TWI518123B - Metal oxide microparticle dispersible paste - Google Patents

Metal oxide microparticle dispersible paste Download PDF

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TWI518123B
TWI518123B TW098138342A TW98138342A TWI518123B TW I518123 B TWI518123 B TW I518123B TW 098138342 A TW098138342 A TW 098138342A TW 98138342 A TW98138342 A TW 98138342A TW I518123 B TWI518123 B TW I518123B
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metal oxide
oxide fine
fine particle
manufactured
weight
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TW201022343A (en
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Kenji Yamauchi
Takahiro Asao
Shintaro Moriguchi
Hiroko Miyazaki
Daihei Sugita
Hiroshi Hiraike
Shunsuke Kondo
Hiroji Fukui
Takeharu Morita
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Sekisui Chemical Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G23/00—Compounds of titanium
    • C01G23/04—Oxides; Hydroxides
    • C01G23/047—Titanium dioxide
    • 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
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F5/00—Compounds of magnesium
    • C01F5/02—Magnesia
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    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G19/00—Compounds of tin
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G19/00—Compounds of tin
    • C01G19/02—Oxides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G49/00—Compounds of iron
    • C01G49/02—Oxides; Hydroxides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G9/00—Compounds of zinc
    • C01G9/02—Oxides; Hydroxides
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/05—Alcohols; Metal alcoholates
    • C08K5/053—Polyhydroxylic alcohols
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/06—Ethers; Acetals; Ketals; Ortho-esters
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/10—Esters; Ether-esters
    • C08K5/101—Esters; Ether-esters of monocarboxylic acids
    • C08K5/103—Esters; Ether-esters of monocarboxylic acids with polyalcohols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C08L101/02—Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
    • 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
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
    • C09D11/037—Printing inks characterised by features other than the chemical nature of the binder characterised by the pigment
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/22—Rheological behaviour as dispersion, e.g. viscosity, sedimentation stability
    • 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
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2217—Oxides; Hydroxides of metals of magnesium
    • C08K2003/222—Magnesia, i.e. magnesium oxide
    • 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
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2231—Oxides; Hydroxides of metals of tin
    • 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
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2237—Oxides; Hydroxides of metals of titanium
    • C08K2003/2241—Titanium dioxide
    • 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
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2296—Oxides; Hydroxides of metals of zinc

Description

金屬氧化物微粒子分散糊料Metal oxide microparticle dispersion paste

本發明係關於一種藉由改善金屬氧化物微粒子之分散性而實現優異之網版印刷性的金屬氧化物微粒子分散漿料。進而，本發明係關於一種含有該金屬氧化物微粒子分散漿料之金屬氧化物微粒子分散糊料、使用該金屬氧化物微粒子分散漿料或該金屬氧化物微粒子分散糊料之金屬氧化物薄膜之製造方法、以及利用該金屬氧化物薄膜之製造方法所獲得之金屬氧化物薄膜。The present invention relates to a metal oxide fine particle-dispersed slurry which achieves excellent screen printing properties by improving the dispersibility of metal oxide fine particles. Further, the present invention relates to a metal oxide fine particle dispersion paste containing the metal oxide fine particle dispersion slurry, and a metal oxide thin film using the metal oxide fine particle dispersion slurry or the metal oxide fine particle dispersion paste. A method and a metal oxide thin film obtained by the method for producing a metal oxide thin film.

近年來，隨著金屬氧化物之細微化技術之進步，業界製造出許多金屬氧化物，並將該等金屬氧化物用於透明電極、抗靜電劑等各種用途。例如於氧化錫中摻雜有銦之ITO(Indium Tin Oxide，氧化銦錫)作為用於製造電漿顯示器面板、液晶顯示器面板等之透明電極材料而受到關注。又，氧化鎂因其耐衝擊性或電子釋放特性而廣泛地用作電漿顯示器用前面板之電介質體保護層。In recent years, with the advancement of the finening technology of metal oxides, many metal oxides have been produced in the industry, and these metal oxides have been used for various purposes such as transparent electrodes and antistatic agents. For example, ITO (Indium Tin Oxide) in which tin oxide is doped with tin oxide has attracted attention as a transparent electrode material for producing a plasma display panel or a liquid crystal display panel. Further, magnesium oxide is widely used as a dielectric protective layer for a front panel for a plasma display panel because of its impact resistance or electron emission characteristics.

先前，作為使用該等金屬氧化物來形成金屬氧化物薄膜之方法，例如使用真空蒸鍍。更具體而言，例如於形成透明電極之情形時，使用如下方法：即藉由真空蒸鍍使金屬氧化物附著於基材表面，並使用光反應性材料進行顯影或者施加遮蔽，藉此形成電極圖案。然而，真空蒸鍍等物理方法在進行真空化時要花費時間，又，必需嚴密地控制裝置，因此期望一種量產性優異且生產效率良好之替代方法。Previously, as a method of forming a metal oxide thin film using the metal oxides, for example, vacuum evaporation was used. More specifically, for example, in the case of forming a transparent electrode, a method of attaching a metal oxide to a surface of a substrate by vacuum evaporation and developing or applying a mask using a photoreactive material, thereby forming an electrode, is used. pattern. However, physical methods such as vacuum vapor deposition take time to perform vacuuming, and it is necessary to strictly control the apparatus. Therefore, an alternative method in which mass productivity is excellent and production efficiency is good is desired.

因此，作為量產性優異之替代方法，例如於專利文獻1中揭示有如下方法：將含有乙醯丙酮銦、乙醯丙酮錫等之糊料塗佈於基板上，進行乾燥後，於燒成時藉由溶膠-凝膠反應來製造ITO透明導電膜。Therefore, as an alternative method of excellent mass productivity, for example, Patent Document 1 discloses a method in which a paste containing indium acesulfate or indium acetonate or the like is applied onto a substrate, dried, and then fired. The ITO transparent conductive film was produced by a sol-gel reaction.

該方法能夠以低成本且簡單地製造ITO透明導電膜，但藉由溶膠-凝膠反應所形成之ITO透明導電膜非常不穩定，難以穩定地獲得具有所需性能之ITO透明導電膜，又，使用沸點較低之乙醯丙酮作為溶劑，存在溶劑易於揮發而使用性差之問題。This method can produce an ITO transparent conductive film at low cost and in a simple manner, but the ITO transparent conductive film formed by the sol-gel reaction is extremely unstable, and it is difficult to stably obtain an ITO transparent conductive film having desired properties, and The use of acetonitrile acetone having a relatively low boiling point as a solvent has a problem that the solvent is easily volatilized and the usability is poor.

因此，作為量產性優異之其他替代方法，是使用藉由網版印刷來塗佈含有金屬氧化物微粒子之分散糊料的方法。於利用網版印刷之方法中，例如藉由網版印刷將使金屬氧化物微粒子分散於乙基纖維素等黏合劑樹脂中而成之糊料塗佈在基板上，其後藉由燒結而形成包含金屬氧化物微粒子之層。Therefore, as another alternative method of excellent mass productivity, a method of applying a dispersion paste containing metal oxide fine particles by screen printing is used. In the method of screen printing, for example, a paste obtained by dispersing metal oxide fine particles in a binder resin such as ethyl cellulose is applied onto a substrate by screen printing, and then formed by sintering. A layer comprising metal oxide microparticles.

