TW201428773A - Conductive composition, electrode, plasma display panel and touch panel - Google Patents
Conductive composition, electrode, plasma display panel and touch panel Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/08—Metals
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/20—Conductive material dispersed in non-conductive organic material
- H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
- H01J11/00—Gas-filled discharge tubes with alternating current induction of the discharge, e.g. alternating current plasma display panels [AC-PDP]; Gas-filled discharge tubes without any main electrode inside the vessel; Gas-filled discharge tubes with at least one main electrode outside the vessel
- H01J11/20—Constructional details
- H01J11/22—Electrodes, e.g. special shape, material or configuration
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/08—Metals
- C08K2003/0812—Aluminium
Abstract
Description
本發明關於一種導電性組成物、電極、電漿顯示面板(以下亦稱為「PDP」)及觸控面板，詳細而言關於一種含鋁粒子，燒成後的導電性、耐酸性、與基材的密著性優異的導電性組成物、使用該組成物的電極、及具有該電極的PDP、觸控面板。 The present invention relates to a conductive composition, an electrode, a plasma display panel (hereinafter also referred to as "PDP"), and a touch panel, and more particularly to an aluminum-containing particle, which is electrically conductive, acid-resistant, and base-based after firing. A conductive composition excellent in adhesion of a material, an electrode using the composition, a PDP having the electrode, and a touch panel.
含鋁的導電性組成物，即所謂導電性糊劑，一直被使用作為PDP、太陽能電池、陶瓷電容等之中的電極材料，從成本層面等來考量，過去以來都被檢討作為含有金或銀這些貴金屬的導電性組成物的代替品。 The conductive composition containing aluminum, which is a conductive paste, has been used as an electrode material among PDPs, solar cells, ceramic capacitors, etc., and has been reviewed as a gold or silver in the past. A substitute for the conductive composition of these precious metals.
為了有效地取得太陽能電池所產生的電力，會在矽晶圓的背面，亦即與受光面相反側的整個表面塗佈含鋁的導電性組成物。若將其以高溫燒成，則會形成鋁．矽合金層，進一步在其下形成有鋁擴散的p+層。 In order to efficiently obtain the electric power generated by the solar cell, an aluminum-containing conductive composition is applied to the back surface of the germanium wafer, that is, the entire surface opposite to the light receiving surface. If it is fired at a high temperature, aluminum will be formed. The tantalum alloy layer is further formed with a p + layer of aluminum diffusion under it.
在PDP之中，為了構成前面玻璃基板上的顯示電極中的輔助電極及背面玻璃基板上的定址電極而使用了含鋁的導電性組成物。輔助電極、定址電極是在各個玻璃基板 上呈條紋狀且互相垂直地形成。另外，任一電極皆以數百μm左右的細間距來形成，然而特別要求定址電極具有高精細度。 In the PDP, an aluminum-containing conductive composition is used to form an auxiliary electrode in the display electrode on the front glass substrate and an address electrode on the back glass substrate. Auxiliary electrode, address electrode is on each glass substrate The strips are striped and formed perpendicular to each other. Further, any of the electrodes is formed with a fine pitch of about several hundred μm, but it is particularly required that the addressed electrode has high definition.
在PDP用的電極之中，導電性在電極圖型的微細化或薄膜化、降低消耗電力等方面是重要的特性。然而，鋁與銀或金相比，導電性較低。甚至鋁會有容易氧化，在燒成等過程中的氧化造成導電性降低的問題，因此目前已經有各文獻提出其解決方法。例如在專利文獻1中，揭示了一種玻璃粉末的量較多的含鋁感光性導電糊劑。 Among the electrodes for PDP, conductivity is an important characteristic in terms of miniaturization or thinning of the electrode pattern, reduction in power consumption, and the like. However, aluminum is less conductive than silver or gold. Even aluminum has a problem that it is easily oxidized, and oxidation during firing or the like causes a decrease in conductivity. Therefore, various methods have been proposed in the literature. For example, Patent Document 1 discloses an aluminum-containing photosensitive conductive paste having a large amount of glass powder.
專利文獻1：日本特許第4862962號公報 Patent Document 1: Japanese Patent No. 4862692
鋁由於容易氧化，因此鋁粒子的表面會被自然氧化的覆膜所覆蓋。因此，導電性組成物通常是藉由燒成而將有機成分燒除以表現出導電性，然而在含鋁粒子的導電性樹脂組成物中，在燒成後鋁粒子彼此的界面也不會融合、結著，會有無法得到所希望的導電性的情形。 Since aluminum is easily oxidized, the surface of the aluminum particles is covered by a naturally oxidized film. Therefore, the conductive composition usually burns the organic component by firing to exhibit conductivity. However, in the conductive resin composition containing aluminum particles, the interface between the aluminum particles does not fuse after firing. If it is closed, there will be a situation where the desired conductivity cannot be obtained.
另一方面，在電漿顯示器背板的製造步驟中，在定址電極上塗佈介電體層且進行燒成之後，構成了間隔壁材(barrier rib)。此間隔壁材一般而言是藉由利用酸的化學蝕刻來進行形狀加工，而會有蝕刻劑滲透至定址電極的 顧慮，因此要求定址電極所使用的導電性組成物具有高耐酸性。另外，若電極與基材的密著性不佳，則會發生電極的剝落等，而可能會成為製品不良的原因，因此要求導電性組成物與基材的密著性優異。 On the other hand, in the manufacturing step of the plasma display back sheet, after the dielectric layer is applied to the address electrode and fired, a barrier rib is formed. The partition wall material is generally shaped by chemical etching using an acid, and an etchant is infiltrated into the addressed electrode. It is a concern that the conductive composition used for the address electrode is required to have high acid resistance. Further, when the adhesion between the electrode and the substrate is not good, peeling of the electrode or the like may occur, which may cause a defect in the product. Therefore, it is required that the conductive composition and the substrate have excellent adhesion.
於是本發明之目的在於提供一種含鋁粒子，燒成後的導電性、耐酸性、與基材的密著性優異的導電性組成物、使用該組成物的電極、PDP及觸控面板。 Accordingly, an object of the present invention is to provide a conductive composition containing aluminum particles, which is excellent in electrical conductivity, acid resistance, and adhesion to a substrate after firing, an electrode using the composition, a PDP, and a touch panel.
本發明人為了解決上述課題潛心檢討的結果，發現藉由在含鋁粒子的導電性組成物之中，使用熱分解終點在特定溫度範圍內之樹脂，可解決上述課題，而使本發明達到完成。 In order to solve the above problems, the present inventors have found that by using a resin having a thermal decomposition end point in a specific temperature range among the conductive compositions containing aluminum particles, the above problems can be solved and the present invention can be completed. .
亦即，本發明之導電性組成物，其特徵為含有(A)鋁粒子與(B)熱分解終點在500~650℃之範圍內之樹脂。 That is, the conductive composition of the present invention is characterized by containing (A) aluminum particles and (B) a resin having a thermal decomposition end point in the range of 500 to 650 °C.
本發明之導電性組成物，其中前述(B)熱分解終點在500~650℃之範圍內之樹脂係以具有雙酚構造之樹脂、聚乙烯縮醛樹脂、具有苯酚酚醛構造之樹脂、及具有甲酚酚醛構造之樹脂之任一種為佳。 In the conductive composition of the present invention, the resin having the (B) thermal decomposition end point in the range of 500 to 650 ° C is a resin having a bisphenol structure, a polyvinyl acetal resin, a resin having a phenol novolak structure, and Any of the resins of the cresol novolac structure is preferred.
另外，本發明之導電性組成物以更含有感光性單體及光聚合起始劑為佳。 Further, the conductive composition of the present invention preferably contains a photosensitive monomer and a photopolymerization initiator.
本發明之電極，其特徵為將上述任一者之導電性組成物燒成而成。 The electrode of the present invention is characterized in that the conductive composition of any of the above is fired.
本發明之電漿顯示面板，其特徵為具有上述電極。 A plasma display panel of the present invention is characterized by having the above electrode.
本發明之觸控面板，其特徵為具有上述電極。 The touch panel of the present invention is characterized by having the above electrode.
藉由本發明，可提供一種含鋁粒子，燒成後的導電性、耐酸性、與基材的密著性優異的導電性組成物、使用該組成物的電極、及具有該電極的PDP、觸控面板。 According to the present invention, it is possible to provide a conductive composition containing aluminum particles, which is excellent in conductivity, acid resistance, and adhesion to a substrate after firing, an electrode using the composition, and a PDP having the electrode. Control panel.
進一步而言，在使用本發明之導電性組成物形成導線的情況，可抑制電阻值隨著其線寬的大小而變動。這種電阻值不易隨著線寬的大小而變動的導電性組成物適合於大型PDP的電極。 Further, in the case where the conductive material is formed using the conductive composition of the present invention, it is possible to suppress the resistance value from fluctuating depending on the magnitude of the line width. The conductive composition whose resistance value does not easily vary with the line width is suitable for the electrode of a large PDP.
圖1係表示實施例之中所使用的樹脂C之TG-DTA測定結果之圖形。 Fig. 1 is a graph showing the results of TG-DTA measurement of the resin C used in the examples.
