TW201800850A - Photosensitive conductive paste and method for manufacturing substrate provided with conductive pattern - Google Patents
Photosensitive conductive paste and method for manufacturing substrate provided with conductive pattern Download PDFInfo
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/24—Electrically-conducting paints
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
- B05D3/02—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by baking
- B05D3/0254—After-treatment
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/40—Layered products comprising a layer of synthetic resin comprising polyurethanes
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
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- G—PHYSICS
- G06—COMPUTING; CALCULATING OR COUNTING
- G06F—ELECTRIC DIGITAL DATA PROCESSING
- G06F3/00—Input arrangements for transferring data to be processed into a form capable of being handled by the computer; Output arrangements for transferring data from processing unit to output unit, e.g. interface arrangements
- G06F3/01—Input arrangements or combined input and output arrangements for interaction between user and computer
- G06F3/03—Arrangements for converting the position or the displacement of a member into a coded form
- G06F3/041—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B5/00—Non-insulated conductors or conductive bodies characterised by their form
- H01B5/14—Non-insulated conductors or conductive bodies characterised by their form comprising conductive layers or films on insulating-supports
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- General Engineering & Computer Science (AREA)
- General Physics & Mathematics (AREA)
- Physics & Mathematics (AREA)
- Human Computer Interaction (AREA)
- Laminated Bodies (AREA)
- Materials For Photolithography (AREA)
- Non-Insulated Conductors (AREA)
- Conductive Materials (AREA)
- Position Input By Displaying (AREA)
- Photosensitive Polymer And Photoresist Processing (AREA)
- Parts Printed On Printed Circuit Boards (AREA)
- Manufacturing Of Printed Circuit Boards (AREA)
- Manufacturing Of Electric Cables (AREA)
Abstract
Description
本發明關於能夠形成微細導電圖案的感光性導電糊及附有使用該感光性導電糊而成的導電圖案之基板的製造方法。 The present invention relates to a photosensitive conductive paste capable of forming a fine conductive pattern and a method for manufacturing a substrate having a conductive pattern formed using the photosensitive conductive paste.
近年，變得能夠藉由光微影法(photolithographic method)製造微細導電圖案。就使用的導電糊，已開發提議有：使導電填料分散於感光性有機成分而成的感光性導電糊(參照專利文獻1及2)。藉由使用這樣的感光性導電糊，變得能夠形成間距數十μm左右的導電圖案，但若因間距的窄化而導電圖案間的空間變得狹窄，則有在圖案間短路的可能性變高這樣的課題。於是，已提議：利用添加紫外線吸收劑的方法，抑制曝光後導電圖案的線增粗，形成直進性良好的導電圖案(參照專利文獻3)。 In recent years, it has become possible to produce fine conductive patterns by a photolithographic method. As a conductive paste to be used, a photosensitive conductive paste in which a conductive filler is dispersed in a photosensitive organic component has been proposed (see Patent Documents 1 and 2). By using such a photosensitive conductive paste, it becomes possible to form a conductive pattern having a pitch of several tens of μm, but if the space between conductive patterns becomes narrow due to the narrowing of the pitch, there is a possibility that a short circuit between the patterns may occur Such a problem. Therefore, it has been proposed to use a method of adding an ultraviolet absorber to suppress the line thickening of the conductive pattern after exposure and to form a conductive pattern with good linearity (see Patent Document 3).
專利文獻1 國際公開第2013/108696號小冊 Patent Document 1 International Publication No. 2013/108696
專利文獻2 國際公開第2013/146107號小冊 Patent Document 2 International Publication No. 2013/146107
專利文獻3 日本特開2013-196998號公報 Patent Document 3 Japanese Patent Application Publication No. 2013-196998
惟，當藉由添加紫外線吸收劑而形成了直進性良好的微細導電圖案時，即便與添加前比較而比電阻值是同等的，亦有線寬變得更細，且電路電阻會提升的課題。 However, when a fine conductive pattern with good linearity is formed by adding an ultraviolet absorber, even if the specific resistance value is the same as that before the addition, the wire width becomes thinner and the circuit resistance increases.
本發明提供一種感光性導電糊，其在形成直進性良好且微細的導電圖案的同時，表現高導電性。 The present invention provides a photosensitive conductive paste that exhibits high conductivity while forming a fine conductive pattern with good straightness.
本發明人等進行深入探討的結果，發現適度地減低有機成分的反應性，有助於形成直進性良好的微細導電圖案，以及表現高導電性兩者。即，藉由適度地減低有機成分的反應性，變得能夠抑制曝光時自由基聚合的暴動，並形成直進性良好的微細導電圖案。又，因為在曝光後的時間點有機成分的反應不會過度進展，會發生加熱時的硬化收縮，而導電填料彼此的接觸機率提升，會表現高導電性。發現：藉由於其含有具有羥基吡啶骨架的化合物作為有機成分，能夠適度地抑制有機成分的反應性，能夠達成形成直進性良好的微細導電圖案，並表現高導電性兩者，而完成本發明。 As a result of intensive investigations by the present inventors, it has been found that moderately reducing the reactivity of organic components contributes to the formation of a fine conductive pattern with good linearity and to exhibit high conductivity. That is, by appropriately reducing the reactivity of the organic component, it becomes possible to suppress the riot of radical polymerization at the time of exposure and form a fine conductive pattern with good linearity. In addition, since the reaction of the organic components does not progress excessively at the time point after the exposure, hardening shrinkage upon heating occurs, and the contact probability between the conductive fillers is increased, and high conductivity is exhibited. The present inventors have found that the present invention has been completed by including a compound having a hydroxypyridine skeleton as an organic component, which can moderately suppress the reactivity of the organic component, and can achieve formation of a fine conductive pattern with good linearity and high conductivity.
本發明為一種感光性導電糊，其含有：導電性粒子(A)、具有不飽和雙鍵的化合物(B)、光聚合起始劑(C)與於一分子中具有羥基吡啶骨架的化合物(D)。 The present invention is a photosensitive conductive paste containing conductive particles (A), a compound (B) having an unsaturated double bond, a photopolymerization initiator (C), and a compound having a hydroxypyridine skeleton in one molecule ( D).
依據本發明感光性導電糊較佳的態樣的話，前述於一分子中具有羥基吡啶骨架的化合物(D)為具有羥甲基的化合物。 According to a preferable aspect of the photosensitive conductive paste of the present invention, the compound (D) having a hydroxypyridine skeleton in one molecule is a compound having a methylol group.
依據本發明感光性導電糊之較佳態樣的話，相對於前述100質量份具有不飽和雙鍵的化合物(B)，前述於一分子中具有羥基吡啶骨架的化合物(D)的含量為0.3~10質量份。 According to a preferred aspect of the photosensitive conductive paste of the present invention, the content of the compound (D) having a hydroxypyridine skeleton in one molecule is 0.3 to 100 parts by mass of the compound (B) having an unsaturated double bond. 10 parts by mass.
依據本發明感光性導電糊之較佳態樣的話，是含有熱硬化性樹脂(E)。 In a preferred embodiment of the photosensitive conductive paste according to the present invention, the photosensitive conductive paste contains a thermosetting resin (E).
依據本發明感光性導電糊之較佳態樣的話，前述熱硬化性樹脂(E)為環氧當量150~500g/當量的環氧樹脂。 According to a preferable aspect of the photosensitive conductive paste of the present invention, the thermosetting resin (E) is an epoxy resin having an epoxy equivalent of 150 to 500 g / equivalent.
本發明能夠藉由在把前述感光性導電糊塗布於基板上之後，在溫度100~300℃下進行硬化(cure)而製造附有導電圖案之基板。 The present invention can manufacture a substrate with a conductive pattern by applying the photosensitive conductive paste on a substrate and then curing the substrate at a temperature of 100 to 300 ° C.
依據本發明的話，可獲得一種比電阻值低的感光性導電糊，其能夠形成直進性良好且微細的導電圖案。 According to the present invention, it is possible to obtain a photosensitive conductive paste having a low specific resistance, which can form a fine conductive pattern with good straightness.
本發明之感光性導電糊能夠適合地利用於用以製造觸控面板用的周圍配線等導電圖案。 The photosensitive conductive paste of the present invention can be suitably used for conductive patterns such as peripheral wirings for manufacturing touch panels.
1‧‧‧最大線寬 1‧‧‧Max line width
2‧‧‧最小線寬 2‧‧‧ minimum line width
A‧‧‧透光圖案 A‧‧‧Translucent pattern
B‧‧‧使用L/S=20/20之光罩而製作出的導電圖案 B‧‧‧Conductive pattern made using a mask with L / S = 20/20
圖1是顯示在實施例的直進性評價中之測定處的示意圖。 FIG. 1 is a schematic diagram showing a measurement place in the linearity evaluation of the example.
圖2是顯示使用於實施例的比電阻評價之光罩之透光圖案的示意圖。 FIG. 2 is a schematic diagram showing a light-transmitting pattern of a photoresist used in the specific resistance evaluation of the embodiment.
本發明之感光性導電糊含有：導電性粒子(A)、具有不飽和雙鍵的化合物(B)、光聚合起始劑(C)與於一分子中具有羥基吡啶骨架的化合物(D)。 The photosensitive conductive paste of the present invention contains conductive particles (A), a compound (B) having an unsaturated double bond, a photopolymerization initiator (C), and a compound (D) having a hydroxypyridine skeleton in one molecule.
藉由本發明之感光性導電糊所獲得之導電圖案，成為了有機成分與無機成分的複合物，導電性粒子(A)彼此藉著熱硬化(heat cure)時的硬化收縮而相互接觸而表現導電性。 The conductive pattern obtained by the photosensitive conductive paste of the present invention becomes a composite of an organic component and an inorganic component, and the conductive particles (A) are brought into contact with each other by the hardening contraction during heat curing, thereby exhibiting conductivity. Sex.