然而，此種使用網版印刷之方法存在以下等諸多問題：通常用作黏合劑樹脂之乙基纖維素之熱分解性差，燒結後之殘留碳較多；因燒結時之高溫下加熱而導致金屬氧化物劣化；為了充分地發揮金屬氧化物之特性而必需使微粒子良好地分散，但因粒子彼此之相互作用較強而產生凝聚，導致分散糊料凝膠化。However, such a method of using screen printing has many problems such as the fact that ethyl cellulose which is generally used as a binder resin has poor thermal decomposition property, and has a large residual carbon after sintering; it is caused by heating at a high temperature during sintering. The oxide is deteriorated; in order to sufficiently exhibit the characteristics of the metal oxide, it is necessary to disperse the fine particles well, but the particles are strongly agglomerated to cause aggregation, and the dispersion paste is gelated.

因此，業界期望一種可獲得具有與利用真空蒸鍍之情形時相同之性能的金屬氧化物薄膜的簡單方法。Therefore, the industry desires a simple method of obtaining a metal oxide film having the same properties as in the case of using vacuum evaporation.

先前技術文獻Prior technical literature

[專利文獻1]日本專利特開2006-49019號公報[Patent Document 1] Japanese Patent Laid-Open Publication No. 2006-49019

本發明之目的在於提供一種藉由改善金屬氧化物微粒子之分散性而實現優異之網版印刷性的金屬氧化物微粒子分散漿料。進而，本發明之目的在於提供一種含有該金屬氧化物微粒子分散漿料之金屬氧化物微粒子分散糊料、使用該金屬氧化物微粒子分散漿料或該金屬氧化物微粒子分散糊料之金屬氧化物薄膜之製造方法、以及利用該金屬氧化物薄膜之製造方法所獲得之金屬氧化物薄膜。An object of the present invention is to provide a metal oxide fine particle-dispersed slurry which achieves excellent screen printing properties by improving the dispersibility of metal oxide fine particles. Further, an object of the present invention is to provide a metal oxide fine particle-dispersed paste containing the metal oxide fine particle-dispersed slurry, and a metal oxide thin film using the metal oxide fine particle-dispersed slurry or the metal oxide fine particle-dispersed paste A manufacturing method and a metal oxide thin film obtained by the method for producing a metal oxide thin film.

本發明係一種金屬氧化物微粒子分散漿料，其係含有金屬氧化物微粒子及有機溶劑者，上述金屬氧化物微粒子之平均粒徑為10～100nm，上述有機溶劑含有多元醇，該多元醇係於1分子中具有2個以上之羥基；分子中之碳原子數相對於羥基數之比低於5；且常溫下之黏度為100mPa‧s以上。The present invention relates to a metal oxide fine particle dispersion slurry which contains metal oxide fine particles and an organic solvent, wherein the metal oxide fine particles have an average particle diameter of 10 to 100 nm, and the organic solvent contains a polyhydric alcohol. There are two or more hydroxyl groups in one molecule; the ratio of the number of carbon atoms in the molecule to the number of hydroxyl groups is less than 5; and the viscosity at normal temperature is 100 mPa·s or more.

以下，對本發明進行詳細說明。Hereinafter, the present invention will be described in detail.

近年來，業界研究於利用網版印刷塗佈不包含黏合劑樹脂之金屬氧化物微粒子分散漿料後進行溶劑乾燥或燒結之方法，來代替藉由真空蒸鍍形成包含金屬氧化物微粒子之層之方法、藉由利用網版印刷塗佈金屬氧化物微粒子分散糊料來形成包含金屬氧化物微粒子之層之方法等。然而，若不使用黏合劑樹脂，則金屬氧化物微粒子之分散狀態惡化，非常難以獲得與利用真空蒸鍍之情形時相同之金屬氧化物薄膜。因此，本發明者等人發現，平均粒徑為10～100nm之金屬氧化物微粒子分散於特定結構之有機溶劑中而成的金屬氧化物微粒子分散漿料由於維持金屬氧化物微粒子之高分散性而提昇網版印刷性，可簡便地製造具有與利用真空蒸鍍之情形時相同之透明性、平滑性、細密性等之金屬氧化物薄膜，從而完成本發明。In recent years, the industry has studied a method of performing solvent drying or sintering by coating a metal oxide fine particle dispersion slurry containing no binder resin by screen printing instead of forming a layer containing metal oxide fine particles by vacuum evaporation. A method of forming a layer containing metal oxide fine particles by coating a metal oxide fine particle-dispersed paste by screen printing. However, if the binder resin is not used, the dispersion state of the metal oxide fine particles is deteriorated, and it is extremely difficult to obtain a metal oxide thin film which is the same as in the case of vacuum vapor deposition. Therefore, the present inventors have found that the metal oxide fine particle-dispersed slurry in which the metal oxide fine particles having an average particle diameter of 10 to 100 nm are dispersed in an organic solvent having a specific structure maintains high dispersibility of the metal oxide fine particles. By improving the screen printing property, the metal oxide film having the same transparency, smoothness, fineness, and the like as in the case of vacuum vapor deposition can be easily produced, and the present invention can be completed.

本發明之金屬氧化物微粒子分散漿料含有金屬氧化物微粒子。The metal oxide fine particle dispersion slurry of the present invention contains metal oxide fine particles.

上述金屬氧化物微粒子之平均粒徑為10～100nm。若平均粒徑低於10nm，則無法把握準確之粒徑。若平均粒徑超過100nm，則即便使用所獲得之金屬氧化物微粒子分散漿料進行網版印刷，亦難以製造具有所需透明性、導電性等之金屬氧化物薄膜。上述金屬氧化物微粒子之平均粒徑之較佳下限為12nm，較佳上限為70nm，更佳下限為15nm，更佳上限為50nm。The metal oxide fine particles have an average particle diameter of 10 to 100 nm. If the average particle diameter is less than 10 nm, the accurate particle diameter cannot be grasped. When the average particle diameter exceeds 100 nm, it is difficult to produce a metal oxide thin film having desired transparency, conductivity, or the like even by screen printing using the obtained metal oxide fine particle dispersion slurry. A preferred lower limit of the average particle diameter of the above metal oxide fine particles is 12 nm, a preferred upper limit is 70 nm, a more preferred lower limit is 15 nm, and a more preferred upper limit is 50 nm.

再者，金屬氧化物微粒子之平均粒徑可藉由使用光學顯微鏡或電子顯微鏡對隨機選出之50個金屬氧化物微粒子之粒徑進行測定，並對所測定之粒徑進行算術平均而求出。Further, the average particle diameter of the metal oxide fine particles can be determined by measuring the particle diameters of the randomly selected 50 metal oxide fine particles using an optical microscope or an electron microscope, and arithmetically averaging the measured particle diameters.

上述金屬氧化物微粒子並無特別限定，較佳為含有例如選自由氧化鋅、氧化銻、氧化矽、氧化錫、氧化銦、氧化鈦、氧化鐵、氧化鎂以及於該等中摻雜有其他金屬之金屬氧化物所構成之群中的至少一種。作為上述摻雜有其他金屬之金屬氧化物，例如可列舉於氧化錫中摻雜有銦之ITO、於氧化鋅中摻雜有鎵之GZO(Gallium doped Zinc Oxide，氧化鋅鎵)等。The metal oxide fine particles are not particularly limited, and preferably contain, for example, zinc oxide, cerium oxide, cerium oxide, tin oxide, indium oxide, titanium oxide, iron oxide, magnesium oxide, and other metals doped therein. At least one of the group consisting of metal oxides. Examples of the metal oxide doped with another metal include ITO doped with tin in tin oxide, and GZO (Gallium doped Zinc Oxide) doped with gallium oxide.