圖2係表示實施例15~19的導電性組成物的線寬與電阻值之關係圖。 Fig. 2 is a graph showing the relationship between the line width and the electric resistance value of the electroconductive compositions of Examples 15 to 19.
圖3係表示比較例3~7的導電性組成物的線寬與電阻值之關係圖。 Fig. 3 is a graph showing the relationship between the line width and the electric resistance value of the electroconductive compositions of Comparative Examples 3 to 7.
本發明之導電性組成物，其特徵為含鋁粒子與熱分解終點在500~650℃之範圍內之樹脂。含有金屬粉或金屬粒子的導電性組成物一般而言是藉由燒成將樹脂成分燒除 使金屬彼此結著而表現出導電性。在燒成步驟後，若樹脂成分或碳化的樹脂成分(以下稱為殘碳)殘存，則會產生氣泡或膨脹，可能會對無機物層的特性造成不良影響。所以，導電性組成物所使用的樹脂一直以來是選擇使用揮發性高者、或燒成後不易產生殘碳者。相對於此，本發明之(B)成分的樹脂，其熱分解終點在500~650℃這樣的較高溫度區域。藉此，本發明之(B)成分的樹脂，在例如600℃左右的燒成步驟中，被認為至少一部分會殘存在組成物中。如上述般，在以往的導電性組成物之中，殘碳一直被認為是不合適的性質。然而，本發明人發現含有熱分解終點在500~650℃之範圍內之樹脂的導電性組成物，在燒成後的導電性、耐酸性、與基材的密著性優異。對於鋁粒子而言，藉由粒子表面被殘碳被覆，可保護鋁不接觸到酸而提升耐酸性，被認為是說明本發明效果的理由之一，然而詳細機制未明。另外還認為殘碳也有助於與基材的密著性。進一步為了抑制殘碳造成覆蓋鋁粒子的氧化膜的成長，還可考慮提升導電性。以下針對各成分作詳細說明。 The electroconductive composition of the present invention is characterized by containing aluminum particles and a resin having a thermal decomposition end point in the range of 500 to 650 °C. A conductive composition containing metal powder or metal particles is generally burned to burn a resin component The metals are bonded to each other to exhibit electrical conductivity. After the baking step, if the resin component or the carbonized resin component (hereinafter referred to as residual carbon) remains, bubbles or swelling may occur, which may adversely affect the characteristics of the inorganic layer. Therefore, the resin used for the conductive composition has been selected from those having high volatility or being hard to generate residual carbon after firing. On the other hand, the resin of the component (B) of the present invention has a thermal decomposition end point in a relatively high temperature region of 500 to 650 °C. Thereby, the resin of the component (B) of the present invention is considered to have at least a part of the resin remaining in the composition in the firing step of, for example, about 600 °C. As described above, among the conventional conductive compositions, residual carbon has been considered to be an unsuitable property. However, the present inventors have found that a conductive composition containing a resin having a thermal decomposition end point in the range of 500 to 650 ° C is excellent in conductivity, acid resistance, and adhesion to a substrate after firing. In the case of aluminum particles, the surface of the particles is covered with residual carbon, which protects the aluminum from acid contact and enhances acid resistance. It is considered to be one of the reasons for explaining the effects of the present invention, but the detailed mechanism is not known. It is also believed that residual carbon also contributes to adhesion to the substrate. Further, in order to suppress the growth of the oxide film covering the aluminum particles caused by the residual carbon, it is also conceivable to improve the conductivity. The components are described in detail below.
(A)鋁粒子只要可使用於導電性組成物，則並未受到特別限制，可使用周知的任一者。(A)鋁粒子的平均粒徑(D50)係以1~6μm為佳，2~5μm為較佳。若鋁粒子的平均粒徑在上述範圍內，則鋁粒子與樹脂的體積取得 平衡，(B)成分所產生的被覆很充足，而且能夠良好地得到本發明之效果。另外，鋁粒子的比表面積會在適當的範圍，可抑制鋁的氧化所造成的影響。 (A) The aluminum particles are not particularly limited as long as they can be used for the conductive composition, and any of the well-known ones can be used. The average particle diameter (D50) of the aluminum particles (A) is preferably 1 to 6 μm, more preferably 2 to 5 μm. If the average particle diameter of the aluminum particles is within the above range, the volume of the aluminum particles and the resin is obtained. In the balance, the coating produced by the component (B) is sufficient, and the effects of the present invention can be satisfactorily obtained. Further, the specific surface area of the aluminum particles is in an appropriate range, and the influence of oxidation of aluminum can be suppressed.
鋁的平均粒徑可藉由例如雷射繞射式粒度分布測定裝置所得到的重量分布曲線中的D50來測定。 The average particle diameter of aluminum can be measured by D50 in a weight distribution curve obtained by, for example, a laser diffraction type particle size distribution measuring apparatus.
(A)鋁粒子的含量，在將(B)成分定為100質量份時，以70~520質量份為佳，100~400質量份為更佳。 (A) The content of the aluminum particles is preferably from 70 to 520 parts by mass, more preferably from 100 to 400 parts by mass, based on 100 parts by mass of the component (B).
(A)鋁粒子係以藉由氮氣霧化法所製造的鋁粒子為佳。氮氣霧化法只要是藉由在氮氣環境中使金屬(鋁)的熔液成為流體，噴吹氮氣使熔液細碎而成為液滴，並使其凝固，而得到金屬粉末之方法，則不受特別限定。 (A) The aluminum particles are preferably aluminum particles produced by a nitrogen atomization method. The nitrogen atomization method is not limited to a method in which a metal (aluminum) melt is made into a fluid in a nitrogen atmosphere, and a nitrogen gas is blown to finely pulverize the melt to form a droplet and solidify it to obtain a metal powder. Specially limited.
本發明之(B)成分所關連的樹脂為熱分解終點在500~650℃之範圍內之樹脂。宜為550~650℃。 The resin to which the component (B) of the present invention is related is a resin having a thermal decomposition end point in the range of 500 to 650 °C. It should be 550~650°C.
本發明之(B)成分所關連的樹脂可發揮黏結劑的機能。熱分解終點定義為使用TG測定裝置(熱重量測定裝置)或TG-DTA測定裝置(熱重量-示差熱同時測定裝置)來測定溫度的上昇造成的樹脂試樣的重量變化，將重量變化對於時間(溫度)描點作圖而製作出TG曲線，不再觀察到加熱造成重量減少時的溫度。 The resin to which the component (B) of the present invention is associated can function as a binder. The thermal decomposition end point is defined as a change in weight of a resin sample caused by an increase in temperature using a TG measuring device (thermogravimetric measuring device) or a TG-DTA measuring device (thermogravimetric-differential heat simultaneous measuring device), and the change in weight with respect to time The (TG) curve was plotted to produce a TG curve, and the temperature at which the weight was reduced by heating was no longer observed.
另外，樹脂的重量平均分子量會依照樹脂骨架而有所不同，而一般而言在2,000~150,000的範圍，進一步以在 5,000~100,000的範圍為佳。若重量平均分子量在上述範圍內，則可抑制無沾黏性能的劣化、曝光後塗膜耐濕性的惡化、顯像時的膜損耗、及解像度的劣化。另外還可抑制顯像性或貯藏安定性的惡化。 In addition, the weight average molecular weight of the resin may vary depending on the resin skeleton, and is generally in the range of 2,000 to 150,000, further A range of 5,000 to 100,000 is preferred. When the weight average molecular weight is within the above range, deterioration of non-sticking performance, deterioration of moisture resistance of the coating film after exposure, film loss at the time of development, and deterioration of resolution can be suppressed. In addition, deterioration in development or storage stability can be suppressed.
可作為(B)成分使用的樹脂，可列舉例如雙酚A型苯氧基樹脂、雙酚F型苯氧基樹脂、雙酚A/雙酚F的共聚型苯氧基樹脂等的苯氧基系樹脂、雙酚A型環氧樹脂、雙酚F型環氧樹脂、雙酚A/雙酚F的共聚型等的環氧樹脂、使前述環氧樹脂的末端發生丙烯酸變性所得到的環氧丙烯酸酯系樹脂、聚乙烯丁醛系樹脂等的聚乙烯縮醛系樹脂、聚酯系樹脂、嵌段共聚物等。(B)成分所關連的樹脂可單獨使用一種或可併用兩種以上。 Examples of the resin which can be used as the component (B) include a phenoxy group such as a bisphenol A type phenoxy resin, a bisphenol F type phenoxy resin, and a copolymerized phenoxy resin of bisphenol A/bisphenol F. An epoxy resin such as a resin, a bisphenol A epoxy resin, a bisphenol F epoxy resin, or a copolymerization type of bisphenol A/bisphenol F, or an epoxy obtained by denaturation of acrylic acid at the end of the epoxy resin A polyvinyl acetal resin such as an acrylate resin or a polyvinyl butyral resin, a polyester resin, a block copolymer or the like. The resin to which the component (B) is related may be used singly or in combination of two or more.