就於本發明之感光性導電糊所含之導電性粒子(A)而言，較佳為包含：銀、金、銅、鉑、鉛、錫、鎳、鋁、鎢、鉬、鉻、鈦以及銦之至少1種的導電性填料，能夠將該等導電性填料以單獨、合金或者混合粉末的形式使用。又，同樣地亦能夠使用利用上述成分被覆樹脂及無機氧化物等絕緣性粒子或者導電性粒子的表面而成的導電性粒子。其中，從導電性的觀點，較佳為銀、金或銅，從成本及穩定性的觀點，更佳為使用銀。 The conductive particles (A) contained in the photosensitive conductive paste of the present invention preferably include: silver, gold, copper, platinum, lead, tin, nickel, aluminum, tungsten, molybdenum, chromium, titanium, and The conductive filler of at least one kind of indium can be used alone, as an alloy, or as a mixed powder. Similarly, conductive particles obtained by coating the surfaces of insulating particles or conductive particles such as resins and inorganic oxides with the above components can also be used. Among them, silver, gold, or copper is preferred from the viewpoint of conductivity, and silver is more preferably used from the viewpoint of cost and stability.
就導電性粒子(A)的形狀來說，將長軸長除以短軸長而得之值，即，縱橫比較佳為1.0~3.0，更佳的態樣為1.0~2.0。將導電性粒子(A)的縱橫比設為1.0以上，會更提高導電性粒子(A)彼此的接觸機率。另一方面，將導電性粒子(A)的縱橫比設為2.0以下，在利用光微影法來形成配線時，曝光光不易被遮蔽，顯影邊限能夠寬廣。 The shape of the conductive particles (A) is a value obtained by dividing the length of the long axis by the length of the short axis, that is, the aspect ratio is preferably 1.0 to 3.0, and the more preferable aspect is 1.0 to 2.0. When the aspect ratio of the conductive particles (A) is 1.0 or more, the probability of contact between the conductive particles (A) is further increased. On the other hand, when the aspect ratio of the conductive particles (A) is set to 2.0 or less, when the wiring is formed by the photolithography method, the exposure light is not easily blocked, and the development margin can be broadened.
導電性粒子(A)的縱橫比是使用掃描式電子顯微鏡(SEM)或穿透式電子顯微鏡(TEM)以倍率15000倍觀察導電性粒子(A)，隨意地選擇100個導電性粒子的一次粒子，測定各個長軸長及短軸長，從兩者的平均值求得縱橫比。 The aspect ratio of the conductive particles (A) is to observe the conductive particles (A) using a scanning electron microscope (SEM) or a transmission electron microscope (TEM) at a magnification of 15,000 times, and randomly select primary particles of 100 conductive particles. The lengths of the major and minor axes are measured, and the aspect ratio is obtained from the average of the two.
導電性粒子(A)的粒徑較佳為0.05~5.0μm，更佳為0.1~2.0μm。若將導電性粒子(A)的粒徑設為0.05μm以上，則粒子間的相互作用弱，易保持在糊中之導電性粒子(A)的分散狀態。若將導電性粒子(A)的粒徑設為5.0μm以下，則所製造出之導電圖案的表面平滑度、圖案精密度及尺寸精密度能夠提升。 The particle diameter of the conductive particles (A) is preferably 0.05 to 5.0 μm, and more preferably 0.1 to 2.0 μm. When the particle diameter of the conductive particles (A) is 0.05 μm or more, the interaction between the particles is weak, and the dispersed state of the conductive particles (A) in the paste is easily maintained. When the particle diameter of the conductive particles (A) is 5.0 μm or less, the surface smoothness, pattern accuracy, and dimensional accuracy of the produced conductive pattern can be improved.
感光性導電糊含有之導電性粒子(A)的粒徑，是藉由利用電子顯微鏡觀察，隨意地選擇20個導電性粒子的一次粒子，測定各個的最大寬度，利用求得該等的平均值而算出。 The particle diameter of the conductive particles (A) contained in the photosensitive conductive paste is determined by arbitrarily selecting primary particles of 20 conductive particles by observation with an electron microscope, measuring the maximum width of each, and obtaining the average value of these And figure it out.
導電性粒子(A)的含量，相對於導電糊中全部固體成分較佳為60~95質量%，更佳為75~90質量%。若導電性粒子(A)相對於全部固體成分之含量為60質量%以上，則硬化時導電性粒子(A)彼此的接觸機率提升，所製造出之導電圖案的比電阻及斷線機率變低。若導電性粒子(A)相對於全部固體成分的含量為95質量%以下，則在曝光步驟中塗膜的透光性提升，微細的圖案化變得容易。於此處所謂全部固體成分是稱除去溶劑，感光性導電糊的全部構成成分。 The content of the conductive particles (A) is preferably 60 to 95% by mass, and more preferably 75 to 90% by mass relative to the total solid content in the conductive paste. When the content of the conductive particles (A) with respect to the total solid content is 60% by mass or more, the probability of contact between the conductive particles (A) during curing is increased, and the specific resistance and the probability of disconnection of the conductive pattern produced are reduced. . When the content of the conductive particles (A) with respect to the total solid content is 95% by mass or less, the light transmittance of the coating film is improved in the exposure step, and fine patterning becomes easy. Here, the term “all solid components” refers to all constituent components of the photosensitive conductive paste except for the removal of the solvent.
於本發明之感光性導電糊所含之具有不飽和雙鍵的化合物(B)，例如可舉：苯乙烯、對-甲基苯乙烯、鄰-甲基苯乙烯、間-甲基苯乙烯、α-甲基苯乙烯、氯甲基苯乙烯或者羥基甲基苯乙烯等苯乙烯類、丙烯酸系單體、丙烯酸系共聚物、環氧羧酸酯化合物、及1-乙烯基-2-吡咯啶酮。 Examples of the compound (B) having an unsaturated double bond contained in the photosensitive conductive paste of the present invention include styrene, p-methylstyrene, o-methylstyrene, m-methylstyrene, α-methylstyrene, chloromethylstyrene, or hydroxymethylstyrene, such as styrenics, acrylic monomers, acrylic copolymers, epoxy carboxylate compounds, and 1-vinyl-2-pyrrolidine ketone.
就丙烯酸系單體而言，例如可舉：丙烯酸、丙烯酸甲酯、丙烯酸乙酯、丙烯酸2-乙基己酯、丙烯酸正丁酯、丙烯酸異丁酯、異丙烷丙烯酸酯、丙烯酸縮水甘油酯、丁氧基三乙二醇丙烯酸酯、丙烯酸二環戊酯、丙烯酸二環戊烯酯、丙烯酸2-羥基乙酯、丙烯酸異冰片酯、丙烯酸2-羥基丙酯、丙烯酸異癸酯、丙烯酸異辛酯、丙烯酸月桂酯、丙烯酸2-甲氧基乙酯、甲氧基乙二醇丙烯酸酯、甲氧基二乙二醇丙烯酸酯、丙烯酸八氟戊酯、丙烯酸苯氧基乙酯、丙烯酸硬脂酯、丙烯酸三氟乙酯、丙烯酸胺基乙酯、丙烯酸苯酯、丙烯酸苯氧基乙酯、丙烯酸1-萘酯、丙烯酸2-萘酯、硫酚丙烯酸酯(thiophenol acrylate)或者苄硫醇丙烯酸酯(benzyl mercaptan acrylate)、烯丙基化環己基二丙烯酸酯、甲氧基化環己基二丙烯酸酯、1,4-丁二醇二丙烯酸酯、1,3-丁二醇二丙烯酸酯、乙二醇二丙烯酸酯、二乙二醇二丙烯酸酯、三乙二醇二丙烯酸酯、聚乙二醇二丙烯酸酯、新戊二醇二丙烯酸酯、丙二醇二丙烯酸酯、聚丙二醇二丙烯酸酯或者三甘油二丙烯酸酯、三羥甲基丙烷三丙烯酸酯、二-三羥甲基丙烷四丙烯酸酯、二新戊四醇單羥基五丙烯酸 酯或者二新戊四醇六丙烯酸酯、丙烯醯胺、N-甲氧基甲基丙烯醯胺、N-乙氧基甲基丙烯醯胺、N-正丁氧基甲基丙烯醯胺或者N-異丁氧基甲基丙烯醯胺、具有以不飽和酸使環氧基開環而成的羥基之乙二醇二縮水甘油醚的丙烯酸加成物、二乙二醇二縮水甘油醚的丙烯酸加成物、新戊二醇二縮水甘油醚的丙烯酸加成物、甘油二縮水甘油醚的丙烯酸加成物、雙酚A二縮水甘油醚的丙烯酸加成物、雙酚F的丙烯酸加成物或者甲酚酚醛清漆的丙烯酸加成物等環氧丙烯酸酯單體或者γ-丙烯醯氧丙基三甲氧基矽烷，或者，將該等的丙烯醯基取代為甲基丙烯醯基而成的化合物。 Examples of acrylic monomers include acrylic acid, methyl acrylate, ethyl acrylate, 2-ethylhexyl acrylate, n-butyl acrylate, isobutyl acrylate, isopropyl acrylate, glycidyl acrylate, Butoxy triethylene glycol acrylate, dicyclopentyl acrylate, dicyclopentenyl acrylate, 2-hydroxyethyl acrylate, isobornyl acrylate, 2-hydroxypropyl acrylate, isodecyl acrylate, isooctyl acrylate Esters, lauryl acrylate, 2-methoxyethyl acrylate, methoxyethylene glycol acrylate, methoxydiethylene glycol acrylate, octafluoropentyl acrylate, phenoxyethyl acrylate, acrylic stearin Ester, trifluoroethyl acrylate, aminoethyl acrylate, phenyl acrylate, phenoxyethyl acrylate, 1-naphthyl acrylate, 2-naphthyl acrylate, thiophenol acrylate or benzyl mercaptan acrylic acid Ester (benzyl mercaptan acrylate), allyl cyclohexyl diacrylate, methoxylated cyclohexyl diacrylate, 1,4-butanediol diacrylate, 1,3-butanediol diacrylate, ethyl Diol diacrylic acid , Diethylene glycol diacrylate, triethylene glycol diacrylate, polyethylene glycol diacrylate, neopentyl glycol diacrylate, propylene glycol diacrylate, polypropylene glycol diacrylate or triglycerol diacrylate, Trimethylolpropane triacrylate, di-trimethylolpropane tetraacrylate, dipentaerythritol monohydroxypentaacrylic acid Ester or dipentaerythritol hexaacrylate, acrylamide, N-methoxymethacrylamide, N-ethoxymethacrylamide, N-n-butoxymethacrylamide or N -Isobutoxymethacrylamide, acrylic acid adduct of ethylene glycol diglycidyl ether having a hydroxyl group formed by ring opening of an epoxy group with an unsaturated acid, acrylic acid of diethylene glycol diglycidyl ether Adduct, acrylic acid adduct of neopentyl glycol diglycidyl ether, acrylic acid adduct of glycerol diglycidyl ether, acrylic acid adduct of bisphenol A diglycidyl ether, acrylic acid adduct of bisphenol F Either an epoxy acrylate monomer such as an acrylic adduct of cresol novolac, or γ-acrylic acid oxypropyltrimethoxysilane, or a compound obtained by substituting such an acrylic acid group with a methacrylic acid group .