於本發明之金屬氧化物微粒子分散漿料中，上述金屬氧化物微粒子之含量之較佳下限為2重量%，較佳上限為70重量%。若上述金屬氧化物微粒子之含量低於2重量%，則即便使用所獲得之金屬氧化物微粒子分散漿料進行網版印刷，有時亦無法製造均勻之金屬氧化物薄膜。若上述金屬氧化物微粒子之含量超過70重量%，則於所獲得之金屬氧化物微粒子分散漿料中，有時無法獲得充分的上述金屬氧化物微粒子之分散穩定性。In the metal oxide fine particle dispersion slurry of the present invention, a preferred lower limit of the content of the metal oxide fine particles is 2% by weight, and a preferred upper limit is 70% by weight. When the content of the metal oxide fine particles is less than 2% by weight, even if the obtained metal oxide fine particle dispersion slurry is used for screen printing, a uniform metal oxide film may not be produced. When the content of the metal oxide fine particles is more than 70% by weight, sufficient dispersion stability of the metal oxide fine particles may not be obtained in the obtained metal oxide fine particle-dispersed slurry.

本發明之金屬氧化物微粒子分散漿料含有有機溶劑。進而，上述有機溶劑含有1分子中具有2個以上之羥基、分子中之碳原子數相對於羥基數之比低於5且常溫下之黏度為100mPa‧s以上的多元醇(以下，亦簡稱為多元醇)。The metal oxide fine particle dispersion slurry of the present invention contains an organic solvent. Furthermore, the organic solvent contains a polyhydric alcohol having two or more hydroxyl groups in one molecule, a ratio of the number of carbon atoms in the molecule to the number of hydroxyl groups of less than 5, and a viscosity at room temperature of 100 mPa·s or more (hereinafter, also referred to as Polyol).

通常，使用例如水、甲醇、乙醇、異丙醇等高極性溶劑以外之溶劑，並不容易使如上所述之平均粒徑為10～100nm之極其細微的金屬氧化物微粒子分散。又，上述金屬氧化物微粒子分散於此種高極性溶劑中而成之金屬氧化物微粒子分散漿料之黏度非常低，因此若直接使用該金屬氧化物微粒子分散漿料，則只能適應溶劑澆鑄、噴墨、噴霧等步驟，而難以製造厚度為1μm左右之均勻之金屬氧化物薄膜。Usually, a solvent other than a highly polar solvent such as water, methanol, ethanol or isopropyl alcohol is used, and it is not easy to disperse extremely fine metal oxide fine particles having an average particle diameter of 10 to 100 nm as described above. Further, since the metal oxide fine particle dispersion slurry obtained by dispersing the metal oxide fine particles in such a highly polar solvent has a very low viscosity, if the metal oxide fine particle dispersion slurry is directly used, it can only be adapted to solvent casting. It is difficult to produce a uniform metal oxide film having a thickness of about 1 μm by steps such as inkjet or spraying.

本發明之金屬氧化物微粒子分散漿料藉由含有多元醇(該多元醇係於1分子中具有2個以上之羥基；分子中之碳原子數相對於羥基數之比低於5；且常溫下之黏度為100mPa‧s以上)以及視需要之高分子陰離子系分散劑，而可獲得上述金屬氧化物微粒子之良好之分散狀態。又，由於漿料整體之黏度變高，故可使用三輥研磨機等簡單之粉碎裝置直接進行粉碎處理，從而可獲得上述金氧化物微粒子之分散狀態進一步提昇之金屬氧化物微粒子分散漿料。又，以上述方式所獲得之金屬氧化物微粒子分散漿料可直接適應網版印刷、凹版膠印(gravure offset printing)、輥塗機、刮塗機等的各種印刷步驟，從而可製造均勻之金屬氧化物薄膜。The metal oxide fine particle dispersion slurry of the present invention contains a polyol (the polyol has two or more hydroxyl groups in one molecule; the ratio of the number of carbon atoms in the molecule to the number of hydroxyl groups is less than 5; and at normal temperature The viscosity is 100 mPa·s or more and a polymer anionic dispersant as needed, and a good dispersion state of the above metal oxide fine particles can be obtained. In addition, since the viscosity of the entire slurry is increased, the pulverization treatment can be directly performed by using a simple pulverizing apparatus such as a three-roll mill to obtain a metal oxide fine particle-dispersed slurry in which the dispersion state of the gold oxide fine particles is further improved. Moreover, the metal oxide fine particle dispersion slurry obtained in the above manner can directly adapt to various printing steps of screen printing, gravure offset printing, roll coater, knife coater, etc., thereby producing uniform metal oxidation. Film.

上述多元醇於1分子中具有2個以上之羥基。若1分子中之羥基數低於2個，則多元醇之親水性下降，難以良好地分散上述金屬氧化物微粒子。The above polyol has two or more hydroxyl groups in one molecule. When the number of hydroxyl groups in one molecule is less than two, the hydrophilicity of the polyol is lowered, and it is difficult to disperse the metal oxide fine particles well.

又，上述多元醇的分子中之碳原子數相對於羥基數之比低於5。若分子中之碳原子數相對於羥基數之比為5以上，則多元醇之親水性下降，難以良好地分散上述金屬氧化物微粒子。上述多元醇的分子中之碳原子數相對於羥基數之比較佳為1以上。再者，本說明書中，所謂「碳原子數相對於羥基數之比」係指碳原子數除以羥基數所得之值{(碳原子數)/(羥基數)}。Further, the ratio of the number of carbon atoms in the molecule of the above polyol to the number of hydroxyl groups is less than 5. When the ratio of the number of carbon atoms in the molecule to the number of hydroxyl groups is 5 or more, the hydrophilicity of the polyol is lowered, and it is difficult to disperse the metal oxide fine particles well. The ratio of the number of carbon atoms in the molecule of the above polyol to the number of hydroxyl groups is preferably 1 or more. In the present specification, the "ratio of the number of carbon atoms to the number of hydroxyl groups" means a value obtained by dividing the number of carbon atoms by the number of hydroxyl groups {(number of carbon atoms) / (number of hydroxyl groups)}.

上述多元醇於常溫下之黏度為100mPa‧s以上。若常溫下之黏度低於100mPa‧s，則所獲得之金屬氧化物微粒子分散漿料之黏度變低，無法進行利用三輥研磨機等之粉碎處理來提高上述金屬氧化物微粒子之分散性，或者無法進行網版印刷。就可更加良好地粉碎上述金屬氧化物微粒子的方面而言，上述多元醇較佳為於常溫下之黏度為1000mPa‧s以上。又，上述多元醇較佳為於常溫下之黏度為50000mPa‧s以下。The viscosity of the above polyol at normal temperature is 100 mPa ‧ or more. When the viscosity at room temperature is less than 100 mPa·s, the viscosity of the obtained metal oxide fine particle-dispersed slurry becomes low, and the pulverization treatment by a three-roll mill or the like cannot be performed to improve the dispersibility of the metal oxide fine particles, or Screen printing is not possible. In terms of pulverizing the metal oxide fine particles more satisfactorily, the polyol preferably has a viscosity at room temperature of 1000 mPa ‧ s or more. Further, the polyol preferably has a viscosity at room temperature of 50,000 mPa·s or less.

