TWI704417B - Photosensitive conductive paste and method for manufacturing substrate with conductive pattern - Google Patents
Photosensitive conductive paste and method for manufacturing substrate 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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- Position Input By Displaying (AREA)
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Abstract
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)、及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 having an unsaturated double bond (B), a photopolymerization initiator (C), and a compound having a hydroxypyridine skeleton in one molecule (D).
本發明提供一種感光性導電糊,其能夠製造直進性良好,且表現高導電性的微細導電圖案。 The present invention provides a photosensitive conductive paste capable of producing a fine conductive pattern with good straightness and high conductivity.
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 producing a substrate with 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 the photolithographic method. Regarding the conductive paste to be used, a photosensitive conductive paste obtained by dispersing a conductive filler in a photosensitive organic component has been developed and proposed (see
專利文獻1 國際公開第2013/108696號小冊
專利文獻2 國際公開第2013/146107號小冊
專利文獻3 日本特開2013-196998號公報 Patent Document 3 JP 2013-196998 A
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 straightness is formed by adding a UV absorber, even if the specific resistance value is the same as before the addition, the line 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 which forms a fine conductive pattern with good linearity and exhibits high conductivity.
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, they found that moderately reducing the reactivity of organic components contributes to the formation of fine conductive patterns with good straightness and high electrical conductivity. That is, by appropriately reducing the reactivity of the organic component, it becomes possible to suppress the riot of radical polymerization during exposure, and to form a fine conductive pattern with good straightness. In addition, since the reaction of the organic component does not progress excessively at the time point after the exposure, curing shrinkage during heating occurs, and the contact probability of conductive fillers increases, and high conductivity is exhibited. It has been found that by containing a compound having a hydroxypyridine skeleton as an organic component, the reactivity of the organic component can be moderately suppressed, the formation of a fine conductive pattern with good linearity can be achieved, and both high conductivity can be exhibited, and the present invention has been completed.
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 having an unsaturated double bond (B), 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 aforementioned compound (D) having a hydroxypyridine skeleton in one molecule is a compound having a hydroxymethyl 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 relative to 100 parts by mass of the compound (B) having an unsaturated double bond is 0.3~ 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)。 According to a preferable aspect of the photosensitive conductive paste of the present invention, it 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 preferred 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 aforementioned photosensitive conductive paste on a substrate and then curing it 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, a photosensitive conductive paste with a low specific resistance value can be obtained, 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 manufacturing conductive patterns such as peripheral wiring for touch panels.
1‧‧‧最大線寬 1‧‧‧Maximum line width
2‧‧‧最小線寬 2‧‧‧Minimum line width
A‧‧‧透光圖案 A‧‧‧Light transmission pattern
B‧‧‧使用L/S=20/20之光罩而製作出的導電圖案 B‧‧‧Conductive pattern made by using L/S=20/20 mask
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 the measurement locations in the straightness evaluation of the examples.
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 the light transmission pattern of the photomask 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 having an unsaturated double bond (B), 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 in contact with each other due to the curing shrinkage 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 type of indium can be used alone, as an alloy, or as a mixed powder. In the same way, conductive particles obtained by coating the surfaces of insulating particles or conductive particles such as resins and inorganic oxides with the aforementioned components can also be used. Among them, from the viewpoint of conductivity, silver, gold, or copper is preferable, and from the viewpoint of cost and stability, it is more preferable to use silver.
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。 Regarding the shape of the conductive particle (A), a value obtained by dividing the long axis length by the short axis length, that is, the aspect ratio is preferably 1.0 to 3.0, and more preferably 1.0 to 2.0. If the aspect ratio of the conductive particles (A) is 1.0 or more, the contact probability of the conductive particles (A) can be more improved. On the other hand, when the aspect ratio of the conductive particles (A) is 2.0 or less, when the wiring is formed by the photolithography method, the exposure light is not easily shielded, and the development margin can be wide.