就丙烯酸系共聚物而言是稱在可使用的單體即共聚合成分，包含丙烯酸系單體的共聚物。具有羧基之鹼可溶性丙烯酸系共聚物，可藉由使用不飽和羧酸等不飽和酸作為單體而獲得。就不飽和酸而言，例如可舉：丙烯酸、甲基丙烯酸、伊康酸、巴豆酸、馬來酸、延胡索酸或者乙酸乙烯酯，以及該等的酸酐。可藉由使用之不飽和酸的多寡而調整所獲得之丙烯酸系共聚物的酸價。又，藉由使上述丙烯酸系共聚物具有的羧基，與(甲基)丙烯酸縮水甘油酯等具有不飽和雙鍵之化合物進行反應，能夠獲得在側鏈具有反應性不飽和雙鍵之鹼可溶性丙烯酸系共聚物。 The acrylic copolymer is a copolymer containing an acrylic monomer as a copolymerizable component which is a usable monomer. The alkali-soluble acrylic copolymer having a carboxyl group can be obtained by using an unsaturated acid such as an unsaturated carboxylic acid as a monomer. As for the unsaturated acid, for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, or vinyl acetate, and such anhydrides are mentioned. The acid value of the acrylic copolymer obtained can be adjusted by the amount of unsaturated acid used. Further, by reacting a carboxyl group of the acrylic copolymer with a compound having an unsaturated double bond such as glycidyl (meth) acrylate, an alkali-soluble acrylic acid having a reactive unsaturated double bond in a side chain can be obtained. Copolymer.
就環氧羧酸酯化合物而言是稱能夠以環氧化合物與具有不飽和雙鍵的羧基化合物為起始原料而進行合成的化合物。就能夠成為起始原料的環氧化合物而 言，例如可舉：縮水甘油醚類、脂環式環氧樹脂、縮水甘油酯類、縮水甘油胺類或環氧樹脂、更具體地說可舉：甲基縮水甘油醚、乙基縮水甘油醚、丁基縮水甘油醚、乙二醇二縮水甘油醚、二乙二醇二縮水甘油醚、丙二醇二縮水甘油醚、三丙二醇二縮水甘油醚、新戊二醇二縮水甘油醚、雙酚A二縮水甘油醚、氫化雙酚A二縮水甘油醚、雙酚F二縮水甘油醚、雙酚S二縮水甘油醚、雙酚茀二縮水甘油醚、聯苯酚二縮水甘油醚、四甲基聯苯酚縮水甘油醚、三羥甲基丙烷三縮水甘油醚、3’,4’-環氧環己基甲基-3,4-環氧環己烷羧酸酯，以及三級丁基縮水甘油胺。又，作為具有不飽和雙鍵之羧基化合物而言，例如可舉：(甲基)丙烯酸、巴豆酸、肉桂酸以及α-氰基肉桂酸。 The epoxy carboxylic acid ester compound is said to be a compound that can be synthesized using an epoxy compound and a carboxyl compound having an unsaturated double bond as starting materials. Can be used as the starting epoxy compound Examples include, for example, glycidyl ethers, alicyclic epoxy resins, glycidyl esters, glycidylamines, or epoxy resins, and more specifically, methyl glycidyl ether, ethyl glycidyl ether. , Butyl glycidyl ether, ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, bisphenol A bis Glycidyl ether, hydrogenated bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether, bisphenol diglycidyl ether, biphenol diglycidyl ether, tetramethyl biphenol shrink Glyceryl ether, trimethylolpropane triglycidyl ether, 3 ', 4'-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, and tertiary butyl glycidylamine. Examples of the carboxyl compound having an unsaturated double bond include (meth) acrylic acid, crotonic acid, cinnamic acid, and α-cyanocinnamic acid.
使環氧羧酸酯化合物與多元酸酐反應，能夠調整環氧羧酸酯化合物的酸價。就多元酸酐而言，例如可舉：琥珀酸酐、苯二甲酸酐、四氫苯二甲酸酐、六氫苯二甲酸酐、伊康酸酐、3-甲基四氫苯二甲酸酐、4-甲基-六氫苯二甲酸酐、偏苯三甲酸酐及馬來酸酐。藉由使得與上述多元酸酐反應之環氧羧酸酯化合物具有的羧基，與(甲基)丙烯酸縮水甘油酯等具有不飽和雙鍵的化合物反應，能夠調整環氧羧酸酯化合物具有之反應性不飽和雙鍵的量。 By reacting an epoxy carboxylic acid ester compound with a polybasic acid anhydride, the acid value of the epoxy carboxylic acid ester compound can be adjusted. As for the polybasic acid anhydride, for example: succinic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, itaconic anhydride, 3-methyltetrahydrophthalic anhydride, 4-methyl Hexahydrophthalic anhydride, trimellitic anhydride and maleic anhydride. The reactivity of the epoxy carboxylic acid ester compound can be adjusted by reacting the carboxyl group of the epoxy carboxylic acid ester compound that is reacted with the polybasic acid anhydride with a compound having an unsaturated double bond such as glycidyl (meth) acrylate. The amount of unsaturated double bonds.
藉由使環氧羧酸酯化合物具有的羥基，與二異氰酸酯化合物反應，能夠進行胺基甲酸酯化。就二異氰酸酯化合物而言，例如可舉：六亞甲基二異氰酸酯、 四甲基二甲苯二異氰酸酯、萘-1,5-二異氰酸酯、甲苯二異氰酸酯(tolidene diisocyanate)、三甲基六亞甲基二異氰酸酯、異佛酮二異氰酸酯、烯丙基氰基二異氰酸酯，及降莰烷二異氰酸酯。 By reacting a hydroxyl group possessed by the epoxy carboxylic acid ester compound with a diisocyanate compound, urethanization can be performed. As for the diisocyanate compound, for example, hexamethylene diisocyanate, Tetramethylxylene diisocyanate, naphthalene-1,5-diisocyanate, tolidene diisocyanate, trimethylhexamethylene diisocyanate, isophorone diisocyanate, allylcyano diisocyanate, and Norbornane diisocyanate.
為了使得鹼可溶性最適合，具有不飽和雙鍵的化合物(B)的酸價，較佳為30~250mgKOH/g。具有不飽和雙鍵的化合物(B)的酸價為30mgKOH/g以上的話，能夠抑制可溶部分的溶解性。具有不飽和雙鍵的化合物(B)的酸價為250mgKOH/g以下的話，能夠保持顯影容許範圍。具有不飽和雙鍵的化合物(B)的酸價能夠依據JIS K 0070(1992)而測定。 In order to make alkali solubility the most suitable, the acid value of the compound (B) having an unsaturated double bond is preferably 30 to 250 mgKOH / g. When the acid value of the compound (B) having an unsaturated double bond is 30 mgKOH / g or more, the solubility of the soluble portion can be suppressed. When the acid value of the compound (B) having an unsaturated double bond is 250 mgKOH / g or less, the development allowable range can be maintained. The acid value of the compound (B) having an unsaturated double bond can be measured in accordance with JIS K 0070 (1992).