作為上述1分子中具有2個以上之羥基；分子中之碳原子數相對於羥基數之比低於5；且常溫下之黏度為100mPa‧s以上的多元醇，例如可列舉：3-甲基-1,5-戊二醇、甘油、甘油單乙酸酯、2,4-二乙基-1,5-戊二醇、2-乙基-1,3-己二醇、二乙二醇、三乙二醇、丙二醇、丁二醇、乙二醇、戊二醇、己二醇、1,6-己二醇、2-丁烯-1,4-二醇、2-甲基-2,4-戊二醇、2-乙基-2-(羥甲基)-1,3-丙二醇、2,2-二甲基-1,3-丙二醇、2,2-二乙基-1,3-丙二醇、2-乙基-2-丁基-1,3-丙二醇等。其中，就黏度比較高，可使上述金屬氧化物微粒子分散而容易進行利用三輥研磨機等之粉碎處理的方面而言，較佳為丁二醇、戊二醇、己二醇、1,6-己二醇、2-乙基-1,3-己二醇、3-甲基-1,5-戊二醇、甘油、2,4-二乙基-1,5-戊二醇。該等多元醇可單獨使用，亦可併用兩種以上。The polyhydric alcohol having two or more hydroxyl groups in the above-mentioned one molecule; the ratio of the number of carbon atoms in the molecule to the number of hydroxyl groups is less than 5; and the viscosity at normal temperature is 100 mPa·s or more, for example, 3-methyl group -1,5-pentanediol, glycerin, monoglyceride, 2,4-diethyl-1,5-pentanediol, 2-ethyl-1,3-hexanediol, diethylene glycol , triethylene glycol, propylene glycol, butanediol, ethylene glycol, pentanediol, hexanediol, 1,6-hexanediol, 2-butene-1,4-diol, 2-methyl-2 , 4-pentanediol, 2-ethyl-2-(hydroxymethyl)-1,3-propanediol, 2,2-dimethyl-1,3-propanediol, 2,2-diethyl-1, 3-propanediol, 2-ethyl-2-butyl-1,3-propanediol, and the like. Among them, in order to disperse the metal oxide fine particles and to facilitate the pulverization treatment by a three-roll mill or the like, it is preferably butanediol, pentanediol, hexanediol, and 1,6. - hexanediol, 2-ethyl-1,3-hexanediol, 3-methyl-1,5-pentanediol, glycerol, 2,4-diethyl-1,5-pentanediol. These polyols may be used singly or in combination of two or more.

於本發明之金屬氧化物微粒子分散漿料中，上述1分子中具有2個以上之羥基、分子中之碳原子數相對於羥基數之比低於5、且常溫下之黏度為100mPa‧s以上的多元醇之含量之較佳下限為25重量%，較佳上限為85重量%。若上述多元醇之含量低於25重量%，則有時難以使上述金屬氧化物微粒子分散。若上述多元醇之含量超過85重量%，則有時所獲得之金屬氧化物微粒子分散漿料之黏度變低，於進行網版印刷等時使用性下降。In the metal oxide fine particle dispersion slurry of the present invention, the one molecule has two or more hydroxyl groups, the ratio of the number of carbon atoms in the molecule to the number of hydroxyl groups is less than 5, and the viscosity at normal temperature is 100 mPa·s or more. A preferred lower limit of the content of the polyol is 25% by weight, and a preferred upper limit is 85% by weight. When the content of the above polyol is less than 25% by weight, it may be difficult to disperse the above metal oxide fine particles. When the content of the above-mentioned polyol is more than 85% by weight, the viscosity of the obtained metal oxide fine particle-dispersed slurry may be lowered, and the usability may be lowered when screen printing or the like is performed.

本發明之金屬氧化物微粒子分散漿料除了上述1分子中具有2個以上之羥基；分子中之碳原子數相對於羥基數之比低於5；且常溫下之黏度為100mPa‧s以上的多元醇以外，較佳為含有沸點為140℃以上之其他有機溶劑。若沸點低於140℃，則有時於使用所獲得之金屬氧化物微粒子分散漿料進行網版印刷時，在印刷過程中有機溶劑會揮發，使印刷變得困難。The metal oxide fine particle dispersion slurry of the present invention has two or more hydroxyl groups in one molecule; the ratio of the number of carbon atoms in the molecule to the number of hydroxyl groups is less than 5; and the viscosity at room temperature is 100 mPa·s or more. Other than the alcohol, it is preferred to contain another organic solvent having a boiling point of 140 ° C or higher. When the boiling point is lower than 140 ° C, the organic solvent may volatilize during printing during the screen printing using the obtained metal oxide fine particle dispersion slurry, which makes printing difficult.

作為上述沸點為140℃以上之其他有機溶劑，例如可列舉：乙二醇***、乙二醇單丁醚、二乙二醇單***、二乙二醇單甲醚、二乙二醇單異丁醚、三甲基戊二醇單異丁酸酯、二乙二醇單丁醚、乙二醇單己醚、二乙二醇單丁醚、二乙二醇單己醚、丙二醇單丁醚、二乙二醇單***乙酸酯、乙二醇單丁醚乙酸酯、乙二醇單***乙酸酯、二乙二醇單丁醚乙酸酯、二氫松油醇乙酸酯、松油醇乙酸酯、乙酸2-丁氧基乙酯、乙酸2-乙氧基乙酯、乙酸2-甲氧基乙酯、碳酸丙烯酯、松油醇、二氫松油醇、水楊酸甲酯、乳酸乙酯、二丙二醇單甲醚、2-乙基己酸、三甲基己酸、四氫呋喃甲醇、呋喃6醇、2-(苄氧基)乙醇、2-苯氧基乙醇、2-(甲氧基甲氧基)乙醇、三乙二醇單甲醚、三乙二醇、二乙二醇單丁基乙酸酯、二乙二醇單丁醚乙酸酯、苯氧基乙酸酯、乙酸苯氧基乙酯、乙二醇單苯醚、二乙二醇單苯醚、乙二醇單苄醚、二乙二醇單苄醚、丙二醇單苯醚、苄基乙二醇、苯基乙酸甲酯、苯基乙酸乙酯、苯甲酸乙酯、苯甲酸甲酯、γ-丁內酯、二甲亞碸、N-甲基吡咯啶酮、N-甲基乙醯胺、乙醯胺、N,N-二甲基甲醯胺、N-甲基甲醯胺、甲醯胺、TEXANOL(十二碳酯醇)、異佛酮、乳酸丁酯、鄰苯二甲酸二辛酯、己二酸二辛酯、苄醇、甲酚。Examples of the other organic solvent having a boiling point of 140 ° C or higher include ethylene glycol diethyl ether, ethylene glycol monobutyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether, and diethylene glycol monoisobutylene. Ether, trimethylpentanediol monoisobutyrate, diethylene glycol monobutyl ether, ethylene glycol monohexyl ether, diethylene glycol monobutyl ether, diethylene glycol monohexyl ether, propylene glycol monobutyl ether, Diethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, dihydroterpineol acetate, pine Oleic alcohol acetate, 2-butoxyethyl acetate, 2-ethoxyethyl acetate, 2-methoxyethyl acetate, propylene carbonate, terpineol, dihydroterpineol, salicylic acid Methyl ester, ethyl lactate, dipropylene glycol monomethyl ether, 2-ethylhexanoic acid, trimethylhexanoic acid, tetrahydrofuran methanol, furan 6 alcohol, 2-(benzyloxy)ethanol, 2-phenoxyethanol, 2 -(methoxymethoxy)ethanol, triethylene glycol monomethyl ether, triethylene glycol, diethylene glycol monobutyl acetate, diethylene glycol monobutyl ether acetate, phenoxy Acid ester, phenoxyethyl acetate, ethylene glycol Phenyl ether, diethylene glycol monophenyl ether, ethylene glycol monobenzyl ether, diethylene glycol monobenzyl ether, propylene glycol monophenyl ether, benzyl glycol, methyl phenyl acetate, ethyl phenylacetate, benzene Ethyl formate, methyl benzoate, γ-butyrolactone, dimethyl hydrazine, N-methylpyrrolidone, N-methylacetamide, acetamide, N,N-dimethylformamide , N-methylformamide, formamide, TEXANOL (dodecanol), isophorone, butyl lactate, dioctyl phthalate, dioctyl adipate, benzyl alcohol, cresol .