(B)成分係以主鏈具有雙酚構造之樹脂、聚乙烯縮醛樹脂、苯酚酚醛型樹脂、及甲酚酚醛型樹脂之任一者為佳。另外，從可將導電性組成物製成光硬化性組成物的觀點看來，以具有乙烯性不飽和雙鍵的樹脂為佳。另外，為了使本發明之樹脂能夠進行鹼顯像，亦可採用使側鏈羧酸變性而成的含羧基的樹脂。 The component (B) is preferably a resin having a bisphenol structure in its main chain, a polyvinyl acetal resin, a phenol novolak type resin, and a cresol novolac type resin. Further, from the viewpoint that the conductive composition can be made into a photocurable composition, a resin having an ethylenically unsaturated double bond is preferred. Further, in order to enable alkali development of the resin of the present invention, a carboxyl group-containing resin obtained by denaturation of a side chain carboxylic acid may be used.
上述苯氧基樹脂，是指由2價的酚化合物與表鹵醇的反應所得到，或使2價的環氧化合物與2價的酚化合物反應所得到的聚羥基聚醚。2價的酚化合物可列舉雙酚類。苯氧基樹脂可列舉例如具有雙酚A構造(骨架)的苯氧基樹脂、具有雙酚F構造的苯氧基樹脂、具有雙酚S構造的苯氧基樹脂、具有雙酚M構造的苯氧基樹脂、具有雙酚P 構造的苯氧基樹脂、具有雙酚Z構造的苯氧基樹脂等具有雙酚構造的苯氧基樹脂等。其他還可列舉具有酚醛構造、蒽構造、茀構造、二環戊二烯構造、降莰烯構造、萘構造、聯苯構造、金剛烷構造等的骨架構造的苯氧基樹脂等。亦可具有多種上述骨架構造。上述之中，理想的情況以具有雙酚構造為佳。 The phenoxy resin is a polyhydroxy polyether obtained by a reaction of a divalent phenol compound with an epihalohydrin or a divalent epoxy compound and a divalent phenol compound. Examples of the divalent phenol compound include bisphenols. Examples of the phenoxy resin include a phenoxy resin having a bisphenol A structure (skeleton), a phenoxy resin having a bisphenol F structure, a phenoxy resin having a bisphenol S structure, and a benzene having a bisphenol M structure. Oxygen resin with bisphenol P A phenoxy resin having a bisphenol structure such as a phenoxy resin having a structure or a phenoxy resin having a bisphenol Z structure. Other examples include a phenoxy resin having a skeleton structure such as a phenolic structure, a fluorene structure, a fluorene structure, a dicyclopentadiene structure, a norbornene structure, a naphthalene structure, a biphenyl structure, or an adamantane structure. A variety of the above skeleton configurations are also possible. Among the above, it is desirable to have a bisphenol structure.
上述環氧樹脂是使一分子中具有兩個以上的環氧基(環氧乙烷環)的多官能環氧化合物、或該多官能環氧化合物進行聚合所得到的樹脂。前述多官能環氧化合物可列舉環氧化植物油；雙酚A型環氧樹脂；氫醌型環氧樹脂、雙酚型環氧樹脂、硫醚型環氧樹脂；溴化環氧樹脂；酚醛型環氧樹脂；聯苯酚酚醛型環氧樹脂；雙酚F型環氧樹脂；氫化雙酚A型環氧樹脂；縮水甘油基胺型環氧樹脂；海因型環氧樹脂；脂環式環氧樹脂；三羥苯基甲烷型環氧樹脂；聯二甲酚型或聯苯酚型環氧樹脂或該等的混合物；雙酚S型環氧樹脂；雙酚A酚醛型環氧樹脂；四酚基乙烷型環氧樹脂；雜環式環氧樹脂；二縮水甘油基酞酸酯樹脂；四縮水甘油基茬酚乙烷樹脂；含萘基的環氧樹脂；具有二環戊二烯骨架的環氧樹脂；甲基丙烯酸縮水甘油酯共聚合系環氧樹脂；環己基馬來醯亞胺與縮水甘油基甲基丙烯酸酯之共聚合環氧樹脂；環氧變性而成的聚丁二烯橡膠衍生物、CTBN變性環氧樹脂等，而並未受到該等所限定。這些環氧樹脂可單獨或組合兩種以上來使用。該等之中，尤其以雙酚型環氧樹脂為佳。 The epoxy resin is a resin obtained by polymerizing a polyfunctional epoxy compound having two or more epoxy groups (oxirane rings) in one molecule or the polyfunctional epoxy compound. The polyfunctional epoxy compound may, for example, be an epoxidized vegetable oil; a bisphenol A type epoxy resin; a hydroquinone type epoxy resin, a bisphenol type epoxy resin, a thioether type epoxy resin; a brominated epoxy resin; a phenolic type ring; Oxygen resin; biphenol novolac type epoxy resin; bisphenol F type epoxy resin; hydrogenated bisphenol A type epoxy resin; glycidyl amine type epoxy resin; hydantotype epoxy resin; alicyclic epoxy resin ; trihydroxyphenylmethane type epoxy resin; dixylenol type or biphenol type epoxy resin or a mixture of the same; bisphenol S type epoxy resin; bisphenol A phenolic type epoxy resin; tetraphenol B Alkyl epoxy resin; heterocyclic epoxy resin; diglycidyl phthalate resin; tetraglycidyl decyl phenol resin; naphthalene-containing epoxy resin; epoxy having a dicyclopentadiene skeleton Resin; glycidyl methacrylate copolymerized epoxy resin; copolymerized epoxy resin of cyclohexylmaleimide and glycidyl methacrylate; polybutadiene rubber derivative modified by epoxy , CTBN modified epoxy resin, etc., without being limited by these. These epoxy resins may be used singly or in combination of two or more. Among these, a bisphenol type epoxy resin is particularly preferable.
上述環氧丙烯酸酯系樹脂，係使上述環氧樹脂和分子中具有乙烯性不飽和基與羧基的(甲基)丙烯酸或其衍生物發生反應所得到的樹脂。另外還可為與多元酸酐反應而加成了羧基的含羧基的樹脂。例如使雙酚A或雙酚F這些具有雙酚構造的環氧樹脂發生(甲基)丙烯酸變性所得到的具有雙酚構造的環氧丙烯酸酯系樹脂。 The epoxy acrylate-based resin is a resin obtained by reacting the epoxy resin and (meth)acrylic acid or a derivative thereof having an ethylenically unsaturated group and a carboxyl group in the molecule. Further, it may be a carboxyl group-containing resin obtained by reacting a polybasic acid anhydride to form a carboxyl group. For example, an epoxy acrylate resin having a bisphenol structure obtained by denaturation of (meth)acrylic acid with an epoxy resin having a bisphenol structure such as bisphenol A or bisphenol F is used.
含羧基的樹脂的具體例可列舉如以下般的化合物(寡聚物及聚合物之任一者皆可)。 Specific examples of the carboxyl group-containing resin include the following compounds (any of an oligomer and a polymer).
(1)使一分子中具有多個酚性羥基的化合物與環氧乙烷、環氧丙烷等的環氧烷發生反應，並使所得到的反應生成物與含不飽和基的單羧酸發生反應，然後使所得到的反應生成物與多元酸酐發生反應，所得到的含羧基的感光性樹脂。 (1) A compound having a plurality of phenolic hydroxyl groups in one molecule is reacted with an alkylene oxide such as ethylene oxide or propylene oxide, and the obtained reaction product is generated with a monocarboxylic acid containing an unsaturated group. The reaction is carried out, and then the obtained reaction product is reacted with a polybasic acid anhydride to obtain a carboxyl group-containing photosensitive resin.
(2)使2官能或其以上的多官能(固態)環氧樹脂與(甲基)丙烯酸發生反應，在存在於側鏈的羥基加成2鹽基酸酐而成的含羧基的感光性樹脂。 (2) A carboxyl group-containing photosensitive resin obtained by reacting a bifunctional or higher polyfunctional (solid) epoxy resin with (meth)acrylic acid to form a dibasic acid anhydride in a hydroxyl group of a side chain.
(3)使2官能(固態)環氧樹脂的羥基進一步以表氯醇環氧化，使所形成的多官能環氧樹脂與(甲基)丙烯酸發生反應，在所產生的羥基加成2鹽基酸酐而成的含羧基的感光性樹脂。 (3) further epoxidizing the hydroxyl group of the bifunctional (solid) epoxy resin with epichlorohydrin, reacting the formed polyfunctional epoxy resin with (meth)acrylic acid, and adding a 2-salt group to the generated hydroxyl group. A carboxyl group-containing photosensitive resin obtained from an acid anhydride.
(4)使2官能氧雜環丁烷樹脂與己二酸、酞酸、六氫酞酸等的二羧酸發生反應，在所產生的1級羥基加成酞酸酐、四氫酞酸酐、六氫酞酸酐等的2鹽基酸酐而成的含羧基的非感光性聚酯樹脂。 (4) reacting a bifunctional oxetane resin with a dicarboxylic acid such as adipic acid, citric acid or hexahydrophthalic acid to form a hydrazine anhydride, tetrahydrophthalic anhydride, or a hexahydrophthalic acid A carboxyl group-containing non-photosensitive polyester resin obtained by a dibasic acid anhydride such as hydroquinone anhydride.