就本發明之感光性導電糊所含之光聚合起始劑(C)而言，例如可舉：二苯甲酮、鄰苯甲醯基苯甲酸甲酯、4,4’-雙(二甲基胺基)二苯甲酮、4,4’-雙(二乙基胺基)二苯甲酮、4,4’-二氯二苯甲酮、4-苯甲醯基-4’-甲基二苯基酮、茀酮等二苯甲酮衍生物；對三級丁基二氯苯乙酮、4-疊氮基苯亞甲基苯乙酮、2,2’-二乙氧基苯乙酮等苯乙酮衍生物；噻噸酮、2-甲基噻噸酮、2-氯噻噸酮、2-異丙基噻噸酮、二乙基噻噸酮等噻噸酮衍生物；苄基、苄基二甲基縮酮、苄基-β-甲氧基乙基縮醛等苄基衍生物；苯偶姻、苯偶姻甲醚、苯偶姻丁醚等苯偶姻衍生物；1,2-辛烷二酮-1-[4-(苯基硫)-2-(O-苯甲醯基肟)]、乙酮-1-[9-乙基-6-(2-甲基苯甲醯基)-9H-咔唑-3-基]-1-(O-乙醯肟)、1-苯基-1,2-丁二酮-2-(O-甲氧基羰基)肟、1-苯基-丙二酮-2-(O-乙氧基羰基)肟、1-苯基-丙二酮-2-(O-苯甲
醯基)肟、1,3-二苯基-丙三酮-2-(O-乙氧基羰基)肟、1-苯基-3-乙氧基-丙三酮-2-(O-苯甲醯基)肟等肟系化合物；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-酮等α-羥基酮系化合物；2-甲基-(4-甲基苯硫基)-2-
相對於100質量份具有不飽和雙鍵的化合物(B)，光聚合起始劑(C)的含量較佳為0.05~30質量份，更佳為1~10質量份。相對於100質量份具有不飽和雙鍵的化合物(B)，光聚合起始劑(C)的含量若成為0.05質量份以上，則曝光部的硬化密度提升，能夠提高顯影後的殘膜率。相對於100質量份具有不飽和雙鍵的化合物(B)， 光聚合起始劑(C)的含量若成為30質量份以下，則在塗布導電糊所獲得之塗布膜上部之因光聚合起始劑(C)所致之過剩的光吸收受到抑制。其結果，所製造出之導電圖案成為倒錐形狀所致之與基板的密接性降低會受到抑制。 The content of the photopolymerization initiator (C) is preferably 0.05 to 30 parts by mass, and more preferably 1 to 10 parts by mass based on 100 parts by mass of the compound (B) having an unsaturated double bond. With respect to 100 parts by mass of the compound (B) having an unsaturated double bond, if the content of the photopolymerization initiator (C) is 0.05 parts by mass or more, the curing density of the exposed portion is increased, and the residual film rate after development can be increased. With respect to 100 parts by mass of the compound (B) having an unsaturated double bond, When the content of the photopolymerization initiator (C) is 30 parts by mass or less, excessive light absorption by the photopolymerization initiator (C) on the upper part of the coating film obtained by applying the conductive paste is suppressed. As a result, the decrease in adhesion with the substrate caused by the produced conductive pattern having an inverted cone shape is suppressed.
本發明之感光性導電糊能夠與光聚合起始劑(C)一併使含有增感劑。 The photosensitive conductive paste of the present invention can contain a sensitizer together with the photopolymerization initiator (C).
作為增感劑，例如，可舉：2,4-二乙基噻噸酮、異丙基噻噸酮、2,3-雙(4-二乙基胺基苯亞甲基)環戊酮、2,6-雙(4-二甲基胺基苯亞甲基)環己酮、2,6-雙(4-二甲基胺基苯亞甲基)-4-甲基環己酮、米其勒酮(Michler’s ketone)、4,4-雙(二乙基胺基)二苯甲酮、4,4-雙(二甲基胺基)查耳酮、4,4-雙(二乙基胺基)查耳酮、對二甲基胺基苯亞烯丙基二氫茚酮(p-dimethyl amino cinnamylidene indanone)、對二甲基胺基亞苄基二氫茚酮、2-(對二甲基胺基苯基伸乙烯基)異萘并噻唑、1,3-雙(4-二甲基胺基苯基伸乙烯基)異萘并噻唑、1,3-雙(4-二甲基胺基苯亞甲基)丙酮、1,3-羰基雙(4-二乙基胺基苯亞甲基)丙酮、3,3-羰基雙(7-二乙基胺基香豆素)、N-苯基-N-乙基乙醇胺、N-苯基乙醇胺、N-甲苯基二乙醇胺、二甲基胺基苯甲酸異戊酯、二乙基胺基苯甲酸異戊酯、3-苯基-5-苯甲醯基硫代四唑，及1-苯基-5-乙氧基羰基硫代四唑。 Examples of the sensitizer include 2,4-diethylthioxanthone, isopropylthioxanthone, 2,3-bis (4-diethylaminobenzylidene) cyclopentanone, 2,6-bis (4-dimethylaminobenzylidene) cyclohexanone, 2,6-bis (4-dimethylaminobenzylidene) -4-methylcyclohexanone, rice Michler's ketone, 4,4-bis (diethylamino) benzophenone, 4,4-bis (dimethylamino) chalcone, 4,4-bis (diethyl Amine) Chalcone, p-dimethylamino cinnamylidene indanone, p-dimethylamino cinnamylidene indanone, 2- (p-dimethylamino Methylaminophenylphenylvinyl) isonaphthothiazole, 1,3-bis (4-dimethylaminophenylphenylvinyl) isonaphthothiazole, 1,3-bis (4-dimethylamino) Phenylmethylene) acetone, 1,3-carbonylbis (4-diethylaminobenzylidene) acetone, 3,3-carbonylbis (7-diethylaminocoumarin), N-benzene -N-ethylethanolamine, N-phenylethanolamine, N-tolyldiethanolamine, isoamyl dimethylaminobenzoate, isoamyl diethylaminobenzoate, 3-phenyl-5- Benzamidinethiotetrazole, and 1-phenyl-5-ethoxycarbonylthio Tetrazole.
相對於100質量份具有不飽和雙鍵的化合物(B)，增感劑的含量較佳為0.05~10質量份。相對於100質量份具有不飽和雙鍵的化合物(B)，增感劑的含量若成 為0.05質量份以上，則光感度會提升。相對於100質量份具有不飽和雙鍵的化合物(B)，增感劑的含量若成為10質量份以下，則在塗布導電糊所獲得之塗布膜上部，過剩的光吸收受到抑制。其結果，所製造出之導電圖案成為倒錐形狀所致，與基板的密接性降低受到抑制。 The content of the sensitizer is preferably 0.05 to 10 parts by mass based on 100 parts by mass of the compound (B) having an unsaturated double bond. The content of the sensitizer is equal to 100 parts by mass of the compound (B) having an unsaturated double bond. When it is 0.05 parts by mass or more, the light sensitivity is improved. With respect to 100 parts by mass of the compound (B) having an unsaturated double bond, if the content of the sensitizer is 10 parts by mass or less, excessive light absorption is suppressed on the upper part of the coating film obtained by applying the conductive paste. As a result, the produced conductive pattern has an inverted tapered shape, and a decrease in adhesion to the substrate is suppressed.
就於本發明之感光性導電糊所含之於一分子中具有羥基吡啶骨架的化合物(D)而言，例如可舉：2-羥基吡啶、3-羥基吡啶、4-羥基吡啶、2,4-二羥基吡啶、2,4-二羥基喹啉、2,6-二羥基喹啉、2,8-二羥基喹啉、5-羥基-2-甲基吡啶、2-羥基-4-甲基吡啶、2-羥基-5-甲基吡啶、2-羥基-6-甲基吡啶、2,4-二羥基-6-甲基吡啶、2-乙基-3-羥基-6-甲基吡啶、4-溴-2-羥基吡啶、4-氯-2-羥基吡啶、2-羥基-5-碘吡啶、3-羥基異喹啉、2-喹啉酚、3-喹啉酚、2-甲基-4-喹啉酚、吡哆醛-5-磷酸酯、檸嗪酸、6-羥基菸鹼酸，及該等鹽。 Examples of the compound (D) having a hydroxypyridine skeleton in one molecule contained in the photosensitive conductive paste of the present invention include, for example, 2-hydroxypyridine, 3-hydroxypyridine, 4-hydroxypyridine, and 2,4 -Dihydroxypyridine, 2,4-dihydroxyquinoline, 2,6-dihydroxyquinoline, 2,8-dihydroxyquinoline, 5-hydroxy-2-methylpyridine, 2-hydroxy-4-methyl Pyridine, 2-hydroxy-5-methylpyridine, 2-hydroxy-6-methylpyridine, 2,4-dihydroxy-6-methylpyridine, 2-ethyl-3-hydroxy-6-methylpyridine, 4-bromo-2-hydroxypyridine, 4-chloro-2-hydroxypyridine, 2-hydroxy-5-iodopyridine, 3-hydroxyisoquinoline, 2-quinolinol, 3-quinolinol, 2-methyl 4-quinolinol, pyridoxal-5-phosphate, citrazine, 6-hydroxynicotinic acid, and these salts.
其中，具有羥甲基的吡哆醇(pyridoxine)、4-去氧吡哆醇(4-deoxypyridoxine)、吡哆醛(pyridoxal)、吡哆胺(pyridoxamine)、4-吡哆酸(4-pyridoxic acid)、異吡哆醛、2-羥基甲基-3-吡啶醇(2-hydroxymethyl-3-pyridinol)、2-羥基甲基-6-甲基-3-吡啶醇、2,6-雙(羥基甲基)-3-吡啶醇、銀杏毒(ginkgotoxin)、吡哆醇二辛酸酯、吡哆醛肟、6-(羥基甲基)-3,4-吡啶二醇、2-溴-6-(羥基甲基)-3-吡啶醇、2,5-二氯-6-(羥基甲基)-3-吡啶醇、2-氯-6-(羥基甲基)-4-碘-3-吡啶醇、3-(羥基甲基)-6-甲基-4-喹啉酚、吡哆醇-3,4-二 棕櫚酸酯，及該等鹽因為有機成分的反應抑制效果不會過強，而不易發生導電圖案的顯影限度惡化。 Among them, pyridoxine, 4-deoxypyridoxine, pyridoxal, pyridoxamine, 4-pyridoxic acid), isopyridoxal, 2-hydroxymethyl-3-pyridinol, 2-hydroxymethyl-6-methyl-3-pyridinol, 2,6-bis ( (Hydroxymethyl) -3-pyridinol, ginkgotoxin, pyridoxine dicaprylate, pyridoxime, 6- (hydroxymethyl) -3,4-pyridinediol, 2-bromo-6 -(Hydroxymethyl) -3-pyridinol, 2,5-dichloro-6- (hydroxymethyl) -3-pyridinol, 2-chloro-6- (hydroxymethyl) -4-iodo-3- Pyridinol, 3- (hydroxymethyl) -6-methyl-4-quinolinol, pyridoxine-3,4-di Palmitate and these salts will not be too strong because of the effect of suppressing the reaction of organic components, and it is not easy to deteriorate the development limit of the conductive pattern.