於本發明之金屬氧化物微粒子分散漿料中，上述沸點為140℃以上之其他有機溶劑之含量的較佳上限為60重量%。若上述沸點為140℃以上之其他有機溶劑之含量超過60重量%，則有時上述金屬氧化物微粒子之分散穩定性下降。In the metal oxide fine particle dispersion slurry of the present invention, a preferred upper limit of the content of the other organic solvent having a boiling point of 140 ° C or higher is 60% by weight. When the content of the other organic solvent having a boiling point of 140 ° C or higher exceeds 60% by weight, the dispersion stability of the metal oxide fine particles may be lowered.

本發明之金屬氧化物微粒子分散漿料較佳為含有高分子陰離子系分散劑。上述高分子陰離子系分散劑並無特別限定，例如較佳為高分子聚羧酸型分散劑。更具體而言，作為上述高分子陰離子系分散劑，可列舉：花王公司製造之DEMOL EP、POIZ 520、POIZ 521、POIZ 532A、HOMOGENOL L-18、HOMOGENOL 1820、HOMOGENOL L-95、HOMOGENOL L-100等，LION公司製造之POLITY N-100K、POLITY A-530、POLITY A-540、POLITY A-550等，BYK Chemie公司製造之DISPERBYK-102、DISPERBYK-106、DISPERBYK-108、DISPERBYK-110、DISPERBYK-111、BYK-P105等，楠本化成公司製造之HIPLAAD ED-110、HIPLAAD ED-111、HIPLAAD ED-118、HIPLAAD ED-216、HIPLAAD ED-350等，Harima Chemicals 公司製造之No4310、No4793等，第一工業製藥公司製造之DISCOAT N-14、SHALLOL AH、SHALLOL AN等，Croda公司製造之KD-4、KD-8、KD-9、KD-15等，東邦化學公司製造之RS-610、RS-710、SM-210等。本發明之金屬氧化物微粒子分散漿料藉由含有此種高分子陰離子系分散劑，可抑制上述金屬氧化物微粒子之凝聚而提高分散性。The metal oxide fine particle dispersion slurry of the present invention preferably contains a polymer anionic dispersant. The polymer anionic dispersant is not particularly limited, and for example, a polymer polycarboxylic acid type dispersant is preferred. More specifically, examples of the polymer anionic dispersant include DEMOL EP, POIZ 520, POIZ 521, POIZ 532A, HOMOGENOL L-18, HOMOGENOL 1820, HOMOGENOL L-95, and HOMOGENOL L-100 manufactured by Kao Corporation. Etc., POLITY N-100K, POLITY A-530, POLITY A-540, POLITY A-550 manufactured by LION, DISPERBYK-102, DISPERBYK-106, DISPERBYK-108, DISPERBYK-110, DISPERBYK- manufactured by BYK Chemie 111, BYK-P105, etc., HIPLAAD ED-110, HIPLAAD ED-111, HIPLAAD ED-118, HIPLAAD ED-216, HIPLAAD ED-350, etc. manufactured by Nanben Chemical Co., Ltd., No. 4310, No.4793, etc. manufactured by Harima Chemicals Co., Ltd., first Industrial pharmaceutical company's DISCOAT N-14, SHALLOL AH, SHALLOL AN, etc., Croda's KD-4, KD-8, KD-9, KD-15, etc., Dongbang Chemical Co., Ltd. RS-610, RS-710 , SM-210, etc. When the metal oxide fine particle dispersion slurry of the present invention contains such a polymer anionic dispersant, aggregation of the metal oxide fine particles can be suppressed to improve dispersibility.

於本發明之金屬氧化物微粒子分散漿料中，上述高分子陰離子系分散劑之含量之較佳下限為0.1重量%，較佳上限為10重量%。若上述高分子陰離子系分散劑之含量偏離上述範圍，則有時無法良好地分散上述金屬氧化物微粒子。上述高分子陰離子系分散劑之含量之更佳下限為0.3重量%，更佳上限為7重量%。In the metal oxide fine particle dispersion slurry of the present invention, a preferred lower limit of the content of the polymer anionic dispersant is 0.1% by weight, and a preferred upper limit is 10% by weight. When the content of the polymer anionic dispersant is out of the above range, the metal oxide fine particles may not be well dispersed. A more preferred lower limit of the content of the above polymer anionic dispersant is 0.3% by weight, and a more preferred upper limit is 7% by weight.

為了促進塗佈後之平整性，本發明之金屬氧化物微粒子分散漿料亦可含有非離子系界面活性劑。In order to promote flatness after coating, the metal oxide fine particle dispersion slurry of the present invention may further contain a nonionic surfactant.

上述非離子系界面活性劑並無特別限定，較佳為HLB值(Hydrophile Lipophile Balance Number，親水親油平衡值)為10以上且20以下之非離子系界面活性劑。再者，HLB值係表示界面活性劑之親水性、親油性之指標，已提出有幾種計算方法。例如對於酯系界面活性劑，有如下方法：當皂化值設為S，且構成界面活性劑之脂肪酸之酸值設為A時，將20(1─S/A)之值定義為HLB值。The nonionic surfactant is not particularly limited, and is preferably a nonionic surfactant having an HLB value (Hydrophile Lipophile Balance Number) of 10 or more and 20 or less. Further, the HLB value indicates an index of hydrophilicity and lipophilicity of the surfactant, and several calculation methods have been proposed. For example, for the ester-based surfactant, there is a method in which the value of 20 (1 - S/A) is defined as the HLB value when the saponification value is S and the acid value of the fatty acid constituting the surfactant is A.

上述非離子系界面活性劑最佳為使伸烷醚加成於脂肪鏈上而成之非離子系界面活性劑，具體而言，例如可列舉聚氧乙烯月桂醚、聚氧乙烯鯨蠟醚。The nonionic surfactant is preferably a nonionic surfactant obtained by adding an alkylene oxide to an aliphatic chain. Specific examples thereof include polyoxyethylene lauryl ether and polyoxyethylene cetyl ether.

於本發明之金屬氧化物微粒子分散漿料中，上述非離子系界面活性劑之含量之較佳上限為5重量%。上述非離子系界面活性劑之熱分解性良好，但若大量添加，則有時對使用所獲得之金屬氧化物微粒子分散漿料而製造之金屬氧化物薄膜的性能造成不良影響。In the metal oxide fine particle dispersion slurry of the present invention, a preferred upper limit of the content of the nonionic surfactant is 5% by weight. The nonionic surfactant is excellent in thermal decomposition property. However, when it is added in a large amount, the performance of the metal oxide thin film produced by using the obtained metal oxide fine particle dispersion slurry may be adversely affected.

本發明之金屬氧化物微粒子分散漿料亦可含有密合促進劑。The metal oxide fine particle dispersion slurry of the present invention may further contain an adhesion promoter.