(5)在上述(1)~(4)的樹脂進一步加成一分子內具有一個環氧基與一個以上的(甲基)丙烯醯基的化合物而成的含羧基的感光性樹脂。 (5) The carboxyl group-containing photosensitive resin obtained by further adding a compound having one epoxy group and one or more (meth)acryl fluorenyl groups in one molecule to the resin of the above (1) to (4).
此外，在本說明書之中，(甲基)丙烯酸酯是指總稱丙烯酸酯、甲基丙烯酸酯及該等的混合物的用語，並且其他類似的表現亦相同。 Further, in the present specification, (meth) acrylate means a term collectively referred to as acrylate, methacrylate, and the like, and other similar expressions are also the same.
如前述般的含羧基的樹脂在主幹聚合物的側鏈具有多個羧基，因此可藉由稀鹼水溶液來顯像。 Since the carboxyl group-containing resin as described above has a plurality of carboxyl groups in the side chain of the main polymer, it can be visualized by a dilute aqueous alkali solution.
另外，前述含羧基的樹脂的酸價在40~200mgKOH/g的範圍為適當，較佳為在45~120mgKOH/g的範圍。若含羧基的樹脂的酸價為40mgKOH/g以上，則鹼顯像性變良好，另一方面，若為200mgKOH/g以下，則顯像液造成曝光部的溶解會受到抑制，可抑制導線變細至必要以上，或曝光部與未曝光部沒有區別而被顯像液溶解剝離這些現象的發生，可輕易地描繪出正常的電極圖型。 Further, the acid value of the carboxyl group-containing resin is suitably in the range of 40 to 200 mgKOH/g, preferably in the range of 45 to 120 mgKOH/g. When the acid value of the carboxyl group-containing resin is 40 mgKOH/g or more, the alkali developability is improved. On the other hand, when it is 200 mgKOH/g or less, the dissolution of the exposed portion is suppressed by the developing liquid, and the wire can be suppressed. If it is more than necessary, or if the exposed portion is not separated from the unexposed portion and the developing solution is dissolved and peeled off, the normal electrode pattern can be easily drawn.
上述聚乙烯縮醛系樹脂是藉由使聚乙烯醇樹脂以醛類縮醛化所得到。上述醛類並不受特別限定，可列舉例如甲醛、乙醛、戊酮醛、丁醛、戊醛、己醛、庚醛、2-乙基己醛、環己醛、呋喃醛、苯甲醛、2-甲基苯甲醛、3-甲基苯甲醛、4-甲基苯甲醛、對羥基苯甲醛、間羥基苯甲醛、苯乙醛、β-苯基戊酮醛等，以丁醛為佳。這些醛可單獨使用一種或可併用兩種以上。聚乙烯縮醛系樹脂係以聚乙烯丁醛系樹脂為佳。 The polyvinyl acetal resin is obtained by acetalizing a polyvinyl alcohol resin with an aldehyde. The aldehyde is not particularly limited, and examples thereof include formaldehyde, acetaldehyde, ketone aldehyde, butyraldehyde, valeraldehyde, hexanal, heptaldehyde, 2-ethylhexanal, cyclohexanal, furaldehyde, benzaldehyde, and the like. 2-methylbenzaldehyde, 3-methylbenzaldehyde, 4-methylbenzaldehyde, p-hydroxybenzaldehyde, m-hydroxybenzaldehyde, phenylacetaldehyde, β-phenylpentanone aldehyde, etc., preferably butyraldehyde. These aldehydes may be used alone or in combination of two or more. The polyvinyl acetal resin is preferably a polyvinyl butyral resin.
上述聚酯系樹脂係以高分子型共聚芳香族聚酯樹脂為 佳。上述嵌段共聚物係以A-B-A、或A-B-A'型嵌段共聚物為佳。A或A'係以含有聚(甲基)丙烯酸甲酯(PMMA)、聚苯乙烯(PS)等為佳，B係以含有聚丙烯酸正丁酯(PBA)、聚丁二烯(PB)等為佳。 The above polyester resin is a polymer type copolymerized aromatic polyester resin. good. The above block copolymer is preferably an A-B-A or A-B-A' type block copolymer. A or A' is preferably composed of poly(methyl) methacrylate (PMMA), polystyrene (PS), etc., and B contains polybutyl acrylate (PBA), polybutadiene (PB), etc. It is better.
(B)成分係以具有芳香環的樹脂為佳，尤其以具有雙酚構造之樹脂、具有苯酚酚醛構造之樹脂、及具有甲酚酚醛構造之樹脂為佳。另外，(B)成分係以苯氧基系樹脂、聚乙烯縮醛系樹脂、聚酯系樹脂、嵌段共聚物為佳。該等之中，以苯氧基系樹脂、聚乙烯縮醛系樹脂、聚酯系樹脂為較佳。 The component (B) is preferably a resin having an aromatic ring, and particularly preferably a resin having a bisphenol structure, a resin having a phenol novolak structure, and a resin having a cresol novolac structure. Further, the component (B) is preferably a phenoxy resin, a polyvinyl acetal resin, a polyester resin or a block copolymer. Among these, a phenoxy resin, a polyvinyl acetal resin, and a polyester resin are preferable.
在不損及本發明效果的範圍，本發明之導電性組成物亦可含有上述(B)成分所關連之樹脂以外的其他樹脂。其他樹脂可列舉例如過去以來在導電性組成物之中作為有機黏結劑所使用的樹脂，且熱分解終點在500~650℃之範圍外的樹脂。 The conductive composition of the present invention may contain other resins than the resin to which the component (B) is concerned, insofar as the effects of the present invention are not impaired. Examples of the other resin include resins which have been used as an organic binder among the conductive compositions in the past, and which have a thermal decomposition end point outside the range of 500 to 650 °C.
這種有機黏結劑可列舉例如聚酯樹脂、胺甲酸乙酯變性聚酯樹脂、環氧變性聚酯樹脂、丙烯酸變性聚酯樹脂等的各種變性聚酯樹脂、聚醚胺甲酸乙酯樹脂、聚碳酸酯胺甲酸乙酯樹脂、丙烯酸胺甲酸乙酯樹脂、氯乙烯-醋酸乙烯酯共聚物、環氧樹脂、酚樹脂、丙烯酸樹脂、聚乙烯丁醛樹脂、聚醯胺醯亞胺、聚醯亞胺、聚醯胺、硝基纖維素、纖維素．醋酸酯．丁酸酯(CAB)、纖維素．醋酸酯．丙 酸酯(CAP)等的變性纖維素類等。 Examples of such an organic binder include various modified polyester resins such as a polyester resin, an urethane-modified polyester resin, an epoxy-modified polyester resin, an acrylic modified polyester resin, a polyether urethane resin, and a poly Carbonate urethane resin, urethane acrylate resin, vinyl chloride-vinyl acetate copolymer, epoxy resin, phenol resin, acrylic resin, polyvinyl butyral resin, polyamidoximine, poly Amine, polyamine, nitrocellulose, cellulose. Acetate. Butyrate (CAB), cellulose. Acetate. C Denatured celluloses such as acid esters (CAP).
為了對組成物賦予光硬化性，本發明之導電性組成物係以含有可藉由顯像來形成圖型的感光性單體為佳。感光性單體為分子中具有乙烯性不飽和鍵的化合物，是用來調整黏度、促進光硬化性或提升顯像性。這種化合物，可採用慣用且周知的聚酯(甲基)丙烯酸酯、聚醚(甲基)丙烯酸酯、胺甲酸乙酯(甲基)丙烯酸酯、碳酸酯(甲基)丙烯酸酯、環氧(甲基)丙烯酸酯、胺甲酸乙酯(甲基)丙烯酸酯，具體而言可列舉丙烯酸2-羥乙酯、丙烯酸2-羥丙酯等的丙烯酸羥烷酯類；乙二醇、甲氧基四乙二醇、聚乙二醇、丙二醇等的甘醇的二丙烯酸酯類；N,N-二甲基丙烯醯胺、N-羥甲基丙烯醯胺、N,N-二甲基胺丙基丙烯醯胺等的丙烯醯胺類；丙烯酸N,N-二甲基胺乙酯、丙烯酸N,N-二甲基胺丙酯等的丙烯酸胺烷酯類；己二醇、三羥甲基丙烷、季戊四醇、二季戊四醇、參-羥乙基異氰尿酸酯等的多元醇或該等的環氧乙烷加成物、環氧丙烷加成物、或ε-己內酯加成物等的多價丙烯酸酯類；丙烯酸苯氧酯、雙酚A二丙烯酸酯、及這些酚類的環氧乙烷加成物或環氧丙烷加成物等的多價丙烯酸酯類；甘油二縮水甘油醚、甘油三縮水甘油醚、三羥甲基丙烷三縮水甘油醚、三縮水甘油基異氰尿酸酯等的縮水甘油醚之多價丙烯酸酯類；不受限於以上所述，使聚醚多元醇、聚碳酸酯二醇、 羥基末端聚丁二烯、聚酯多元醇等的多元醇直接發生丙烯酸酯化，或透過二異氰酸酯發生胺甲酸乙酯丙烯酸酯化的丙烯酸酯類及三聚氰胺丙烯酸酯、及對應於上述丙烯酸酯的各甲基丙烯酸酯類之至少任一種等。 In order to impart photocurability to the composition, the conductive composition of the present invention preferably contains a photosensitive monomer which can be patterned by development. The photosensitive monomer is a compound having an ethylenically unsaturated bond in the molecule, and is used to adjust viscosity, promote photocurability, or enhance developability. As such a compound, conventional and well-known polyester (meth) acrylate, polyether (meth) acrylate, urethane (meth) acrylate, carbonate (meth) acrylate, epoxy can be used. (meth) acrylate and ethyl urethane (meth) acrylate, specific examples thereof include hydroxyalkyl acrylates such as 2-hydroxyethyl acrylate and 2-hydroxypropyl acrylate; ethylene glycol and methoxy Diacrylates of glycols such as tetraethylene glycol, polyethylene glycol, and propylene glycol; N,N-dimethyl decylamine, N-methylol acrylamide, N,N-dimethylamine Acrylamides such as propyl acrylamide; amide alkyl acrylates such as N,N-dimethylaminoethyl acrylate and N,N-dimethylaminopropyl acrylate; hexanediol, trishydroxyl Polyol such as propane, pentaerythritol, dipentaerythritol, cis-hydroxyethyl isocyanurate or the like, or such ethylene oxide adduct, propylene oxide adduct, or ε-caprolactone adduct And other polyvalent acrylates; phenoxy acrylate, bisphenol A diacrylate, and polyvalent acrylates such as ethylene oxide adducts or propylene oxide adducts of these phenols; Multivalent acrylates of glycidyl ethers such as oleo-glycidyl ether, glycerol triglycidyl ether, trimethylolpropane triglycidyl ether, triglycidyl isocyanurate, etc.; not limited to the above To make polyether polyols, polycarbonate diols, Polyols such as hydroxy-terminated polybutadiene and polyester polyol are directly acrylated, or acrylates and melamine acrylates which are acrylated by diisocyanate, and acrylates corresponding to the above acrylates At least any one of methacrylates and the like.