相對於100質量份具有不飽和雙鍵的化合物(B)，於一分子中具有羥基吡啶骨架的化合物(D)的含量較佳含有0.3~10質量份，更佳含有0.5~5重量份。相對於100質量份具有不飽和雙鍵的化合物(B)，於一分子中具有羥基吡啶骨架的化合物(D)的含量若成為0.3質量份以上，則因為會防範曝光時光自由基反應的暴動而導電圖案的直進性提升，又，因導電圖案之樹脂成分的硬化在硬化前的時間點不會過度進行，而不會妨礙硬化時的硬化收縮而導電性粒子(A)彼此的接觸機率提升，比電阻值會降低。相對於100質量份具有不飽和雙鍵的化合物(B)，於一分子中具有羥基吡啶骨架的化合物(D)的含量若成為10質量份以下，則光自由基反應不會被過度地抑制，因而微細的圖案化成為可能。 The content of the compound (D) having a hydroxypyridine skeleton in one molecule is preferably 0.3 to 10 parts by mass, and more preferably 0.5 to 5 parts by weight based on 100 parts by mass of the compound (B) having an unsaturated double bond. With respect to 100 parts by mass of the compound (B) having an unsaturated double bond, if the content of the compound (D) having a hydroxypyridine skeleton in one molecule is 0.3 parts by mass or more, the riot of photoradical reaction during exposure will be prevented The straightness of the conductive pattern is improved, and because the hardening of the resin component of the conductive pattern does not proceed excessively at the time before hardening, and it does not hinder the hardening shrinkage during hardening, the contact probability of the conductive particles (A) with each other is increased. The specific resistance value decreases. With respect to 100 parts by mass of the compound (B) having an unsaturated double bond, if the content of the compound (D) having a hydroxypyridine skeleton in one molecule is 10 parts by mass or less, the photoradical reaction is not excessively suppressed. Therefore, fine patterning becomes possible.
能夠使本發明之感光性導電糊含有熱硬化性樹脂(E)。就熱硬化性樹脂(E)可舉：環氧樹脂、酚樹脂、尿素樹脂、三聚氰胺樹脂、不飽和聚酯樹脂、矽樹脂及聚胺基甲酸酯等。就熱硬化性樹脂(E)，其中，較佳為環氧樹脂，在環氧樹脂之中，較佳為環氧當量為150~500g/當量的環氧樹脂。藉由將環氧樹脂的環氧當量設為150g/當量以上，能夠獲得塗布膜的保存穩定性的感光性導電糊。藉由將環氧樹脂的環氧當量設為500g/當量以下，能夠獲得與樹脂薄膜及玻璃基板般的各種基板的密接性高的導電圖案。 The photosensitive conductive paste of the present invention can contain a thermosetting resin (E). Examples of the thermosetting resin (E) include epoxy resin, phenol resin, urea resin, melamine resin, unsaturated polyester resin, silicone resin, and polyurethane. Among the thermosetting resins (E), epoxy resins are preferred, and among epoxy resins, epoxy resins having an epoxy equivalent of 150 to 500 g / equivalent are preferred. When the epoxy equivalent of an epoxy resin is 150 g / equivalent or more, the photosensitive conductive paste of the storage stability of a coating film can be obtained. By setting the epoxy equivalent of the epoxy resin to 500 g / equivalent or less, a conductive pattern with high adhesion to various substrates such as resin films and glass substrates can be obtained.
所謂環氧當量是指，包含1當量之環氧基的樹脂的質量，將從結構式求出的分子量，除以在該結構中所含之環氧基的數量而求得。 The term "epoxy equivalent" refers to the mass of a resin containing one equivalent of epoxy groups, and is obtained by dividing the molecular weight determined from the structural formula by the number of epoxy groups contained in the structure.
相對於100質量份具有不飽和雙鍵的化合物(B)，環氧樹脂的含量較佳為1~100質量份的範圍內，更佳為30~80質量份。藉由相對於100重量份具有不飽和雙鍵的化合物(B)，環氧樹脂的含量是設為1質量份以上，使密接性提升的效果易充分地發揮，而藉由把相對於100重量份具有不飽和雙鍵的化合物(B)的含量設為100質量份以下，能夠獲得塗布膜的保存穩定性特別高的感光性導電糊。 The content of the epoxy resin is preferably within a range of 1 to 100 parts by mass, and more preferably 30 to 80 parts by mass, with respect to 100 parts by mass of the compound (B) having an unsaturated double bond. The content of the epoxy resin is set to 1 part by mass or more with respect to 100 parts by weight of the compound (B) having an unsaturated double bond, so that the effect of improving the adhesiveness is easily exerted sufficiently. The content of the compound (B) having an unsaturated double bond in an amount of 100 parts by mass or less can obtain a photosensitive conductive paste having particularly high storage stability of the coating film.
就環氧樹脂而言，較佳為環氧當量為150~500g/當量的範圍內者，更佳為200~500g/當量的範圍內者。就具體例而言，可舉：乙二醇改性環氧樹脂、雙酚A型環氧樹脂、溴化環氧樹脂、雙酚F型環氧樹脂、酚醛清漆型環氧樹脂、脂環式環氧樹脂、縮水甘油胺型環氧樹脂、縮水甘油醚型環氧樹脂，及雜環式環氧樹脂等。 As for the epoxy resin, the epoxy equivalent is preferably in the range of 150 to 500 g / equivalent, and more preferably in the range of 200 to 500 g / equivalent. Specific examples include: glycol modified epoxy resin, bisphenol A type epoxy resin, brominated epoxy resin, bisphenol F type epoxy resin, novolac type epoxy resin, alicyclic type Epoxy resin, glycidylamine epoxy resin, glycidyl ether epoxy resin, and heterocyclic epoxy resin.
能夠使本發明之感光性導電糊含有溶劑。就溶劑例如可舉：N,N-二甲基乙醯胺、N,N-二甲基甲醯胺、N-甲基-2-吡咯啶酮、二甲基咪唑啶酮、二甲亞碸、γ-丁內酯、乳酸乙酯、1-甲氧基-2-丙醇、1-乙氧基-2-丙醇、乙二醇單-正丙醚、二丙酮醇、四氫糠醇、丙二醇單甲醚乙酸酯、二乙二醇單***乙酸酯、二乙二醇單甲醚、二乙二醇單***乙酸酯(以下稱「DMEA」)、二乙二醇單丁 醚、二乙二醇、及2,2,4,-三甲基-1,3-戊二醇單異丁酸酯，較佳為沸點為150℃以上的溶劑。沸點若為150℃以上，則溶劑的揮發受到抑制而能夠抑制導電糊的增黏。 The photosensitive conductive paste of the present invention can contain a solvent. Examples of the solvent include N, N-dimethylacetamide, N, N-dimethylformamide, N-methyl-2-pyrrolidone, dimethylimidazolidone, and dimethylimine , Γ-butyrolactone, ethyl lactate, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, ethylene glycol mono-n-propyl ether, diacetone alcohol, tetrahydrofurfuryl alcohol, Propylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether acetate (hereinafter referred to as "DMEA"), diethylene glycol monobutyl ether Ether, diethylene glycol, and 2,2,4, -trimethyl-1,3-pentanediol monoisobutyrate are preferably solvents having a boiling point of 150 ° C or higher. When the boiling point is 150 ° C or higher, the volatilization of the solvent is suppressed, and the thickening of the conductive paste can be suppressed.
在不損及其期望的特性的範圍的話，本發明之感光性導電糊，能夠使之含有在分子內不具有不飽和雙鍵的非感光性聚合物、塑化劑、流平劑、界面活性劑、矽烷耦合劑、消泡劑、及顏料等添加劑。 The photosensitive conductive paste of the present invention can contain a non-photosensitive polymer having no unsaturated double bond in the molecule, a plasticizer, a leveling agent, and an interfacial activity, so long as the desired characteristics are not impaired. Additives, silane coupling agents, defoamers, and pigments.
就非感光性聚合物，例如可舉：聚對苯二甲酸乙二酯、聚醯亞胺前驅物及已經閉環之聚醯亞胺。 As the non-photosensitive polymer, for example, polyethylene terephthalate, a polyimide precursor, and a polyimide that has been closed-loop can be mentioned.
就塑化劑，例如可舉：苯二甲酸二丁酯、苯二甲酸二辛酯、聚乙二醇及甘油。 Examples of the plasticizer include dibutyl phthalate, dioctyl phthalate, polyethylene glycol, and glycerin.
就流平劑，例如可舉：特殊乙烯系聚合物以及特殊丙烯酸系聚合物。 As the leveling agent, for example, special vinyl polymers and special acrylic polymers can be mentioned.
就矽烷耦合劑，例如可舉：甲基三甲氧基矽烷、二甲基二乙氧基矽烷、苯基三乙氧基矽烷、六甲基二矽氮烷、3-甲基丙烯醯氧基丙基三甲氧基矽烷、3-縮水甘油氧基丙基三甲氧基矽烷(3-glycidoxypropyltrimethoxysilane)，及乙烯基三甲氧基矽烷。 As for the silane coupling agent, for example: methyltrimethoxysilane, dimethyldiethoxysilane, phenyltriethoxysilane, hexamethyldisilazane, 3-methacryloxypropane Trimethoxysilane, 3-glycidoxypropyltrimethoxysilane, and vinyltrimethoxysilane.