上述密合促進劑並無特別限定，較佳為胺基矽烷系矽烷偶合劑。作為上述胺基矽烷系矽烷偶合劑，例如可列舉：N-2-(胺基乙基)-3-胺基丙基甲基二甲氧基矽烷、N-2-(胺基乙基)-3-胺基丙基三甲氧基矽烷、N-2-(胺基乙基)-3-胺基丙基三乙氧基矽烷、3-胺基丙基三甲氧基矽烷、3-胺基丙基三乙氧基矽烷、3-三乙氧基矽烷基-N-(1,3-二甲基-亞丁基)丙基胺、N-苯基-3-胺基丙基三甲氧基矽烷。The adhesion promoter is not particularly limited, and is preferably an amino decane decane coupling agent. The above-mentioned amino decane-based decane coupling agent may, for example, be N-2-(aminoethyl)-3-aminopropylmethyldimethoxydecane or N-2-(aminoethyl)- 3-aminopropyltrimethoxydecane, N-2-(aminoethyl)-3-aminopropyltriethoxydecane, 3-aminopropyltrimethoxydecane, 3-aminopropyl Triethoxy decane, 3-triethoxydecyl-N-(1,3-dimethyl-butylene)propylamine, N-phenyl-3-aminopropyltrimethoxydecane.

又，作為上述胺基矽烷系矽烷偶合劑以外之密合促進劑，例如可使用：3-縮水甘油氧基丙基三甲氧基矽烷、3-縮水甘油氧基丙基甲基二乙氧基矽烷、3-縮水甘油氧基丙基三乙氧基矽烷等縮水甘油基矽烷系矽烷偶合劑，二甲基二甲氧基矽烷，四甲氧基矽烷，四乙氧基矽烷，苯基三甲氧基矽烷，二苯基二甲氧基矽烷等。該等可單獨使用，亦可併用兩種以上。Further, as the adhesion promoter other than the above-described aminodecane-based decane coupling agent, for example, 3-glycidoxypropyltrimethoxydecane or 3-glycidoxypropylmethyldiethoxydecane can be used. , glycidyl decane decane coupling agent such as 3-glycidoxypropyl triethoxy decane, dimethyl dimethoxy decane, tetramethoxy decane, tetraethoxy decane, phenyl trimethoxy Decane, diphenyldimethoxydecane, and the like. These may be used singly or in combination of two or more.

為了表現出對於玻璃基板之密合力，本發明之金屬氧化物微粒子分散漿料亦可進一步含有低熔點玻璃微粒子。In order to exhibit the adhesion to the glass substrate, the metal oxide fine particle-dispersed slurry of the present invention may further contain low-melting glass fine particles.

上述低熔點玻璃微粒子並無特別限定，例如可列舉：矽酸鹽玻璃、鉛玻璃、鋅玻璃、硼玻璃、CaO-Al2O3-SiO2系無機玻璃、MgO-Al2O3-SiO2系無機玻璃、LiO2-Al2O3-SiO2系無機玻璃。其中，較佳為熔點為600℃以下之低熔點玻璃。The low-melting-point glass fine particles are not particularly limited, and examples thereof include bismuth silicate glass, lead glass, zinc glass, borosilicate glass, CaO-Al 2 O 3 -SiO 2 -based inorganic glass, and MgO-Al 2 O 3 -SiO 2 . It is an inorganic glass and a LiO 2 -Al 2 O 3 -SiO 2 inorganic glass. Among them, a low melting point glass having a melting point of 600 ° C or less is preferred.

製造本發明之金屬氧化物微粒子分散漿料之方法並無特別限定，例如可列舉於混合各成分後，使用三輥研磨機等粉碎裝置進行粉碎處理之方法。尤其於上述1分子中具有2個以上之羥基；分子中之碳原子數相對於羥基數之比低於5；且常溫下之黏度為100mPa‧s以上的多元醇之中，使用常溫下之黏度為1000mPa‧s以上之多元醇時，有時可藉由使用三輥研磨機進行漿料之粉碎處理，而獲得與利用珠磨機處理所獲得之分散狀態接近的分散狀態。The method for producing the metal oxide fine particle-dispersed slurry of the present invention is not particularly limited, and examples thereof include a method of mixing the respective components and then performing a pulverization treatment using a pulverizing apparatus such as a three-roll mill. In particular, in the above-mentioned one molecule, two or more hydroxyl groups are used; the ratio of the number of carbon atoms in the molecule to the number of hydroxyl groups is less than 5; and the viscosity at a normal temperature is 100 mPa·s or more, and the viscosity at normal temperature is used. In the case of a polyol of 1000 mPa·s or more, the pulverization treatment of the slurry may be carried out by using a three-roll mill to obtain a dispersion state close to the dispersion state obtained by the treatment with a bead mill.

藉由對本發明之金屬氧化物微粒子分散漿料中添加黏合劑樹脂，可獲得更適合網版印刷等之印刷步驟之糊料。By adding a binder resin to the metal oxide fine particle dispersion slurry of the present invention, a paste which is more suitable for a printing step such as screen printing can be obtained.

含有本發明之金屬氧化物微粒子分散漿料及黏合劑樹脂之金屬氧化物微粒子分散糊料亦為本發明之一。The metal oxide fine particle dispersion paste containing the metal oxide fine particle dispersion slurry of the present invention and the binder resin is also one of the inventions.

上述黏合劑樹脂並無特別限定，例如較佳為纖維素樹脂、(甲基)丙烯酸樹脂、聚醚樹脂、聚縮醛樹脂、聚乙烯縮醛樹脂。其中，就熱分解性較高且燒結後之殘留碳較少的方面而言，最佳為(甲基)丙烯酸樹脂。The binder resin is not particularly limited, and for example, a cellulose resin, a (meth)acrylic resin, a polyether resin, a polyacetal resin, or a polyvinyl acetal resin is preferable. Among them, the (meth)acrylic resin is preferred in terms of high thermal decomposition property and less residual carbon after sintering.

作為上述(甲基)丙烯酸樹脂，例如可列舉：(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸丙酯、(甲基)丙烯酸正丁酯、(甲基)丙烯酸第三丁酯、(甲基)丙烯酸異丁酯、(甲基)丙烯酸環己酯、(甲基)丙烯酸2-乙基己酯、(甲基)丙烯酸異莰酯、(甲基)丙烯酸正硬脂酯、(甲基)丙烯酸苄酯等(甲基)丙烯酸單體之同元聚合物，以及該等(甲基)丙烯酸單體與具有聚環氧烷結構之(甲基)丙烯酸單體的共聚物。作為上述聚環氧烷結構，例如可列舉：聚環氧丙烷、聚甲基環氧乙烷、聚乙基環氧乙烷、聚氧雜環丁烷、聚氧雜環戊烷。再者，本說明書中，所謂(甲基)丙烯酸酯係指丙烯酸酯及/或甲基丙烯酸酯。Examples of the (meth)acrylic resin include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, n-butyl (meth)acrylate, and (methyl). Tert-butyl acrylate, isobutyl (meth)acrylate, cyclohexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isodecyl (meth)acrylate, (meth)acrylic acid a homopolymer of a (meth)acrylic monomer such as n-stearyl ester or benzyl (meth)acrylate, and the (meth)acrylic monomer and a (meth)acrylic acid having a polyalkylene oxide structure Copolymer. Examples of the polyalkylene oxide structure include polypropylene oxide, polymethylethylene oxide, polyethylethylene oxide, polyoxetane, and polyoxolane. In the present specification, the term "(meth)acrylate" means acrylate and/or methacrylate.