在摻合的情況，適合的摻合量係以每100質量份(B)成分中摻合5~200質量份為佳。 In the case of blending, a suitable blending amount is preferably 5 to 200 parts by mass per 100 parts by mass of the component (B).
為了對組成物賦予感光性而能夠藉由顯像來形成圖型，本發明之導電性組成物係以含有光聚合起始劑為佳。光聚合起始劑可採用周知的任一者，而其中以具有肟酯基的肟酯系光聚合起始劑、α-胺基苯乙酮系光聚合起始劑、醯基膦氧化物系光聚合起始劑、二茂鈦系光聚合起始劑為佳。光聚合起始劑可單獨使用一種或可併用兩種以上。 In order to impart sensitivity to the composition, it is possible to form a pattern by development, and the conductive composition of the present invention preferably contains a photopolymerization initiator. The photopolymerization initiator may be any of known ones, and among them, an oxime ester photopolymerization initiator having an oxime ester group, an α-aminoacetophenone photopolymerization initiator, a mercaptophosphine oxide system A photopolymerization initiator and a titanocene photopolymerization initiator are preferred. The photopolymerization initiator may be used alone or in combination of two or more.
肟酯系光聚合起始劑係具有下述一般式(1)所表示之部分構造(肟酯基)的光聚合起始劑。 The oxime ester photopolymerization initiator is a photopolymerization initiator having a partial structure (an oxime group) represented by the following general formula (1).
肟酯系光聚合起始劑，市售品可列舉BASF Japan公司製的CGI-325、Irgacure(註冊商標)OXE01、Irgacure OXE02、ADEKA公司製的N-1919、Adeka Arkls(註冊商標)NCI-831等。 The oxime ester photopolymerization initiator, commercially available products include CGI-325 manufactured by BASF Japan Co., Ltd., Irgacure (registered trademark) OXE01, Irgacure OXE02, N-1919 manufactured by ADEKA, and Adeka Arkls (registered trademark) NCI-831. Wait.
在使用肟酯系光聚合起始劑的情況，摻合量係以設定在相對於(B)成分100質量份為0.01~5質量份為佳。如果在0.01質量份以上，則光硬化性充足，可抑制硬化物的剝離或耐藥品性等的硬化物特性的降低。另一方面，如果在5質量份以下，則可避免硬化物表面的光線吸收過度，可確保深部的硬化性。較佳為相對於(B)成分100質量份佔0.5~3質量份。 In the case of using an oxime ester photopolymerization initiator, the blending amount is preferably 0.01 to 5 parts by mass based on 100 parts by mass of the component (B). When the amount is 0.01 parts by mass or more, the photocurability is sufficient, and deterioration of the cured product such as peeling of the cured product or chemical resistance can be suppressed. On the other hand, when it is 5 parts by mass or less, excessive light absorption on the surface of the cured product can be avoided, and the hardenability in the deep portion can be ensured. It is preferably 0.5 to 3 parts by mass based on 100 parts by mass of the component (B).
α-胺基苯乙酮系光聚合起始劑，具體而言可列舉2-甲基-1-〔4-(甲基硫代)苯基〕-2-嗎啉基丙酮-1、2-苄基-2-二甲基胺基-1-(4-嗎啉基苯基)-丁-1-酮、2-(二甲基胺基)-2-〔(4-甲基苯基)甲基〕-1-〔4-(4-嗎啉基)苯基〕-1-丁酮、N,N-二甲基胺基苯乙酮等。市售品可列舉BASF Japan公司製的Irgacure 907、Irgacure 369、Irgacure 379等。 The α-aminoacetophenone photopolymerization initiator is specifically 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinylacetone-1, 2- Benzyl-2-dimethylamino-1-(4-morpholinylphenyl)-butan-1-one, 2-(dimethylamino)-2-[(4-methylphenyl) Methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone, N,N-dimethylaminoacetophenone and the like. Commercially available products include Irgacure 907, Irgacure 369, and Irgacure 379 manufactured by BASF Japan.
醯基膦氧化物系光聚合起始劑，具體而言可列舉 2,4,6-三甲基苯甲醯基二苯膦氧化物、雙(2,4,6-三甲基苯甲醯基)-苯膦氧化物、雙(2,6-二甲氧基苯甲醯基)-2,4,4-三甲基-戊基膦氧化物等。市售品可列舉BASF Japan公司製的LUCIRIN(註冊商標)TPO、Irgacure 819等。 A mercaptophosphine oxide photopolymerization initiator, specifically 2,4,6-trimethylbenzimidyldiphenylphosphine oxide, bis(2,4,6-trimethylbenzylidene)-phenylphosphine oxide, bis(2,6-dimethoxy Benzobenzhydryl)-2,4,4-trimethyl-pentylphosphine oxide and the like. Commercially available products include LUCIRIN (registered trademark) TPO and Irgacure 819 manufactured by BASF Japan.
在使用α-胺基苯乙酮系光聚合起始劑或醯基膦氧化物系光聚合起始劑的情況，各摻合量係以相對於(B)成分100質量份佔0.01~15質量份為佳。如果在0.01質量份以上，則光硬化性充足，可抑制硬化物的剝離或耐藥品性等的硬化物特性的降低。另一方面，如果在15質量份以下，則減少逸散氣體的效果充足，進一步可避免硬化物表面的光線吸收過度，可確保深部的硬化性。較佳為相對於(B)成分100質量份佔0.5~10質量份。 In the case of using an α-aminoacetophenone photopolymerization initiator or a mercaptophosphine oxide photopolymerization initiator, each blending amount is 0.01 to 15 by mass based on 100 parts by mass of the component (B). It is better. When the amount is 0.01 parts by mass or more, the photocurability is sufficient, and deterioration of the cured product such as peeling of the cured product or chemical resistance can be suppressed. On the other hand, if it is 15 parts by mass or less, the effect of reducing the fugitive gas is sufficient, and further, the light absorption on the surface of the cured product can be prevented from being excessive, and the hardenability in the deep portion can be ensured. It is preferably 0.5 to 10 parts by mass based on 100 parts by mass of the component (B).
另外，光聚合起始劑還適合採用BASF Japan公司製的Irgacure-389、二茂鈦系光聚合起始劑的Irgacure-784。 Further, as the photopolymerization initiator, Irgacure-389 manufactured by BASF Japan Co., Ltd., or Irgacure-784 of a titanocene photopolymerization initiator is suitably used.
除了光聚合起始劑之外，還適合使用光起始助劑或增感劑。光起始助劑或增感劑可列舉安息香化合物、苯乙酮化合物、蒽醌化合物、噻噸酮化合物、縮酮化合物、二苯酮化合物、3級胺化合物、及山酮化合物等。這些化合物也有可作為光聚合起始劑使用的情形，而以與光聚合起始劑合併使用為佳。另外，光起始助劑或增感劑可單獨使用一種或可併用兩種以上。 In addition to the photopolymerization initiator, photoinitiating aids or sensitizers are also suitable. Examples of the photoinitiator or the sensitizer include a benzoin compound, an acetophenone compound, an anthraquinone compound, a thioxanthone compound, a ketal compound, a benzophenone compound, a tertiary amine compound, and a ketone compound. These compounds are also used as a photopolymerization initiator, and are preferably used in combination with a photopolymerization initiator. Further, the photoinitiating aid or the sensitizer may be used alone or in combination of two or more.