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) with a scanning electron microscope (SEM) or a transmission electron microscope (TEM) at a magnification of 15000 times, and randomly select 100 primary particles of the conductive particles , Measure each major axis length and minor axis length, and obtain the aspect ratio 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 size of the conductive particles (A) is preferably 0.05 to 5.0 μm, more preferably 0.1 to 2.0 μm. When the particle size of the conductive particles (A) is 0.05 μm or more, the interaction between the particles is weak, and the dispersion state of the conductive particles (A) in the paste is easily maintained. If the particle size of the conductive particles (A) is 5.0 μm or less, the surface smoothness, pattern precision, and dimensional precision 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 size of the conductive particles (A) contained in the photosensitive conductive paste was observed with an electron microscope, randomly selected 20 primary particles of conductive particles, measured the maximum width of each, and obtained the average value 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. If the content of the conductive particles (A) relative to the total solid content is 60% by mass or more, the probability of contact between the conductive particles (A) during curing increases, and the specific resistance and the probability of wire breakage of the manufactured conductive pattern are reduced . If 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. The term "all solids" as used herein refers to all components of the photosensitive conductive paste except for 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。 The compound (B) having an unsaturated double bond contained in the photosensitive conductive paste of the present invention includes, for example, styrene, p-methylstyrene, o-methylstyrene, m-methylstyrene, Styrenes such as α-methylstyrene, chloromethylstyrene or hydroxymethylstyrene, 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。 For acrylic monomers, for example, 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 Ester, lauryl acrylate, 2-methoxyethyl acrylate, methoxyglycol acrylate, methoxydiethylene glycol acrylate, octafluoropentyl acrylate, phenoxyethyl acrylate, stearyl acrylate 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), allylated cyclohexyl diacrylate, methoxylated cyclohexyl diacrylate, 1,4-butanediol diacrylate, 1,3-butanediol diacrylate, ethyl Glycol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, polyethylene glycol diacrylate, neopentyl glycol diacrylate, propylene glycol diacrylate, polypropylene glycol diacrylate or triethylene glycol diacrylate Glycerol diacrylate, trimethylolpropane triacrylate, di-trimethylolpropane tetraacrylate, dineopentaerythritol monohydroxy pentaacrylate Ester or dineopentaerythritol hexaacrylate, acrylamide, N-methoxymethacrylamide, N-ethoxymethacrylamide, N-n-butoxymethacrylamide or N -Isobutoxy methacrylamide, acrylic acid adduct of ethylene glycol diglycidyl ether with hydroxyl group formed by opening the epoxy group with unsaturated acid, acrylic acid of diethylene glycol diglycidyl ether Adducts, acrylic acid adducts of neopentyl glycol diglycidyl ether, acrylic acid adducts of glycerol diglycidyl ether, acrylic acid adducts of bisphenol A diglycidyl ether, acrylic acid adducts of bisphenol F Or epoxy acrylate monomers such as acrylic adducts of cresol novolac or γ-acryloxypropyl trimethoxysilane, or compounds obtained by substituting these acryloxy groups with methacryloxy groups .
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 refers to a copolymer containing an acrylic monomer as a monomer that can be used, that is, a copolymerization component. 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. Examples of unsaturated acids include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, or vinyl acetate, and anhydrides of these. The acid value of the obtained acrylic copolymer can be adjusted by the amount of unsaturated acid used. Furthermore, by reacting the 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 the side chain can be obtained Department of copolymers.