上述(甲基)丙烯酸樹脂較佳為具有源自甲基丙烯酸甲酯之鏈段。藉由具有源自甲基丙烯酸甲酯之鏈段，能夠以較少之黏合劑樹脂量而獲得具有適合於網版印刷之黏度的金屬氧化物微粒子分散糊料。其中，作為黏合劑樹脂，最佳為使用甲基丙烯酸甲酯之同元聚合物即聚甲基丙烯酸甲酯(以下，亦稱為PMMA(Polymethylmethacrylate))。The above (meth)acrylic resin preferably has a segment derived from methyl methacrylate. By having a segment derived from methyl methacrylate, it is possible to obtain a metal oxide fine particle-dispersed paste having a viscosity suitable for screen printing with a small amount of binder resin. Among them, as the binder resin, polymethyl methacrylate (hereinafter also referred to as PMMA (Polymethylmethacrylate)) which is a homopolymer of methyl methacrylate is preferably used.

上述(甲基)丙烯酸樹脂較佳為於分子末端具有極性基，最佳為於分子末端具有羧酸。The above (meth)acrylic resin preferably has a polar group at the molecular terminal, and preferably has a carboxylic acid at the molecular terminal.

進而，上述(甲基)丙烯酸樹脂更佳為僅於分子末端具有極性基。分子末端之極性基吸附於上述金屬氧化物微粒子上，發揮抑制上述金屬氧化物微粒子之凝聚而提高分散性之作用。又，上述(甲基)丙烯酸樹脂即使於分子末端具有極性基，對熱分解性所造成之影響亦較少。然而，於將(甲基)丙烯酸、(甲基)丙烯酸羥基乙酯等具有極性基之(甲基)丙烯酸單體作為單體成分進行聚合之情形時，所獲得之(甲基)丙烯酸樹脂之側鏈具有極性基，該等(甲基)丙烯酸樹脂之熱分解性極差且燒結後之殘留碳亦較多，因此於用於製造透明電極等時之情形時，有時對光之透射性或導電性造成不良影響。Further, the above (meth)acrylic resin is more preferably a polar group only at the molecular terminal. The polar group at the terminal of the molecule is adsorbed on the metal oxide fine particles, and acts to suppress aggregation of the metal oxide fine particles to improve dispersibility. Further, even if the (meth)acrylic resin has a polar group at the molecular terminal, it has little effect on thermal decomposition property. However, when a (meth)acrylic acid monomer having a polar group such as (meth)acrylic acid or hydroxyethyl (meth)acrylate is polymerized as a monomer component, the obtained (meth)acrylic resin is used. The side chain has a polar group, and the (meth)acrylic resin has extremely poor thermal decomposition property and a large amount of residual carbon after sintering. Therefore, when it is used for the production of a transparent electrode or the like, light transmission is sometimes performed. Or conductivity causes adverse effects.

但是，若為不妨礙所得(甲基)丙烯酸樹脂之熱分解性的量，則亦可添加具有極性基之(甲基)丙烯酸單體進行聚合。上述具有極性基之(甲基)丙烯酸單體並無特別限定，例如可列舉：(甲基)丙烯酸、(甲基)丙烯酸羥基乙酯、(甲基)丙烯酸羥基丙酯、琥珀酸2-(甲基)丙烯醯氧基乙酯、依康酸。However, if it does not interfere with the thermal decomposition property of the obtained (meth)acrylic resin, the (meth)acrylic monomer having a polar group may be added and polymerized. The (meth)acrylic monomer having a polar group is not particularly limited, and examples thereof include (meth)acrylic acid, hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, and succinic acid 2-( Methyl) propylene methoxyethyl ester, isoconic acid.

當將上述(甲基)丙烯酸樹脂聚合或共聚合時，上述具有極性基之(甲基)丙烯酸單體之添加量之較佳上限為5重量%。若上述具有極性基之(甲基)丙烯酸單體之添加量超過5重量%，則有時所獲得之(甲基)丙烯酸樹脂之熱分解性變得極差，且燒結後之殘留碳亦變多。When the (meth)acrylic resin is polymerized or copolymerized, a preferred upper limit of the amount of the above-mentioned (meth)acrylic monomer having a polar group is 5% by weight. When the amount of the (meth)acrylic monomer having a polar group is more than 5% by weight, the thermal decomposition property of the obtained (meth)acrylic resin may be extremely poor, and the residual carbon after sintering may also become many.

上述(甲基)丙烯酸樹脂之製造方法並無特別限定，例如可列舉利用自由基聚合法、活性自由基聚合法、引發轉移終止劑(iniferter)聚合法、陰離子聚合法、活性陰離子聚合法等先前公知之方法將上述(甲基)丙烯酸單體聚合或共聚合之方法。The method for producing the (meth)acrylic resin is not particularly limited, and examples thereof include a radical polymerization method, a living radical polymerization method, an inductive polymerization method, an anionic polymerization method, and a living anionic polymerization method. A method of polymerizing or copolymerizing the above (meth)acrylic monomer is known.

又，上述僅於分子末端具有極性基之(甲基)丙烯酸樹脂之製造方法並無特別限定，例如可列舉：於具有極性基之鏈轉移劑之存在下，利用自由基聚合法、活性自由基聚合法、引發轉移終止劑聚合法、陰離子聚合法、活性陰離子聚合法等先前公知之方法，將上述(甲基)丙烯酸單體聚合或共聚合之方法；以及於具有極性基之聚合起始劑之存在下，利用自由基聚合法、活性自由基聚合法、引發轉移終止劑聚合法、陰離子聚合法、活性陰離子聚合法等先前公知之方法，將上述(甲基)丙烯酸單體聚合或共聚合之方法。該等方法可單獨使用，亦可併用兩種以上。再者，上述僅於(甲基)丙烯酸樹脂之分子末端導入有極性基的情況，例如可藉由13C-NMR確認。Further, the method for producing the (meth)acrylic resin having a polar group only at the molecular terminal is not particularly limited, and examples thereof include a radical polymerization method and an active radical in the presence of a chain transfer agent having a polar group. a previously known method such as a polymerization method, an initiating transfer terminator polymerization method, an anionic polymerization method, a living anionic polymerization method, or the like, a method of polymerizing or copolymerizing the above (meth)acrylic monomer; and a polymerization initiator having a polar group In the presence of the above, the (meth)acrylic monomer is polymerized or copolymerized by a conventionally known method such as a radical polymerization method, a living radical polymerization method, an initiating transfer terminator polymerization method, an anionic polymerization method, or a living anionic polymerization method. The method. These methods may be used singly or in combination of two or more. Further, in the case where the polar group is introduced only at the molecular terminal of the (meth)acrylic resin, it can be confirmed, for example, by 13 C-NMR.

上述具有極性基之鏈轉移劑並無特別限定，例如可列舉：具有羥基作為極性基之硫醇基丙二醇、硫甘油，具有羧基作為極性基之硫醇基琥珀酸、硫醇基乙酸，具有胺基作為極性基之胺基乙硫醇。The chain transfer agent having a polar group is not particularly limited, and examples thereof include a thiol propylene glycol having a hydroxyl group as a polar group, thioglycerol, a thiol succinic acid having a carboxyl group as a polar group, a thiol acetic acid, and an amine. The group serves as a polar group of amino ethanethiol.