本發明之導電性組成物即使不含玻璃料，對基材的密著性也很優異，因此可降低玻璃料的含量。但是如果只有少量，則亦可含有玻璃料。從可得到高導電性的觀點看來，以不含玻璃料為佳。 Since the conductive composition of the present invention does not contain a glass frit, it is excellent in adhesion to a substrate, so that the content of the glass frit can be reduced. However, if there is only a small amount, it can also contain glass frit. From the viewpoint of obtaining high conductivity, it is preferred that the glass frit is not contained.
玻璃料並未受到特別限定，而可使用以氧化鉛、氧化鉍、氧化鋅、氧化鋰、或鹼硼矽酸鹽為主成分者。 The glass frit is not particularly limited, and those containing lead oxide, cerium oxide, zinc oxide, lithium oxide, or alkali borosilicate can be used as a main component.
玻璃粒子的平均粒徑(D50)可藉由雷射繞射-散射法來測定，宜為0.3~5.0μm，較佳為0.5~3.0μm。若平均粒徑為0.3μm以上，則可確保產率，可避免成本提高，另一方面，如果在5.0μm以下，則可使薄膜容易形成或燒成時容易均勻收縮，可抑制導線形狀或緻密性的劣化。 The average particle diameter (D50) of the glass particles can be measured by a laser diffraction-scattering method, and is preferably 0.3 to 5.0 μm, preferably 0.5 to 3.0 μm. When the average particle diameter is 0.3 μm or more, the yield can be ensured, and the cost can be avoided. On the other hand, if it is 5.0 μm or less, the film can be easily formed or easily shrunk uniformly, and the shape or density of the wire can be suppressed. Sexual deterioration.
藉由將玻璃料的軟化點定在例如550℃以下，可使導電性優異。 By setting the softening point of the glass frit to, for example, 550 ° C or lower, conductivity can be excellent.
在含有玻璃料的情況，摻合量不受特別限定，而宜為組成物全體中15質量%以下，較佳為4質量%以下，最佳為0%。只要軟化點高的玻璃料的量不過剩，即可抑制密著性的降低。 In the case of containing a glass frit, the blending amount is not particularly limited, and is preferably 15% by mass or less, preferably 4% by mass or less, and most preferably 0%, based on the entire composition. As long as the amount of the glass frit having a high softening point is not excessive, the decrease in the adhesion can be suppressed.
進一步為了使玻璃料均勻地分散在導電性組成物中，亦可添加分散劑。分散劑只要可使玻璃料均勻地分散於導電性組成物中，則並未受到特別限定。分散劑可列舉聚羧酸型高分子界面活性劑、變性丙烯酸系嵌段共聚物、具有顏料親和性基的丙烯酸共聚物、具有鹼性或酸性的顏料吸附基的嵌段共聚物、具有顏料親和性基的變性聚烷氧基化物、聚胺基醯胺鹽與聚酯的組合，或極性酸酯與高分子醇 的組合，酸性聚合物之烷基銨鹽、具有顏料親和性基的高分子量嵌段共聚物，特殊變性尿素等。上述分散劑可單獨使用一種或可併用兩種以上。 Further, in order to uniformly disperse the glass frit in the conductive composition, a dispersing agent may be added. The dispersing agent is not particularly limited as long as the glass frit can be uniformly dispersed in the conductive composition. Examples of the dispersant include a polycarboxylic acid type polymer surfactant, a denatured acrylic block copolymer, an acrylic copolymer having a pigment affinity group, a block copolymer having a basic or acidic pigment adsorption group, and a pigment affinity. Combination of denatured polyalkoxylates, polyamine guanamine salts and polyesters, or polar acid esters and high molecular alcohols A combination of an alkylammonium salt of an acidic polymer, a high molecular weight block copolymer having a pigment affinity group, a specially modified urea, and the like. These dispersing agents may be used alone or in combination of two or more.
本發明之導電性組成物亦可含有脂肪酸。藉由含有脂肪酸，可期待保存安定性的提升。脂肪酸可為飽和脂肪酸、不飽和脂肪酸任一者，而宜為具有兩個以上不飽和鍵的不飽和脂肪酸。脂肪酸的具體例可列舉山萮酸、油酸、次亞麻油酸、硬脂酸、硫代二醋酸等。在摻合脂肪酸的情況，摻合量宜為相對於(B)成分100質量份佔0.1~5。 The conductive composition of the present invention may also contain a fatty acid. By containing fatty acids, it is expected that the preservation stability will be improved. The fatty acid may be either a saturated fatty acid or an unsaturated fatty acid, and is preferably an unsaturated fatty acid having two or more unsaturated bonds. Specific examples of the fatty acid include behenic acid, oleic acid, linoleic acid, stearic acid, thiodiacetic acid, and the like. In the case of blending a fatty acid, the blending amount is preferably 0.1 to 5 parts by mass based on 100 parts by mass of the component (B).
為了提升組成物的保存安定性，抑制膠體化或流動性的降低造成塗佈作業性的惡化，本發明之導電性組成物亦可添加上述脂肪酸以外的安定劑。安定劑可採用具有與導電性組成物中的鋁發生錯合化或形成鹽等效果的化合物。具體而言，可列舉例如硝酸、硫酸、鹽酸、硼酸等的各種無機酸；蟻酸、醋酸、乙醯醋酸、檸檬酸、酞酸、苯磺酸、磺胺酸等各種的有機酸；磷酸、亞磷酸、次亞磷酸、磷酸甲酯、磷酸乙酯、磷酸丁酯、磷酸苯酯、亞磷酸乙酯、亞磷酸二苯酯、單(2-甲基丙烯醯氧基乙基)酸式磷酸酯、二(2-甲基丙烯醯氧基乙基)酸式磷酸酯等的各種磷酸化合物(無機磷酸、有機磷酸)等的酸，以磷酸、磷 酸酯、有機酸為佳。市售品可列舉Lightester P-1M(共榮社化學公司製)等。上述安定劑可單獨使用一種或可併用兩種以上。 In order to improve the storage stability of the composition, it is possible to suppress the deterioration of the colloidal property or the fluidity, and the coating workability is deteriorated. The conductive composition of the present invention may be added with a stabilizer other than the above fatty acid. The stabilizer may be a compound having an effect of causing misalignment or formation of a salt with aluminum in the conductive composition. Specific examples thereof include various inorganic acids such as nitric acid, sulfuric acid, hydrochloric acid, and boric acid; various organic acids such as formic acid, acetic acid, acetamidine acetic acid, citric acid, citric acid, benzenesulfonic acid, and sulfamic acid; and phosphoric acid and phosphorous acid. , hypophosphorous acid, methyl phosphate, ethyl phosphate, butyl phosphate, phenyl phosphate, ethyl phosphite, diphenyl phosphite, mono(2-methylpropenyloxyethyl) acid phosphate, Acids such as various phosphoric acid compounds (inorganic phosphoric acid, organic phosphoric acid) such as bis(2-methylpropenyloxyethyl) acid phosphate, and phosphoric acid and phosphorus Acid esters and organic acids are preferred. Commercially available products include Lightester P-1M (manufactured by Kyoeisha Chemical Co., Ltd.) and the like. These stabilizers may be used alone or in combination of two or more.
安定劑的摻合量宜為相對於(B)成分100質量份佔0.05~10質量份，較佳為0.1~5質量份。 The blending amount of the stabilizer is preferably 0.05 to 10 parts by mass, preferably 0.1 to 5 parts by mass, per 100 parts by mass of the component (B).
為了調整組成物的黏度，本發明之導電性組成物亦可含有有機溶劑。有機溶劑只要可使(B)成分所關連的樹脂溶解，則可採用周知且慣用的物質。可列舉例如甲苯、二甲苯、醋酸乙酯、醋酸丁酯、甲醇、乙醇、異丙醇、異丁醇、1-丁醇、二丙酮醇、乙二醇單丁醚、丙二醇單***、丙二醇單甲醚醋酸酯、萜品醇、甲基乙基酮、卡必醇、卡必醇醋酸酯、丁基卡必醇、丁基卡必醇醋酸酯等。亦可因應必要含有該等的兩種以上。 In order to adjust the viscosity of the composition, the conductive composition of the present invention may also contain an organic solvent. As long as the organic solvent can dissolve the resin associated with the component (B), a well-known and conventional one can be used. For example, toluene, xylene, ethyl acetate, butyl acetate, methanol, ethanol, isopropanol, isobutanol, 1-butanol, diacetone alcohol, ethylene glycol monobutyl ether, propylene glycol monoethyl ether, propylene glycol single Methyl ether acetate, terpineol, methyl ethyl ketone, carbitol, carbitol acetate, butyl carbitol, butyl carbitol acetate, and the like. Two or more of these may be included as necessary.