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 carboxylate compound is a compound that can be synthesized using an epoxy compound and a carboxyl compound having an unsaturated double bond as starting materials. Can become the epoxy compound of the starting material and Examples include: glycidyl ethers, alicyclic epoxy resins, glycidyl esters, glycidylamines or epoxy resins, 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 two Glycidyl ether, hydrogenated bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether, bisphenol diglycidyl ether, diphenol diglycidyl ether, tetramethyl diphenol glycidyl ether Glyceryl ether, trimethylolpropane triglycidyl ether, 3',4'-epoxycyclohexylmethyl-3,4-epoxycyclohexane carboxylate, and tributyl glycidylamine. In addition, examples of the carboxy 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。 The epoxy carboxylate compound and the polybasic acid anhydride are reacted to adjust the acid value of the epoxy carboxylate compound. For polybasic acid anhydrides, for example, succinic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, itaconic anhydride, 3-methyltetrahydrophthalic anhydride, 4-methyl Base-hexahydrophthalic anhydride, trimellitic anhydride and maleic anhydride. By reacting the carboxyl group of the epoxy carboxylate compound that reacts with the above-mentioned polybasic acid anhydride with a compound having an unsaturated double bond such as glycidyl (meth)acrylate, the reactivity of the epoxy carboxylate compound can be adjusted 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 the hydroxyl group of the epoxy carboxylate compound with the diisocyanate compound, urethane can be carried out. As for the diisocyanate compound, for example, hexamethylene diisocyanate, Tetramethylxylene diisocyanate, naphthalene-1,5-diisocyanate, tolidene diisocyanate, trimethylhexamethylene diisocyanate, isophorone diisocyanate, allyl cyano 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 optimize alkali solubility, 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 part can be suppressed. When the acid value of the compound (B) having an unsaturated double bond is 250 mgKOH/g or less, the allowable development 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-啉基丙烷-1-酮、2-苄基-2-二甲基胺基-1-(4-啉基苯基)-丁烷-1-酮、2-二甲基胺基-2-(4-甲基苄基)-1-(4-啉-4-基-苯基)丁烷-1-酮等α-胺基烷基苯酮系化合物;2,4,6-三甲基苯甲醯基-二苯基-氧化膦、雙(2,4,6-三甲基苯甲醯基)-苯基氧化膦等氧化膦系化合物;萘磺醯氯、喹啉磺醯氯等芳香族磺醯氯系化合物;蒽醌、2-三級丁基蒽醌、2-戊基蒽醌、β-氯蒽醌、蒽酮、苯并蒽酮、二苯并環庚酮(dibenzosuberone)、亞甲基蒽酮、2,6-雙(對疊氮基亞苄基)環己酮、6-雙(對疊氮基亞苄基)-4-甲基環己酮、2,6-雙(對疊氮基亞苄基)環己酮、6-雙(對疊氮基亞苄基)-4-甲基環己酮、N-苯基硫吖啶酮、4,4’-偶氮雙異丁腈、二苯基二硫化物、苯并噻唑二硫化物、三苯基膦、樟腦醌、四溴化碳、三溴苯基碸、過氧化苯甲醯等,特佳可使用光感度高的肟系化合物。 The photopolymerization initiator (C) contained in the photosensitive conductive paste of the present invention includes, for example, benzophenone, methyl phthalate, 4,4'-bis(dimethyl Amino) benzophenone, 4,4'-bis(diethylamino) benzophenone, 4,4'-dichlorobenzophenone, 4-benzyl-4'-methanone Benzophenone derivatives such as benzophenone and quinone; p-tertiary butyldichloroacetophenone, 4-azidobenzylidene acetophenone, 2,2'-diethoxybenzene Acetophenone derivatives such as ethyl ketone; thioxanthone derivatives such as thioxanthone, 2-methylthioxanthone, 2-chlorothioxanthone, 2-isopropylthioxanthone and diethylthioxanthone; Benzyl derivatives such as benzyl, benzyl dimethyl ketal, and benzyl-β-methoxyethyl acetal; benzoin derivatives such as benzoin, benzoin methyl ether, and benzoin butyl ether ; 1,2-octanedione-1-[4-(phenylsulfide)-2-(O-benzyl oxime)], ethyl ketone-1-[9-ethyl-6-(2- Methylbenzyl)-9H-carbazol-3-yl)-1-(O-acetoxime), 1-phenyl-1,2-butanedione-2-(O-methoxycarbonyl) )Oxime, 1-phenyl-propanedione-2-(O-ethoxycarbonyl)oxime, 1-phenyl-propanedione-2-(O-benzyl)oxime, 1,3-bis Phenyl-glycerol-2-(O-ethoxycarbonyl)oxime, 1-phenyl-3-ethoxy-glycerol-2-(O-benzyl)oxime and other oxime compounds; 