本發明之感光性導電糊是使用例如：三輥磨機、球磨機或者行星式球磨機等分散機或者混煉機所製造。 The photosensitive conductive paste of the present invention is produced using, for example, a three-roll mill, a ball mill, or a planetary ball mill such as a disperser or a kneader.
本發明之附有導電圖案之基板的製造方法是在把本發明之感光性導電糊塗布於基板上，進行乾燥、曝光並顯影之後，在100~300℃的溫度下進行硬化。 In the method for manufacturing a substrate with a conductive pattern of the present invention, the photosensitive conductive paste of the present invention is coated on a substrate, dried, exposed, and developed, and then cured at a temperature of 100 to 300 ° C.
藉由將本發明之感光性導電糊塗布於基板上而獲得塗布膜。就塗布感光性導電糊的基板，例如可舉：聚對苯二甲酸乙二酯薄膜(以下稱為PET薄膜)、聚醯亞胺薄膜、聚酯薄膜、芳綸薄膜(aramid film)、環氧樹脂基板、聚醚醯亞胺樹脂基板、聚醚酮樹脂基板、聚碸系樹脂基板、玻璃基板、矽晶圓、氧化鋁基板、氮化鋁基板、碳化矽基板、加飾層形成基板，及絕緣層形成基板。 A coating film is obtained by coating the photosensitive conductive paste of the present invention on a substrate. As the substrate coated with the photosensitive conductive paste, for example, polyethylene terephthalate film (hereinafter referred to as PET film), polyimide film, polyester film, aramid film, epoxy Resin substrate, polyetherimide resin substrate, polyetherketone resin substrate, polyfluorene-based resin substrate, glass substrate, silicon wafer, alumina substrate, aluminum nitride substrate, silicon carbide substrate, decorative layer forming substrate, and The insulating layer forms a substrate.
就把本發明之感光性導電糊塗布於基板的方法，例如可舉：使用了旋轉器的旋轉塗佈、噴霧塗布、輥塗、網版印刷或者使用了刮刀塗布機(blade coater)、模塗布機、壓延塗佈機(calender coater)、彎月形塗佈機或者棒塗布機的塗布。 The method for applying the photosensitive conductive paste of the present invention to a substrate may be, for example, spin coating using a spinner, spray coating, roll coating, screen printing, or using a blade coater or die coating. Machine, calender coater, meniscus coater or bar coater.
所獲得之塗布膜的膜厚，能夠因應塗布的方法或者感光性導電糊的全部固體成分濃度或者黏度等而適宜決定，但乾燥後的膜厚較佳成為0.1~50μm。膜厚能夠使用如Surfcom(註冊商標)1400(東京精密(股)製)般的探針式輪廓儀而測定。更具體地說，分別利用探針式輪廓儀(測定長度：1mm、掃描速度：0.3mm/秒)測定隨意地選擇出的3個位置的膜厚，藉由求得該等的平均值而算出。 The film thickness of the obtained coating film can be appropriately determined according to the coating method or the total solid content concentration or viscosity of the photosensitive conductive paste, but the film thickness after drying is preferably 0.1 to 50 μm. The film thickness can be measured using a probe-type profiler such as Surfcom (registered trademark) 1400 (manufactured by Tokyo Precision Co., Ltd.). More specifically, the thicknesses of three randomly selected locations were measured with a probe-type profiler (measurement length: 1 mm, scanning speed: 0.3 mm / sec), and calculated by calculating the average of these values. .
塗布膜是進行乾燥而使溶劑揮發。就將塗布膜進行乾燥而揮發除去溶劑的方法而言，例如，可舉：藉由烘箱、熱板或者紅外線等所致的加熱乾燥及真空乾燥。加熱溫度較佳為50~180℃，加熱時間較佳為1分~數小時。 The coating film is dried to volatilize the solvent. The method of drying the coating film to volatilize and remove the solvent includes, for example, heating drying and vacuum drying by an oven, a hot plate, or infrared rays. The heating temperature is preferably 50 to 180 ° C, and the heating time is preferably 1 minute to several hours.
乾燥後的塗布膜是透過任意的圖案形成用遮罩，藉由光微影法進行曝光。就曝光的光源而言，較佳可用水銀燈的i線(365nm)、h線(405nm)或g線(436nm)。 The dried coating film was exposed by a photolithography method through a mask for arbitrary pattern formation. As for the light source for exposure, the i-line (365 nm), h-line (405 nm), or g-line (436 nm) of a mercury lamp is preferably used.
曝光後的塗布膜是使用顯影而進行顯影，並溶解除去未曝光部而獲得期望的圖案。就進行鹼性顯影時的顯影液而言，例如可舉：氫氧化四甲銨、二乙醇胺、二乙基胺基乙醇、氫氧化鈉、氫氧化鉀、碳酸鈉、碳酸鉀、三乙胺、二乙胺、甲胺、二甲胺、乙酸二甲基胺基乙酯、二甲基胺基乙醇、甲基丙烯酸二甲基胺基乙酯、環己胺、乙二胺或者己二胺的水溶液。 The exposed coating film is developed using development, and a non-exposed portion is dissolved and removed to obtain a desired pattern. Examples of the developer used in the alkaline development include tetramethylammonium hydroxide, diethanolamine, diethylaminoethanol, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, triethylamine, Diethylamine, methylamine, dimethylamine, dimethylaminoethyl acetate, dimethylaminoethanol, dimethylaminoethyl methacrylate, cyclohexylamine, ethylenediamine or hexamethylenediamine Aqueous solution.
於該等水溶液可添加：N-甲基-2-吡咯啶酮、N,N-二甲基甲醯胺、N,N-二甲基乙醯胺、二甲亞碸或者γ-丁內酯等極性溶劑；甲醇、乙醇或者異丙醇等醇類；乳酸乙酯或者丙二醇單甲醚乙酸酯等酯類；環戊酮、環己酮、異丁基酮或者甲基異丁基酮等酮類；及界面活性劑。 In these aqueous solutions, you can add: N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethylformamide or γ-butyrolactone Isopolar solvents; alcohols such as methanol, ethanol or isopropanol; esters such as ethyl lactate or propylene glycol monomethyl ether acetate; cyclopentanone, cyclohexanone, isobutyl ketone, or methyl isobutyl ketone, etc. Ketones; and surfactants.
就進行有機顯影時的顯影液而言，例如，可舉：N-甲基-2-吡咯啶酮、N-乙醯基-2-吡咯啶酮、N,N-二甲基乙醯胺、N,N-二甲基甲醯胺、二甲亞碸或者六甲基磷醯三胺(hexamethylphosphortriamide)等極性溶劑或該等極性溶劑與甲醇、乙醇、異丙醇、二甲苯、水、甲基卡必醇、及乙基卡必醇的混合溶液。 Examples of the developer used in the organic development include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N, N-dimethylacetamide, Polar solvents such as N, N-dimethylformamide, dimethylformamide or hexamethylphosphortriamide or such polar solvents with methanol, ethanol, isopropanol, xylene, water, methyl A mixed solution of carbitol and ethyl carbitol.
就顯影的方法而言，例如可舉：一邊使基板靜置或者旋轉並將顯影液噴灑在塗布膜面的方法、將基板浸漬於顯影液中的方法，及一邊將基板浸漬於顯影液中一邊施加超音波的方法。 As the development method, for example, a method in which the substrate is allowed to stand or rotate and the developer is sprayed on the coating film surface, a method in which the substrate is immersed in the developer, and a substrate is immersed in the developer Method of applying ultrasound.
藉由顯影所獲得之導電圖案，能夠施行由淋洗液進行的淋洗處理。於此處，就淋洗液，例如可舉：水或者在水添加有乙醇或者異丙醇等醇類或乳酸乙酯或者丙二醇單甲醚乙酸酯等酯類而成的水溶液。 The conductive pattern obtained by the development can be subjected to a rinsing treatment using an eluent. Here, the eluent may be, for example, water or an aqueous solution obtained by adding alcohols such as ethanol or isopropanol, or ethyl lactate or propylene glycol monomethyl ether acetate to the water.
所獲得之導電圖案，在溫度100~300℃下進行硬化。硬化的溫度較佳為120~180℃。硬化溫度若低於100℃，樹脂成分的體積收縮量不會變大，比電阻不會充分地變低。硬化的溫度若超過300℃，則在耐熱性低的基板等材料上製造導電圖案會變得困難。 The obtained conductive pattern is hardened at a temperature of 100 to 300 ° C. The curing temperature is preferably 120 to 180 ° C. When the curing temperature is lower than 100 ° C, the volume shrinkage of the resin component does not increase, and the specific resistance does not sufficiently decrease. When the curing temperature exceeds 300 ° C., it becomes difficult to produce a conductive pattern on a material such as a substrate having low heat resistance.
就把所獲得之導電圖案予以硬化的方法，例如可舉：由烘箱、惰性烘箱(inert oven)或者熱板進行的加熱乾燥、由紫外線燈、紅外線加熱器、鹵素加熱器或者氙氣閃光燈等電磁波，或者由微波進行的加熱乾燥，或者真空乾燥。所製造之導電圖案的硬度藉由加熱而變高，能夠抑制因與其它構件的接觸所致之缺損及剝離等，進一步並能夠使與基板的密接性提升。 The method for hardening the obtained conductive pattern includes, for example, heating and drying by an oven, an inert oven or a hot plate, electromagnetic waves such as an ultraviolet lamp, an infrared heater, a halogen heater, or a xenon flash lamp. Either heat drying by microwave, or vacuum drying. The hardness of the produced conductive pattern is increased by heating, and it is possible to suppress defects and peeling due to contact with other members, and further improve the adhesion with the substrate.