只要不損及本發明效果，在本發明之導電性組成物中亦可摻合形成電極或電氣配線所使用的含鋁導電性組成物一般所摻合的成分。這種成分可列舉黏結劑、著色劑、表面處理劑、消泡劑、整平劑、表面張力降低劑、稀釋劑、可塑化劑、填料、偶合劑、抗氧化劑、分散劑等。另外還可含有銀粒子、銅粒子等鋁以外的導電粉。 The conductive composition of the present invention may be blended with a component which is generally blended with the aluminum-containing conductive composition used for forming an electrode or an electric wiring, as long as the effect of the present invention is not impaired. Examples of such a component include a binder, a colorant, a surface treatment agent, an antifoaming agent, a leveling agent, a surface tension reducing agent, a diluent, a plasticizer, a filler, a coupling agent, an antioxidant, a dispersing agent, and the like. Further, a conductive powder other than aluminum such as silver particles or copper particles may be contained.
此外，本發明之感光性導電性組成物可藉由三輥磨機 等混練而糊劑化。 Further, the photosensitive conductive composition of the present invention can be obtained by a three-roll mill Wait for mixing and paste.
本發明之電極是使用本發明之導電性組成物所形成。電極的形成方法的例子如以下所述。但是並不受其限制。 The electrode of the present invention is formed using the conductive composition of the present invention. Examples of the method of forming the electrode are as follows. But it is not limited by it.
藉由絲網印刷將本發明之導電性組成物以既定圖型塗佈在例如作為PDP的前面板的玻璃基板，然後進行燒成，可形成PDP用電極。 The conductive composition of the present invention is applied to a glass substrate as a front plate of a PDP in a predetermined pattern by screen printing, and then fired to form an electrode for PDP.
另外，在對本發明之導電性組成物賦予感光性的情況，亦可藉由光蝕刻法來進行圖型形成。例如將本發明之導電性組成物以絲網印刷法、棒式塗佈機、刮刀式塗佈機等適當的塗佈方法塗佈在玻璃基板而形成塗膜。接下來，為了使所得到的塗膜具有指觸乾燥性，以熱風循環式乾燥爐、遠紅外線乾燥爐等在例如約70~120℃下乾燥5~40分鐘左右，使有機溶劑蒸發，而形成無沾黏的塗膜(乾燥塗膜)。此時，在預先將導電性組成物塗佈在薄膜上，並使其乾燥而形成乾式薄膜的情況，亦可使乾式薄膜層合在基板上。 Further, in the case where the photosensitive composition of the present invention is provided with photosensitivity, pattern formation can be carried out by photolithography. For example, the conductive composition of the present invention is applied onto a glass substrate by a suitable coating method such as a screen printing method, a bar coater or a knife coater to form a coating film. Next, in order to make the obtained coating film have dryness to the touch, it is dried in a hot air circulating drying oven, a far-infrared drying oven, etc., for example, at about 70 to 120 ° C for about 5 to 40 minutes to evaporate the organic solvent. Non-stick coating (dry coating). In this case, when the conductive composition is applied to the film in advance and dried to form a dry film, the dry film may be laminated on the substrate.
接下來使所得到的乾燥塗膜圖型曝光。曝光方法可為使用具有既定曝光圖型的負型光罩的接觸曝光及非接觸曝光。曝光光源可採用鹵素燈、高壓水銀燈、雷射光、金屬鹵素燈、黑光燈、無電極燈等。曝光量係以100~800mJ/cm2左右為佳。另外還可使用利用最大波長為350~420nm的雷射發振光源的直接描繪裝置來進行曝光。 Next, the obtained dried coating film pattern is exposed. The exposure method may be contact exposure and non-contact exposure using a negative mask having a predetermined exposure pattern. The exposure light source may be a halogen lamp, a high pressure mercury lamp, a laser beam, a metal halide lamp, a black light lamp, an electrodeless lamp or the like. The exposure amount is preferably about 100 to 800 mJ/cm 2 . Alternatively, exposure can be performed using a direct drawing device using a laser excitation light source having a maximum wavelength of 350 to 420 nm.
進一步使曝光成既定圖型的塗膜顯像。顯像方法可採用噴霧法、浸漬法等。顯像液適合採用例如氫氧化鈉、氫氧化鉀、碳酸鈉、碳酸鉀、矽酸鈉等的金屬鹼水溶液、或單乙醇胺、二乙醇胺、三乙醇胺等的胺水溶液，尤其約1.5wt%以下的濃度的稀鹼水溶液。另外，顯像後為了除去不需要的顯像液，宜進行水洗或酸中和。 Further, the exposure film is exposed to a predetermined pattern to be developed. The development method may employ a spray method, a dipping method, or the like. The developing solution is preferably a metal alkali aqueous solution such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate or sodium citrate, or an aqueous amine solution such as monoethanolamine, diethanolamine or triethanolamine, especially about 1.5% by weight or less. A concentrated aqueous solution of dilute alkali. Further, in order to remove an unnecessary developing liquid after development, it is preferred to carry out water washing or acid neutralization.
在燒成步驟之中，在空氣環境下或氮氣環境下，宜為在650℃以下，較佳為約400~650℃，更佳為約500~600℃將以本發明之導電性組成物形成圖型的玻璃基板實施加熱處理，而形成所希望的電極。此外，此時，昇溫速度係以設定在20℃/分鐘以下為佳。藉由將燒成溫度設定在650℃以下，可防止殘碳的消失。 In the firing step, the conductive composition of the present invention is formed in an air atmosphere or a nitrogen atmosphere, preferably at 650 ° C or lower, preferably about 400 to 650 ° C, more preferably about 500 to 600 ° C. The patterned glass substrate is subjected to a heat treatment to form a desired electrode. Further, at this time, the temperature increase rate is preferably set to 20 ° C / min or less. By setting the firing temperature to 650 ° C or lower, the disappearance of residual carbon can be prevented.
本發明之電極適合使用在PDP或觸控面板，然而並不受該等所限制。觸控面板用電極可列舉引出線電極。 The electrodes of the present invention are suitable for use in PDPs or touch panels, but are not limited by them. The electrode for the touch panel can be cited as a lead wire electrode.
以下在實施例中對本發明作較具體的說明，而本發明並不受以下的實施例、比較例所限定。 The present invention will be specifically described below in the examples, but the present invention is not limited by the following examples and comparative examples.
對於下述表1所記載的各樹脂，使用TG-DTA測定裝置(Seiko Instruments公司製)，測定樹脂試樣隨著溫度上昇的重量變化。 For each of the resins described in the following Table 1, a TG-DTA measuring device (manufactured by Seiko Instruments Co., Ltd.) was used to measure the change in weight of the resin sample as the temperature increased.
測定溫度條件為室溫~600℃，在所到達的溫度保持 30分鐘。另外，昇溫條件定為20℃/min。將不再觀察到重量減少的溫度定為熱分解終點。將所得到的結果揭示於下述表1。另外，將樹脂C所得到的圖形表示於圖3。 The temperature is measured from room temperature to 600 ° C and is maintained at the temperature reached. 30 minutes. Further, the temperature rising condition was set to 20 ° C / min. The temperature at which weight reduction is no longer observed is defined as the end point of thermal decomposition. The results obtained are disclosed in Table 1 below. Further, the pattern obtained by the resin C is shown in Fig. 3 .
以下述表2所示的比例將各成分混合，並以三輥磨機混練，而製作出導電性組成物。表中的摻合量的單位為質量份。 The components were mixed at a ratio shown in the following Table 2, and kneaded in a three-roll mill to prepare a conductive composition. The unit of the blending amount in the table is parts by mass.
使用200mesh的聚酯網將評估用的各導電性組成物塗佈在玻璃基材整個表面上，接下來，以熱風循環式乾燥爐在80℃下乾燥20分鐘，形成指觸乾燥性的良好的塗膜。然後，使用金屬鹵素燈作為光源，並使組成物上的累計光量成為300mJ/cm2來進行曝光。最後在580~600℃下燒成30分鐘，而製作出形成了電極的測試片。 Each of the conductive compositions for evaluation was applied to the entire surface of the glass substrate using a 200 mesh polyester mesh, and then dried in a hot air circulating drying oven at 80 ° C for 20 minutes to form a good touch dryness. Coating film. Then, exposure was performed using a metal halide lamp as a light source and making the cumulative amount of light on the composition 300 mJ/cm 2 . Finally, it was baked at 580 to 600 ° C for 30 minutes to prepare a test piece in which an electrode was formed.
使用200mesh的聚酯網將評估用的各導電性組成物塗佈在玻璃基材整個表面上，接下來，以熱風循環式乾燥爐在80℃下乾燥20分鐘，形成指觸乾燥性的良好的塗膜。然後，在580~600℃下燒成30分鐘，而製作出形成了電極的測試片。 Each of the conductive compositions for evaluation was applied to the entire surface of the glass substrate using a 200 mesh polyester mesh, and then dried in a hot air circulating drying oven at 80 ° C for 20 minutes to form a good touch dryness. Coating film. Then, it was baked at 580 to 600 ° C for 30 minutes to prepare a test piece in which an electrode was formed.
比電阻值： Specific resistance value:
在三菱化學Analytech製的Loresta GP安裝微小樣品用的四點探針(PSP)，藉由四點探針法對於上述測試片(0.1cm×40cm)進行測定。試樣的膜厚是使用Mitutoyo製的數位測微器(MDC-25MJ)作測定。 A four-point probe (PSP) for a micro sample was attached to a Loresta GP manufactured by Mitsubishi Chemical Analytech, and the test piece (0.1 cm × 40 cm) was measured by a four-point probe method. The film thickness of the sample was measured using a digital micrometer (MDC-25MJ) manufactured by Mitutoyo.