2-hydroxy-2-methyl-1-phenyl-propane-1-one, 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propane -1-ketone and other α-hydroxy ketone compounds; 2-methyl-(4-methylphenylthio)-2- Alkylpropane-1-one, 2-benzyl-2-dimethylamino-1-(4- Alkylphenyl)-butane-1-one, 2-dimethylamino-2-(4-methylbenzyl)-1-(4- Alpha-aminoalkylphenone compounds such as lin-4-yl-phenyl)butan-1-one; 2,4,6-trimethylbenzyl-diphenyl-phosphine oxide, bis( 2,4,6-trimethylbenzyl)-phenylphosphine oxide and other phosphine oxide compounds; naphthalenesulfonyl chloride, quinolinesulfonyl chloride and other aromatic sulfonyl chloride compounds; anthraquinone, 2-tri Grade butyl anthraquinone, 2-pentyl anthraquinone, β-chloroanthraquinone, anthrone, benzoanthrone, dibenzosuberone, methylene anthrone, 2,6-bis(p) Azidobenzylidene) cyclohexanone, 6-bis(p-azidobenzylidene)-4-methylcyclohexanone, 2,6-bis(p-azidobenzylidene)cyclohexanone, 6-bis(p-azidobenzylidene)-4-methylcyclohexanone, N-phenylthioacridone, 4,4'-azobisisobutyronitrile, diphenyl disulfide, benzene Thiazole disulfide, triphenylphosphine, camphorquinone, carbon tetrabromide, tribromophenyl sulfide, benzyl peroxide, etc., especially oxime compounds with high photosensitivity can be used.
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 relative to 100 parts by mass of the compound (B) having an unsaturated double bond. When the content of the photopolymerization initiator (C) is 0.05 parts by mass or more with respect to 100 parts by mass of the compound (B) having an unsaturated double bond, the curing density of the exposed area increases, 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, excess light absorption due to the photopolymerization initiator (C) on the upper portion of the coating film obtained by applying the conductive paste is suppressed. As a result, the reduction in adhesion to the substrate due to the manufactured conductive pattern becoming an inverted tapered 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。 As a sensitizer, for example, 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) Amino) chalcone, p-dimethyl amino cinnamylidene indanone (p-dimethyl amino cinnamylidene indanone), p-dimethylamino benzylidene indanone, 2-(p-dimethylamino cinnamylidene indanone) Methylaminophenyl vinylene) isonaphththiazole, 1,3-bis(4-dimethylaminophenyl vinylene) isonaphththiazole, 1,3-bis(4-dimethylamino) Benzylidene)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- Benzylthiotetrazole, and 1-phenyl-5-ethoxycarbonylthiotetrazole.
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 relative to 100 parts by mass of the compound (B) having an unsaturated double bond. Relative to 100 parts by mass of the compound (B) having an unsaturated double bond, the content of the sensitizer is If it is 0.05 parts by mass or more, the light sensitivity is improved. When the content of the sensitizer is 10 parts by mass or less with respect to 100 parts by mass of the compound (B) having an unsaturated double bond, excess light absorption is suppressed on the upper part of the coating film obtained by applying the conductive paste. As a result, the manufactured conductive pattern becomes an inverted tapered shape, and the 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。 The compound (D) having a hydroxypyridine skeleton in one molecule contained in the photosensitive conductive paste of the present invention includes, for example, 2-hydroxypyridine, 3-hydroxypyridine, 4-hydroxypyridine, 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-3-pyridinol), 2-hydroxymethyl-6-methyl-3-pyridinol, 2,6-bis( (Hydroxymethyl)-3-pyridinol, ginkgotoxin, pyridoxine dicaprylate, pyridoxal oxime, 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 are not too strong because of the reaction inhibition effect of organic components, and the development limit of the conductive pattern is not easily deteriorated.