使用本發明之感光性導電糊所獲得之導電圖案能夠適合地使用於：觸控面板、積層陶瓷電容器(laminated ceramic capacitor)、積層電感器、太陽電池等，其中，可更適合地使用於為了窄邊框化而需求微細化之觸控面板用周圍配線。 The conductive pattern obtained by using the photosensitive conductive paste of the present invention can be suitably used in: touch panels, laminated ceramic capacitors, laminated inductors, solar cells, and the like. Among them, it can be more suitably used for narrow Peripheral wiring for touch panels that require bezels for miniaturization.
接著，關於本發明之感光性導電糊，藉由實施例進行說明。 Next, the photosensitive conductive paste of this invention is demonstrated using an Example.
於各實施例使用的評價方法如下。 The evaluation methods used in the examples are as follows.
<圖案化性的評價方法> <Evaluation method of patternability>
將感光性導電糊以使得乾燥後的膜厚成為4μm的方式塗布在PET薄膜上，在100℃的乾燥烘箱內乾燥5分鐘。把以一定的線與間隙(Line and space)(以下稱為L/S)排列而成的直線群，即將透光圖案設為1個單元，透過分別具有L/S之值不同的10種類單元的光罩，將乾燥後的塗布膜予以曝光及顯影，分別獲得L/S之值不同的10種類圖案。其後，將所獲得之10個圖案在140℃之溫度的乾燥烘箱內任一者皆進行硬化30分鐘，分別獲得L/S之值不同的10種類導電圖案。光罩具有之各單元的L/S之值，線寬L(μm)/間隔S(μm)為250/250、100/100、50/50、40/40、30/30、25/25、20/20、15/15、10/10及7/7。將所獲得之導電圖案以光學顯微鏡進行觀察。確認到是在圖案間無殘渣，且無圖案剝離之，L/S的值為最小的導電圖案。將該L/S之值設為能夠顯影的L/S之值。 The photosensitive conductive paste was coated on a PET film so that the film thickness after drying became 4 μm, and dried in a drying oven at 100 ° C. for 5 minutes. A straight line group formed by a certain line and space (hereinafter referred to as L / S), that is, a light transmission pattern is set as one unit, and 10 types of units each having different L / S values are transmitted through In the photomask, the dried coating film was exposed and developed to obtain 10 types of patterns with different L / S values. Thereafter, each of the obtained 10 patterns was cured in a drying oven at a temperature of 140 ° C. for 30 minutes, and 10 types of conductive patterns having different L / S values were obtained. The L / S value of each unit in the photomask, the line width L (μm) / space S (μm) is 250/250, 100/100, 50/50, 40/40, 30/30, 25/25, 20/20, 15/15, 10/10 and 7/7. The obtained conductive pattern was observed with an optical microscope. It was confirmed that there was no residue between the patterns, and there was no pattern peeling, and the L / S value was the smallest conductive pattern. This value of L / S is set to a value of L / S that can be developed.
曝光是使用曝光装置(PEM-6M；UNION光學股份有限公司製)以曝光量150mJ/cm2(波長365nm換算)進行全線曝光，顯影是使基板浸漬於0.2質量%之Na2CO3溶液30秒之後，施行由超純水進行的淋洗處理而進行。 Exposure was performed using an exposure device (PEM-6M; manufactured by UNION Optical Co., Ltd.) at an exposure amount of 150 mJ / cm 2 (converted to a wavelength of 365 nm). The development was performed by immersing the substrate in a 0.2 mass% Na 2 CO 3 solution for 30 seconds. Thereafter, a rinsing treatment with ultrapure water is performed.
<直進性的評價方法> <Evaluation method of linearity>
針對使用於上述之圖案化性的之評價的導電圖案之L/S之值成為20/20的透光圖案B，隨機地把於圖1所示之線寬為最粗的最大線寬1，與線寬為最細的最小線寬2分別測定10處，並求得各自的平均值。使用所獲得之「平均最大線寬」與「平均最小線寬」，基於下述式(1)算出 從圖案突出的突起的長度。針對直進性，將突起的長度低於2μm者設為「A非常佳」，將2μm以上低於4μm者設為「B佳」，將4μm以上者設為「C差」，並將「A非常地佳」、「B佳」設為合格。 For the light-transmitting pattern B in which the L / S value of the conductive pattern used in the evaluation of the patternability described above is 20/20, the line width shown in FIG. 1 is randomly set to the thickest maximum line width 1, The minimum line width 2 with the thinnest line width was measured at 10 locations, and the respective average values were obtained. Using the obtained "average maximum line width" and "average minimum line width", it is calculated based on the following formula (1) The length of the protrusion protruding from the pattern. For straightness, set the length of the protrusions below 2 μm as “A very good”, set the length of 2 μm or more and less than 4 μm as “B good”, set the length of 4 μm or more as “C difference”, and set “A very "Best place" and "B best" are passed.
突起的長度=(平均最大線寬-平均最小線寬)/2...式(1)。 The length of the protrusion = (average maximum line width-average minimum line width) / 2 ... Equation (1).
<比電阻的評價方法> <Evaluation method of specific resistance>
以使得乾燥後的膜厚成為4μm的方式將感光性導電糊塗布在PET薄膜上，將塗布膜在100℃之溫度的乾燥烘箱內乾燥5分鐘。透過具有如圖2所示之透光圖案A之光罩，將乾燥後的塗布膜進行曝光及顯影而獲得導電圖案。其後，將所獲得之導電圖案在140℃之溫度的乾燥烘箱內進行硬化30分鐘，獲得了比電阻測定用的導電圖案。所獲得之導電圖案的線寬為20μm，線長度為80mm。 A photosensitive conductive paste was applied onto the PET film so that the film thickness after drying was 4 μm, and the coating film was dried in a drying oven at a temperature of 100 ° C. for 5 minutes. A conductive pattern is obtained by exposing and developing the dried coating film through a mask having a light-transmitting pattern A as shown in FIG. 2. Then, the obtained conductive pattern was hardened in a drying oven at a temperature of 140 ° C. for 30 minutes to obtain a conductive pattern for specific resistance measurement. The obtained conductive pattern had a line width of 20 μm and a line length of 80 mm.
曝光及顯影的條件是與上述圖案化性的評價方法設為同樣。藉由電阻計將所獲得之比電阻測定用的導電圖案的各個端部連結來測定電阻值，並基於下述式(2)算出比電阻。 The conditions of exposure and development are the same as the evaluation method of the said patternability. The ends of the obtained conductive patterns for specific resistance measurement were connected by a resistance meter to measure the resistance value, and the specific resistance was calculated based on the following formula (2).
比電阻=電阻值×膜厚×線寬/線長...式(2)。 Specific resistance = resistance value × film thickness × line width / line length ... Equation (2).
於各實施例使用的材料是如下。 The materials used in the examples are as follows.
[導電性粒子(A)] [Conductive particles (A)]
體積平均粒徑為1.0μm的Ag粒子。 Ag particles having a volume average particle diameter of 1.0 μm.
[具有不飽和雙鍵的化合物(B)] [Compound (B) having an unsaturated double bond]
(合成例1：化合物(B-1)) (Synthesis Example 1: Compound (B-1))
共聚合比率(質量基準)：丙烯酸乙酯(以下，稱為EA)/甲基丙烯酸2-乙基己酯(以下，稱為2-EHMA)/苯乙烯(以下，稱為St)/甲基丙烯酸縮水甘油酯(以下，稱為GMA)/丙烯酸(以下，稱為AA)=20/40/20/5/15。 Copolymerization ratio (mass basis): ethyl acrylate (hereinafter referred to as EA) / 2-ethylhexyl methacrylate (hereinafter referred to as 2-EHMA) / styrene (hereinafter referred to as St) / methyl Glycidyl acrylate (hereinafter, referred to as GMA) / acrylic acid (hereinafter, referred to as AA) = 20/40/20/5/15.
在氮氣體環境的反應容器中，饋入150g的DMEA，使用油浴來升溫至80℃的溫度。費1小時將包含20g的EA、40g的2-EHMA、20g的St、15g的AA、0.8g的2,2’-偶氮雙異丁腈及10g的DMEA的混合物滴下於其中。滴下結束後，進一步進行6小時聚合反應。其後，添加1g的氫醌單甲醚而停止聚合反應。繼而，費0.5小時滴下包含5g的GMA、1g的三乙基苄基氯化銨(triethylbenzylammonium chloride)及10g的DMEA的混合物。滴下結束後，進一步進行2小時加成反應。利用甲醇將所獲得之反應溶液予以純化，藉此除去未反應雜質，進一步進行24小時真空乾燥，獲得化合物(B-1)。所獲得之化合物(B-1)的酸價為103mgKOH/g。 In a reaction vessel in a nitrogen atmosphere, 150 g of DMEA was fed, and the temperature was raised to 80 ° C. using an oil bath. It took 1 hour to drop a mixture containing 20 g of EA, 40 g of 2-EHMA, 20 g of St, 15 g of AA, 0.8 g of 2,2'-azobisisobutyronitrile, and 10 g of DMEA. After completion of the dropping, a polymerization reaction was further performed for 6 hours. Thereafter, 1 g of hydroquinone monomethyl ether was added to stop the polymerization reaction. Then, a mixture containing 5 g of GMA, 1 g of triethylbenzylammonium chloride, and 10 g of DMEA was dropped over 0.5 hours. After completion of the dropping, an addition reaction was further performed for 2 hours. The obtained reaction solution was purified with methanol to remove unreacted impurities, and further vacuum-dried for 24 hours to obtain a compound (B-1). The acid value of the obtained compound (B-1) was 103 mgKOH / g.