密著性： Adhesion:
依據交叉切割法(JIS K-5600)，在測試片(2cm× 5cm)的塗膜刻劃出25個間隔1mm的格子狀。於其上貼膠帶，由撕開後的狀態進行密著性的評估。此外，比較例2無法得到耐酸性，因此並未作評估。 According to the cross cutting method (JIS K-5600), in the test piece (2cm × The coating film of 5 cm) was engraved with 25 grids of 1 mm intervals. The tape was attached thereto, and the adhesion was evaluated from the state after the tearing. Further, in Comparative Example 2, acid resistance could not be obtained, and therefore it was not evaluated.
完全沒有剝落：◎、表層的一部分剝落：○、表層全體剝落：△、全體由基材界面剝落：× No peeling at all: ◎, part of the surface layer peeled off: ○, the whole surface peeling: △, the whole peeling off from the substrate interface: ×
耐酸性：將測試片在0.3質量%的硝酸水溶液中浸漬10分鐘。 然後與上述密著性的評估同樣的方式評估耐酸性。 Acid resistance: The test piece was immersed in a 0.3% by mass aqueous solution of nitric acid for 10 minutes. The acid resistance was then evaluated in the same manner as the above evaluation of the adhesion.
完全沒有剝落：◎、表層的一部分剝落：○、表層全體剝落：△、全體由基材界面剝落：× No peeling at all: ◎, part of the surface layer peeled off: ○, the whole surface peeling: △, the whole peeling off from the substrate interface: ×
解像性： Resolution:
使用200mesh的聚酯網將評估用的各導電性組成物塗佈在玻璃基材整個表面上，接下來，以熱風循環式乾燥爐在80℃下乾燥20分鐘，形成指觸乾燥性的良好的塗膜。然後，使用金屬鹵素燈作為光源，使用線寬40μm及20μm的負型光罩，並使組成物上的累計光量成為 300mJ/cm2來進行曝光，然後使用液溫30℃的0.4wt%Na2CO3水溶液，將顯像時間定為10秒鐘或20秒鐘以進行顯像，經過水洗之後，以氣刀乾燥。然後，在580~600℃下燒成30分鐘。 Each of the conductive compositions for evaluation was applied to the entire surface of the glass substrate using a 200 mesh polyester mesh, and then dried in a hot air circulating drying oven at 80 ° C for 20 minutes to form a good touch dryness. Coating film. Then, using a metal halide lamp as a light source, a negative mask having a line width of 40 μm and 20 μm was used, and the cumulative amount of light on the composition was 300 mJ/cm 2 for exposure, and then 0.4 wt% Na 2 at a liquid temperature of 30 ° C was used. For the CO 3 aqueous solution, the development time was set to 10 seconds or 20 seconds for development, and after washing with water, it was dried with an air knife. Then, it was baked at 580 to 600 ° C for 30 minutes.
觀察測試片上可否形成40μm的線及20μm的線，選擇最小線寬。此外，由於比較例2無法得到耐酸性，因此並未作評估。 It is observed whether a 40 μm line and a 20 μm line can be formed on the test piece, and the minimum line width is selected. Further, since Comparative Example 2 failed to obtain acid resistance, it was not evaluated.
以與上述實施例同樣的方式，如下述表4所記載般摻合各成分，而製作出感光性導電性樹脂組成物，並且進行評估。將所得到的結果揭示於下述表5。 In the same manner as in the above Example, each component was blended as described in the following Table 4, and a photosensitive conductive resin composition was produced and evaluated. The results obtained are disclosed in Table 5 below.
以與上述實施例同樣的方式，如下述表6所記載般摻合各成分，而製作出感光性導電性組成物，並且進行評 估。將所得到的結果揭示於下述表7。 In the same manner as in the above Example, each component was blended as described in the following Table 6, and a photosensitive conductive composition was produced and evaluated. estimate. The results obtained are disclosed in Table 7 below.
使用200mesh的聚酯網將實施例3的導電性組成物塗佈在玻璃基材整個表面上，接下來，以熱風循環式乾燥爐在80℃下乾燥20分鐘，形成指觸乾燥性的良好的塗膜。然後，使用金屬鹵素燈作為光源，使用線寬70、80、90、100、110、120μm的負型光罩，並使組成物上的累計光量成為300mJ/cm2來進行曝光，然後使用液溫30℃的0.4wt%Na2CO3水溶液，將顯像時間定為10秒鐘或20秒鐘以進行顯像，經過水洗之後，以氣刀乾燥。然後在600℃下燒成30分鐘。 The conductive composition of Example 3 was coated on the entire surface of the glass substrate using a 200 mesh polyester mesh, and then dried in a hot air circulating drying oven at 80 ° C for 20 minutes to form a good touch dryness. Coating film. Then, using a metal halide lamp as a light source, a negative type mask having a line width of 70, 80, 90, 100, 110, and 120 μm was used, and the integrated light amount on the composition was 300 mJ/cm 2 for exposure, and then the liquid temperature was used. The development time was set to 10 seconds or 20 seconds for a development time of a 0.4 wt% Na 2 CO 3 aqueous solution at 30 ° C, and after water washing, it was dried with an air knife. It was then baked at 600 ° C for 30 minutes.
對於各線寬的圖型測定長度100cm的電阻值。將此時的電阻值與下述實施例16~19的電阻值一併表示於圖2。 A resistance value of 100 cm in length was measured for each line width pattern. The resistance value at this time is shown together with the resistance values of the following Examples 16 to 19 in Fig. 2 .
在實施例3的組成中，以組成物總量的3%來摻合玻 璃料A(軟化點515℃、有機溶劑與搖變劑混合)，調製出導電性組成物，除此之外與實施例15相同。 In the composition of Example 3, the glass was blended at 3% of the total amount of the composition. The same procedure as in Example 15 was carried out except that the glass material A (softening point: 515 ° C, organic solvent and a rocking agent was mixed) to prepare a conductive composition.
將玻璃料A的含量定為組成物總量的7%，除此之外與實施例16相同。 The same procedure as in Example 16 was carried out except that the content of the glass frit A was set to 7% of the total amount of the composition.
在實施例3的組成中，以組成物總量的3%來摻合玻璃料B(軟化點595℃、有機溶劑與搖變劑混合)，調製出導電性組成物，除此之外與實施例15相同。 In the composition of Example 3, the glass frit B (softening point: 595 ° C, organic solvent and a rocking agent) was blended in an amount of 3% of the total amount of the composition to prepare a conductive composition, and other examples were carried out. Example 15 is the same.
將玻璃料B的含量定為組成物總量的7%，除此之外與實施例18相同。 The same procedure as in Example 18 was carried out except that the content of the glass frit B was set to 7% of the total amount of the composition.
除了使用比較例1的導電性組成物來代替實施例3，與實施例15同樣地測定電阻值。將電阻值與下述比較例4~7的電阻值一併表示於圖3。 The resistance value was measured in the same manner as in Example 15 except that the conductive composition of Comparative Example 1 was used instead of Example 3. The resistance value is shown in Fig. 3 together with the resistance values of Comparative Examples 4 to 7 below.
在比較例1的組成中，以組成物總量的3%來摻合玻璃料A(軟化點515℃、有機溶劑與搖變劑混合)，調製 出導電性組成物，除此之外與比較例3相同。 In the composition of Comparative Example 1, the glass frit A was blended with 3% of the total amount of the composition (softening point 515 ° C, organic solvent mixed with a shaker), and prepared. The same procedure as in Comparative Example 3 was carried out except that the conductive composition was produced.
將玻璃料A的含量定為組成物總量的6%，除此之外與比較例4相同。 The content of the glass frit A was determined to be 6% of the total amount of the composition, except that it was the same as in Comparative Example 4.
在比較例1的組成中，以組成物總量的3%來摻合玻璃料B(軟化點595℃、有機溶劑與搖變劑混合)，調製出導電性組成物，除此之外與比較例3相同。 In the composition of Comparative Example 1, glass frit B (softening point 595 ° C, organic solvent mixed with a rocking agent) was blended at 3% of the total amount of the composition to prepare a conductive composition, and other comparisons were made. Example 3 is the same.
將玻璃料B的含量定為組成物總量的6%，除此之外與比較例6相同。 The content of the glass frit B was determined to be 6% of the total amount of the composition, and otherwise the same as Comparative Example 6.
以與上述實施例同樣的方式，如下述表8所記載般摻合各成分，而製作出感光性導電性樹脂組成物，與上述實施例15同樣地使用形成線寬的圖型的測試片來評估耐酸性。將所得到的結果揭示於下述表9。此外，玻璃料的摻合量的括弧內的數值為相對於組成物全體的質量%。 In the same manner as in the above-mentioned Example, each component was blended as described in the following Table 8, and a photosensitive conductive resin composition was produced. Similarly to the above-described Example 15, a test piece having a line width pattern was used. Evaluate acid resistance. The results obtained are disclosed in Table 9 below. Further, the numerical value in the parentheses of the blending amount of the glass frit is the mass % with respect to the entire composition.
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