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 0.3-10 parts by weight, and more preferably 0.5-5 parts by weight relative to 100 parts by weight 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 with respect to 100 parts by mass of the compound (B) having an unsaturated double bond, it will prevent the riot of radical reactions due to exposure to light. The straightness of the conductive pattern is improved, and since the curing of the resin component of the conductive pattern does not proceed excessively at the time point before curing, the curing shrinkage during curing is not hindered, and the probability of contact between the conductive particles (A) is increased, The specific resistance value will decrease. If the content of the compound (D) having a hydroxypyridine skeleton in one molecule is 10 parts by mass or less relative to 100 parts by mass of the compound (B) having an unsaturated double bond, the photoradical reaction will not be 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. Regarding the thermosetting resin (E), among them, epoxy resin is preferred, and among epoxy resins, epoxy resin having an epoxy equivalent of 150 to 500 g/equivalent is preferred. By setting the epoxy equivalent of the epoxy resin to 150 g/equivalent or more, a photosensitive conductive paste with storage stability of the 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 a resin film and a glass substrate 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 epoxy equivalent refers to the mass of a resin containing 1 equivalent of epoxy groups, and is obtained by dividing the molecular weight obtained 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 in the range of 1 to 100 parts by mass, and more preferably 30 to 80 parts by mass relative to 100 parts by mass of the compound (B) having an unsaturated double bond. With respect to 100 parts by weight of the compound (B) having an unsaturated double bond, the content of the epoxy resin is set to 1 part by mass or more, so that the effect of improving the adhesion is easily fully exhibited. If the content of the compound (B) having an unsaturated double bond is 100 parts by mass or less, a photosensitive conductive paste having particularly high storage stability of the coating film can be obtained.
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。 Regarding the epoxy resin, those having an epoxy equivalent in the range of 150 to 500 g/equivalent are preferable, and those in the range of 200 to 500 g/equivalent are more preferable. Specific examples include: glycol modified epoxy resin, bisphenol A epoxy resin, brominated epoxy resin, bisphenol F epoxy resin, novolac epoxy resin, alicyclic epoxy resin Epoxy resin, glycidylamine type epoxy resin, glycidyl ether type epoxy resin, and heterocyclic epoxy resin, etc.
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 solvents include: N,N-dimethylacetamide, N,N-dimethylformamide, N-methyl-2-pyrrolidone, dimethylimidazolidinone, dimethylsulfoxide , 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, diethylene glycol, and 2,2,4,-trimethyl-1,3-pentanediol monoisobutyrate are preferably solvents with a boiling point of 150°C or higher. If 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。 As long as the desired characteristics are not impaired, the photosensitive conductive paste of the present invention can be made to contain a non-photosensitive polymer without unsaturated double bonds in the molecule, a plasticizer, a leveling agent, and an interface active Additives such as 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。 Examples of non-photosensitive polymers include polyethylene terephthalate, polyimide precursors, and ring-closed polyimides.
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。 As the plasticizer, for example, dibutyl phthalate, dioctyl phthalate, polyethylene glycol and glycerin can be mentioned.
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, a special vinyl polymer and a special acrylic polymer 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-methacryloxypropyl Trimethoxysilane, 3-glycidoxypropyltrimethoxysilane (3-glycidoxypropyltrimethoxysilane), and vinyl trimethoxysilane.
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 manufactured using a disperser or kneader such as a three-roll mill, a ball mill, or a planetary ball mill.