(合成例2：化合物(B-2)) (Synthesis Example 2: Compound (B-2))
在氮氣體環境的反應溶液中，饋入164g的卡必醇乙酸酯(carbitol acetate)、287g的EOCN-103S(日本化藥(股)製)、96g的AA、2g的2,6-二-三級丁基-對甲酚以及2g的三苯基膦，在98℃之溫度下使反應至反應液的酸價成為0.5mgKOH/g以下為止，獲得環氧羧酸酯化合物。繼而，在該反應液饋入57g的卡必醇乙酸酯及137g的四氫苯二甲酸酐，在95℃的溫度下使反應4小時，獲得化合物(B-2)。所獲得之化合物(B-2)的酸價為97mgKOH/g。 In a reaction solution in a nitrogen gas environment, 164 g of carbitol acetate, 287 g of EOCN-103S (manufactured by Nippon Kayaku Co., Ltd.), 96 g of AA, and 2 g of 2,6-diamine were fed. -Tributyl-p-cresol and 2 g of triphenylphosphine were reacted at a temperature of 98 ° C. until the acid value of the reaction solution became 0.5 mgKOH / g or less to obtain an epoxy carboxylic acid ester compound. Then, 57 g of carbitol acetate and 137 g of tetrahydrophthalic anhydride were fed to the reaction solution, and the reaction was performed at a temperature of 95 ° C for 4 hours to obtain a compound (B-2). The acid value of the obtained compound (B-2) was 97 mgKOH / g.
(合成例3：化合物(B-3)) (Synthesis Example 3: Compound (B-3))
在氮氣體環境的反應容器中，饋入123g的RE-310S(日本化藥(股)製)、47g的AA、0.3g的氫醌單甲醚及0.5g的三苯基膦，在98℃的溫度下使反應至反應液的酸價成為0.5mgKOH/g以下為止，獲得環氧羧酸酯化合物。其後，將252g的卡必醇乙酸酯、89g的2,2-雙(二羥甲基)-丙酸、0.4g的2-甲基氫醌及47g的螺甘油(spiroglycol)加入於該反應溶液，升溫至45℃之溫度。以使得反應溫度不超過65℃的方式，將162g的三甲基六亞甲基二異氰酸酯緩緩滴下於該溶液。滴下結束後，使反應溫度提升至80℃，藉由紅外線吸收光譜測定法，使反應6小時至2250cm-1附近的吸收消失，獲得化合物(B-3)。所獲得之化合物(B-3)的酸價為80.0mgKOH/g。 In a reaction vessel under a nitrogen atmosphere, 123 g of RE-310S (manufactured by Nippon Kayaku Co., Ltd.), 47 g of AA, 0.3 g of hydroquinone monomethyl ether, and 0.5 g of triphenylphosphine were fed, and the temperature was 98 ° C The reaction was continued until the acid value of the reaction solution became 0.5 mgKOH / g or less, and an epoxy carboxylic acid ester compound was obtained. Thereafter, 252 g of carbitol acetate, 89 g of 2,2-bis (dimethylol) -propionic acid, 0.4 g of 2-methylhydroquinone, and 47 g of spiroglycol were added thereto. The reaction solution was warmed to a temperature of 45 ° C. 162 g of trimethylhexamethylene diisocyanate was slowly dropped into the solution so that the reaction temperature did not exceed 65 ° C. After the completion of the dropping, the reaction temperature was increased to 80 ° C., and the absorption in the vicinity of 2250 cm −1 for 6 hours was eliminated by infrared absorption spectrometry to obtain compound (B-3). The acid value of the obtained compound (B-3) was 80.0 mgKOH / g.
[光聚合起始劑(C)] [Photopolymerization initiator (C)]
IRGACURE(註冊商標)OXE01(日本汽巴(Ciba Japan)(股)製，肟系化合物)(以下，稱為OXE01) IRGACURE (registered trademark) OXE01 (made by Ciba Japan (stock), oxime-based compound) (hereinafter, referred to as OXE01)
IRGACURE(註冊商標)369(日本汽巴(股)製，α-胺基烷基苯酮系化合物)(以下，稱為IC369)。 IRGACURE (registered trademark) 369 (manufactured by Ciba Corporation, α-aminoalkyl phenone compound) (hereinafter, referred to as IC369).
[熱硬化性樹脂(E)] [Thermosetting resin (E)]
環氧樹脂(E-1)：三菱化學(股)製，JER(註冊商標)828(環氧當量188) Epoxy resin (E-1): Mitsubishi Chemical Corporation, JER (registered trademark) 828 (epoxy equivalent 188)
環氧樹脂(E-2)：(股)ADEKA製，Adeka Resin(註冊商標)EPR-4030(環氧當量380) Epoxy resin (E-2): (share) Made by ADEKA, Adeka Resin (registered trademark) EPR-4030 (epoxy equivalent 380)
環氧樹脂(E-3)：三菱化學(股)製，JER(註冊商標)1002(環氧當量650)。 Epoxy resin (E-3): manufactured by Mitsubishi Chemical Corporation, JER (registered trademark) 1002 (epoxy equivalent 650).
[實施例1] [Example 1]
將10.0g的化合物(B-1)、0.50g的OXE01、5.0g的DMEA及0.5g的2-羥基吡啶置入100mL潔淨瓶(clean bottle)，利用自轉-公轉真空混合機「除泡練太郎」ARE-310(註冊商標；(股)Thinky製)進行混合，獲得16.0g的樹脂溶液(固體成分68.8質量%)。 10.0 g of the compound (B-1), 0.50 g of OXE01, 5.0 g of DMEA, and 0.5 g of 2-hydroxypyridine were placed in a 100 mL clean bottle. "ARE-310 (registered trademark; manufactured by Thinky) was mixed to obtain 16.0 g of a resin solution (solid content: 68.8% by mass).
將所獲得之16.0g的樹脂溶液與62.3g的Ag粒子混合，使用三輥磨機(EXAKT M-50；EXAKT公司製)進行混煉，獲得78.3g的感光性導電糊。於表1顯示感光性導電糊的組成。 The obtained 16.0 g of the resin solution and 62.3 g of Ag particles were mixed and kneaded using a three-roll mill (EXAKT M-50; manufactured by EXAKT) to obtain 78.3 g of a photosensitive conductive paste. Table 1 shows the composition of the photosensitive conductive paste.
使用所獲得之感光性導電糊，分別評價導電圖案的圖案化性、直進性及比電阻。成為圖案化性的評價指標之能夠顯影的L/S之值為15/15，確認到被進行了良好的圖案加工。又，導電圖案之突起的長度為2.7μm，確認到直進性為「佳」。進一步，導電圖案的比電阻為6.0×10-5Ωcm。將評價結果顯示於表2。 The obtained photosensitive conductive paste was used to evaluate the patternability, linearity, and specific resistance of the conductive pattern, respectively. The developable L / S value serving as an evaluation index of patternability was 15/15, and it was confirmed that good pattern processing was performed. The length of the protrusions of the conductive pattern was 2.7 μm, and it was confirmed that the straightness was “good”. Further, the specific resistance of the conductive pattern was 6.0 × 10 -5 Ωcm. The evaluation results are shown in Table 2.
[實施例2~11] [Examples 2 to 11]
以與實施例1相同的方法製作在表1所示之組成的感光性導電糊，並與實施例1同樣地進行評價。將評價結果顯示於表2。 A photosensitive conductive paste having the composition shown in Table 1 was produced in the same manner as in Example 1 and evaluated in the same manner as in Example 1. The evaluation results are shown in Table 2.
[比較例1~2] [Comparative Examples 1 to 2]
以與實施例1相同的方法製造在表1所示之組成的感光性導電糊，並與實施例1同樣地進行評價。將評價結果顯示於表2。 A photosensitive conductive paste having a composition shown in Table 1 was produced in the same manner as in Example 1 and evaluated in the same manner as in Example 1. The evaluation results are shown in Table 2.
如於表2所示般，實施例1~11的感光性導電糊，任一者皆能製造圖案化性、直進性及導電性優良的導電圖案。另一方面，比較例1及2的感光性導電糊，無法製作直進性優良的導電圖案，且、比電阻高。 As shown in Table 2, each of the photosensitive conductive pastes of Examples 1 to 11 can produce a conductive pattern having excellent patternability, linearity, and conductivity. On the other hand, the photosensitive conductive pastes of Comparative Examples 1 and 2 were unable to produce a conductive pattern having excellent straightness and had a high specific resistance.
本發明之感光性導電糊能夠適合地利用來用以製造觸控面板用之周圍配線等的導電圖案。 The photosensitive conductive paste of the present invention can be suitably used to produce a conductive pattern such as a peripheral wiring for a touch panel.
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| JP3239772B2 (en) * | 1995-10-09 | 2001-12-17 | 信越化学工業株式会社 | Chemically amplified positive resist material |
| JP4048777B2 (en) * | 2001-12-27 | 2008-02-20 | 東レ株式会社 | Transparent conductive paste, display member and plasma display panel using the same, and method for manufacturing plasma display panel member |
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| TW200420694A (en) * | 2003-04-15 | 2004-10-16 | Taiyo Ink Mfg Co Ltd | Photo-curable thermosetting conductive composition, conductive circuit using the conductive composition, and forming method thereof |
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| JP5650363B2 (en) * | 2007-04-27 | 2015-01-07 | 信越ポリマー株式会社 | Conductive circuit and method for forming the same |
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| WO2014208445A1 (en) * | 2013-06-27 | 2014-12-31 | 東レ株式会社 | Electroconductive paste, method for manufacturing an electroconductive pattern, and touch panel |
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