductivity cannot be obtained. In Comparative Example 3, sufficient conductivity was not obtained. It is estimated that the content of the conductive metal fine particles (A) in the photocurable resin composition containing the metal fine particles is outside the range of the present invention, so that a large amount of photocurable resin or the like exists between the metal fillers to form an electric resistance. Therefore, conductivity cannot be obtained.
比較例7中雖呈現低的比電阻,顯影後之線間,可見到多數金屬微粒子間之接觸(短路部分)。金屬微粒子之平均粒徑大時,粒子間容易接觸,認為雖可得到高的導電性,惟其反面,亦呈現電路的高機率短路。 In Comparative Example 7, although a low specific resistance was exhibited, contact between a plurality of metal fine particles (short-circuit portion) was observed between the lines after development. When the average particle diameter of the metal fine particles is large, the particles are easily contacted, and it is considered that although high conductivity is obtained, the reverse side also exhibits a high probability of short circuit.
本發明之含有金屬微粒子之光硬化性樹脂組成物、電氣佈線電路圖案之製造方法以及電氣佈線電路基板,可有效地利用在各種電氣佈線電路基板的製造領域中。 The photocurable resin composition containing metal fine particles, the method for producing an electric wiring circuit pattern, and the electric wiring circuit substrate of the present invention can be effectively utilized in the field of manufacturing various electric wiring circuit boards.
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JP5858197B2 (en) * | 2013-10-16 | 2016-02-10 | 日立化成株式会社 | Laminated body including conductive fiber, photosensitive conductive film, method for manufacturing conductive pattern, conductive pattern substrate, and touch panel |
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CN104916346A (en) * | 2015-01-05 | 2015-09-16 | 深圳市思迈科新材料有限公司 | Low-temperature curing photosensitive conductive silver slurry composition |
JP6406618B2 (en) * | 2015-03-25 | 2018-10-17 | 株式会社大阪ソーダ | Reactive resin composition and its use |
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