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。 The method for manufacturing a substrate with a conductive pattern of the present invention is to apply the photosensitive conductive paste of the present invention on the substrate, dry, expose and develop, and then cure it 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 applying the photosensitive conductive paste of the present invention on a substrate. Examples of substrates coated with photosensitive conductive paste include polyethylene terephthalate film (hereinafter referred to as PET film), polyimide film, polyester film, aramid film, epoxy Resin substrates, polyetherimide resin substrates, polyetherketone resin substrates, polycarbonate resin substrates, glass substrates, silicon wafers, alumina substrates, aluminum nitride substrates, silicon carbide substrates, decorative layer forming substrates, and The insulating layer forms the 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 of applying the photosensitive conductive paste of the present invention to a substrate includes, for example, spin coating using a spinner, spray coating, roll coating, screen printing, or use of a blade coater (blade coater), 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 0.1-50 μm. The film thickness can be measured using a probe profiler such as Surfcom (registered trademark) 1400 (manufactured by Tokyo Seimitsu Co., Ltd.). More specifically, the film thickness of three randomly selected positions is measured with a probe profiler (measurement length: 1mm, scanning speed: 0.3mm/sec), and the average value is calculated. .
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, heat 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 is exposed through an arbitrary pattern forming mask and is exposed by photolithography. As for the light source for exposure, the i-line (365nm), h-line (405nm) or g-line (436nm) 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 coated film after exposure is developed using development, and the unexposed part is dissolved and removed to obtain a desired pattern. As for the developer during alkaline development, for example, 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。 To these aqueous solutions can be added: N-methyl-2-pyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethylsulfide or γ-butyrolactone And other polar 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。 As for the developer for organic development, for example, N-methyl-2-pyrrolidone, N-acetyl-2-pyrrolidone, N,N-dimethylacetamide, Polar solvents such as N,N-dimethylformamide, dimethylsulfide, or hexamethylphosphortriamide, or such polar solvents and 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。 The development method includes, for example, a method of allowing the substrate to stand or rotate and spraying the developer on the surface of the coating film, a method of immersing the substrate in the developer, and immersing the substrate in the developer. The 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 development can be rinsed with a rinse liquid. Here, the rinsing liquid includes, for example, water or an aqueous solution obtained by adding alcohols such as ethanol or isopropanol to water, or esters such as ethyl lactate or propylene glycol monomethyl ether acetate.
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 cured at a temperature of 100~300℃. The curing temperature is preferably 120 to 180°C. If the curing temperature is lower than 100°C, the volume shrinkage of the resin component does not increase, and the specific resistance does not decrease sufficiently. If the curing temperature exceeds 300°C, it becomes difficult to manufacture conductive patterns on materials such as substrates with 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 of hardening the obtained conductive pattern includes, for example, heating and drying by an oven, inert oven, or hot plate, and electromagnetic waves such as ultraviolet lamps, infrared heaters, halogen heaters, or xenon flash lamps. Either heating and drying by microwave or vacuum drying. The hardness of the produced conductive pattern is increased by heating, it is possible to suppress chipping and peeling due to contact with other members, and to further improve the adhesion to 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, etc. Among them, it can be more suitably used for narrow Peripheral wiring for touch panels that require miniaturization due to frame size.
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 the present invention will be described with examples.
於各實施例使用的評價方法如下。 The evaluation method used in each example is as follows.
<圖案化性的評價方法> <Method for evaluating patterning properties>
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 the 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 group of straight lines arranged with a certain line and space (hereinafter referred to as L/S), that is, the light transmission pattern is set as one unit, and 10 types of units with different values of L/S are passed through Expose and develop the dried coating film to obtain 10 types of patterns with different L/S values. After that, the obtained 10 patterns were cured in a drying oven at a temperature of 140° C. for 30 minutes to obtain 10 types of conductive patterns with different L/S values. The value of L/S of each unit of the mask, 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 no pattern peeling, and the L/S value was the smallest conductive pattern. Let the value of L/S be the 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 is to use an exposure device (PEM-6M; manufactured by UNION Optical Co., Ltd.) to perform full-line exposure with an exposure amount of 150mJ/cm 2 (converted to a wavelength of 365nm). Development is to immerse the substrate in a 0.2 mass% Na 2 CO 3 solution for 30 seconds After that, rinsing treatment with ultrapure water is performed.
<直進性的評價方法> <Method of evaluating straightness>
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 whose L/S value of the conductive pattern used in the evaluation of the patternability is 20/20, the line width shown in FIG. 1 is randomly set to the thickest
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。 The photosensitive conductive paste was coated on the PET film so that the film thickness after drying became 4 μm, and the coated film was dried in a drying oven at a temperature of 100° C. for 5 minutes. Through the photomask with the light-transmitting pattern A shown in FIG. 2, the dried coating film is exposed and developed to obtain a conductive pattern. After that, the obtained conductive pattern was cured in a drying oven at a temperature of 140° C. for 30 minutes to obtain a conductive pattern for measuring specific resistance. The line width of the obtained conductive pattern was 20 μm, and the line length was 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 above-mentioned evaluation method of patternability. The resistance value was measured by connecting the respective ends of the obtained conductive pattern for measuring the specific resistance with a resistance meter, 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 each example 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 with a volume average particle diameter of 1.0 μm.
[具有不飽和雙鍵的化合物(B)] [Compound with unsaturated double bond (B)]
(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 (based on mass): 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 an oil bath was used to raise the temperature to 80°C. 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 was dropped in 1 hour. After the dropping, the polymerization reaction was further carried out for 6 hours. After that, 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 (triethylbenzylammonium chloride), and 10 g of DMEA was dropped over 0.5 hours. After completion of the dropping, the addition reaction was further carried out for 2 hours. The obtained reaction solution was purified with methanol to remove unreacted impurities, and further subjected to vacuum drying for 24 hours to obtain 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 the reaction solution in a nitrogen atmosphere, 164 g of carbitol acetate, 287 g of EOCN-103S (manufactured by Nippon Kayaku Co., Ltd.), 96 g of AA, 2 g of 2,6-di -Tertiary butyl-p-cresol and 2 g of triphenylphosphine are reacted at a temperature of 98°C until the acid value of the reaction liquid becomes 0.5 mgKOH/g or less to obtain an epoxy carboxylate compound. Then, 57 g of carbitol acetate and 137 g of tetrahydrophthalic anhydride were fed into the reaction liquid, and the reaction was carried out 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 in a nitrogen atmosphere, 123g of RE-310S (manufactured by Nippon Kayaku Co., Ltd.), 47g of AA, 0.3g of hydroquinone monomethyl ether and 0.5g of triphenylphosphine were fed into the reaction vessel at 98°C. The reaction was allowed to proceed at a temperature of 1500 until the acid value of the reaction liquid became 0.5 mgKOH/g or less to obtain an epoxy carboxylate compound. 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 to the The reaction solution was heated to a temperature of 45°C. 162 g of trimethylhexamethylene diisocyanate was slowly dropped onto the solution so that the reaction temperature did not exceed 65°C. After completion of the dropping, the reaction temperature was raised to 80°C, and the absorption at around 2250 cm -1 after 6 hours of reaction 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 (manufactured by Ciba Japan Co., Ltd., 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 Co., Ltd., α-aminoalkylphenone 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): manufactured by 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): (Stock) ADEKA product, 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%)。 Put 10.0g of compound (B-1), 0.50g of OXE01, 5.0g of DMEA, and 0.5g of 2-hydroxypyridine into a 100mL clean bottle, and use a rotation-revolution vacuum mixer "Defoaming Nintaro" "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 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。 Using the obtained photosensitive conductive paste, the patternability, linearity, and specific resistance of the conductive pattern were evaluated. The value of developable L/S, which is an evaluation index of patternability, was 15/15, and it was confirmed that good patterning was performed. In addition, the length of the protrusion 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 is 6.0×10 -5 Ωcm. The evaluation results are shown in Table 2.
[實施例2~11] [Examples 2~11]
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 1~2]
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。 The photosensitive conductive paste of the composition shown in Table 1 was produced by the same method as Example 1, and it evaluated similarly to 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, any of the photosensitive conductive pastes of Examples 1 to 11 can produce conductive patterns with excellent patternability, linearity, and conductivity. On the other hand, the photosensitive conductive pastes of Comparative Examples 1 and 2 could not produce a conductive pattern with excellent linearity, and had 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 manufacture conductive patterns such as peripheral wiring for touch panels.
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