上述具有極性基之聚合起始劑並無特別限定，例如可列舉：對薄荷烷過氧化氫(「PERMENTA H」，日油公司製造)、二異丙基苯過氧化氫(「PERCUMYL P」，日油公司製造)、1,2,3,3-四甲基丁基過氧化氫(「PEROCTA H」，日油公司製造)、異丙苯過氧化氫(「PERCUMYL H-80」，日油公司製造)、第三丁基過氧化氫(「PERBUTYL H-69」，日油公司製造)、過氧化環己酮(「PERHEXA H」，日油公司製造)、1,1,3,3-四甲基丁基過氧化氫、第三丁基過氧化氫、第三戊基過氧化氫、過氧化二琥珀酸(「PEROYLSA」，日油公司製造)。又，亦可使用含有氮元素或酸基之各種偶氮系起始劑。The polymerization initiator having a polar group is not particularly limited, and examples thereof include p-menthane hydrogen peroxide ("PERMENTA H", manufactured by Nippon Oil Co., Ltd.) and diisopropylbenzene hydroperoxide ("PERCUMYL P", Made by Nippon Oil Co., Ltd., 1,2,3,3-tetramethylbutyl hydroperoxide ("PEROCTA H", manufactured by Nippon Oil Co., Ltd.), cumene hydroperoxide ("PERCUMYL H-80", Nippon Oil Manufactured by the company, tert-butyl hydroperoxide ("PERBUTYL H-69", manufactured by Nippon Oil Co., Ltd.), cyclohexanone peroxide ("PERHEXA H", manufactured by Nippon Oil Co., Ltd.), 1,1,3,3- Tetramethylbutyl hydroperoxide, tert-butyl hydroperoxide, third amyl hydroperoxide, and disuccinic acid peroxide ("PEROYLSA", manufactured by Nippon Oil Co., Ltd.). Further, various azo-based initiators containing a nitrogen element or an acid group can also be used.

上述(甲基)丙烯酸樹脂之由聚苯乙烯換算之重量平均分子量之較佳下限為5000，較佳上限為50000。若重量平均分子量低於5000，則有時無法獲得具有網版印刷所必需之黏度之金屬氧化物微粒子分散糊料。若重量平均分子量超過50000，則有時因所獲得之金屬氧化物微粒子分散糊料之分散性下降、或者變得易於產生拉絲，故印刷性惡化。重量平均分子量之更佳上限為40000，進而更佳之上限為30000。於使用由聚苯乙烯換算之重量平均分子量為5000～30000之(甲基)丙烯酸樹脂之情形時，利用網版印刷所形成之圖像變得特別鮮明。A preferred lower limit of the weight average molecular weight of the (meth)acrylic resin in terms of polystyrene is 5,000, and a preferred upper limit is 50,000. When the weight average molecular weight is less than 5,000, a metal oxide fine particle-dispersed paste having a viscosity necessary for screen printing may not be obtained. When the weight average molecular weight exceeds 50,000, the dispersibility of the metal oxide fine particle-dispersed paste obtained may be lowered or the drawing may be easily generated, so that the printability may be deteriorated. A higher upper limit of the weight average molecular weight is 40,000, and a more preferred upper limit is 30,000. When a (meth)acrylic resin having a weight average molecular weight of 5,000 to 30,000 in terms of polystyrene is used, an image formed by screen printing becomes particularly conspicuous.

再者，由聚苯乙烯換算之重量平均分子量係藉由例如使用SHOKO公司製造之管柱LF-804作為管柱，來進行GPC(Gel Permeation Chromatography，凝膠滲透層析法)測定而算出。In addition, the weight average molecular weight in terms of polystyrene is calculated by GPC (Gel Permeation Chromatography) measurement using, for example, a column LF-804 manufactured by SHOKO Co., Ltd. as a column.

上述纖維素樹脂並無特別限定，例如較佳為乙基纖維素、羧甲基纖維素。The cellulose resin is not particularly limited, and for example, ethyl cellulose or carboxymethyl cellulose is preferred.

上述聚醚樹脂並無特別限定，例如可列舉聚乙二醇、聚丙二醇、聚丁二醇等。其中，就與上述多元醇(該多元醇係於1分子中具有2個以上之羥基；分子中之碳原子數相對於羥基數之比低於5；且常溫下之黏度為100mPa‧s以上)相溶性良好的方面而言，較佳為聚乙二醇與聚丙二醇之共聚物The polyether resin is not particularly limited, and examples thereof include polyethylene glycol, polypropylene glycol, and polybutylene glycol. In addition, the polyol (the polyol has two or more hydroxyl groups in one molecule; the ratio of the number of carbon atoms in the molecule to the number of hydroxyl groups is less than 5; and the viscosity at normal temperature is 100 mPa·s or more) In terms of good compatibility, a copolymer of polyethylene glycol and polypropylene glycol is preferred.

上述聚縮醛樹脂並無特別限定，較佳為與上述聚醚樹脂同樣地具有伸乙基、伸丙基、四亞甲基等單元之聚縮醛樹脂。The polyacetal resin is not particularly limited, and is preferably a polyacetal resin having a unit such as an ethyl group, a propyl group or a tetramethylene group, similarly to the above polyether resin.

上述聚乙烯縮醛樹脂較佳為藉由利用醛將聚乙烯醇加以縮醛化而獲得之聚乙烯縮醛樹脂。The polyvinyl acetal resin is preferably a polyvinyl acetal resin obtained by acetalizing polyvinyl alcohol with an aldehyde.

上述聚乙烯醇較佳為藉由將甲酸乙烯酯、乙酸乙烯酯、丙酸乙烯酯、新戊酸乙烯酯等乙烯酯之聚合物加以皂化而獲得之聚乙烯醇。上述乙烯酯就經濟性而言，更佳為乙酸乙烯酯。The polyvinyl alcohol is preferably a polyvinyl alcohol obtained by saponifying a polymer of a vinyl ester such as vinyl acetate, vinyl acetate, vinyl propionate or vinyl pivalate. The above vinyl ester is more preferably vinyl acetate in terms of economy.

又，上述聚乙烯醇較佳為藉由將上述乙烯酯與α-烯烴之共聚物加以皂化而獲得之聚乙烯醇。藉由使用α-烯烴，聚乙烯縮醛樹脂之氫鍵結力下降，其結果可提昇所獲得之金屬氧化物微粒子分散糊料之黏度的經時穩定性或印刷性。作為上述α-烯烴，例如可列舉：乙烯、丙烯、異丙烯、丁烯、異丁烯、戊烯、己烯、環己烯、環己基乙烯、環己基丙烯。其中，較佳為乙烯。Further, the polyvinyl alcohol is preferably a polyvinyl alcohol obtained by saponifying a copolymer of the above vinyl ester and an α-olefin. By using an α-olefin, the hydrogen bonding strength of the polyvinyl acetal resin is lowered, and as a result, the temporal stability or printability of the viscosity of the obtained metal oxide fine particle-dispersed paste can be improved. Examples of the α-olefin include ethylene, propylene, isopropylene, butylene, isobutylene, pentene, hexene, cyclohexene, cyclohexylethylene, and cyclohexylpropene. Among them, ethylene is preferred.

又，作為上述聚乙烯醇，亦可使用藉由於硫乙酸、硫醇基丙酸等硫醇化合物之存在下，將上述乙烯酯與乙烯共聚合，其後進行皂化而獲得之末端改質聚乙烯醇。Further, as the polyvinyl alcohol, a terminal modified polyethylene obtained by copolymerizing the vinyl ester with ethylene in the presence of a thiol compound such as thioacetic acid or thiolpropionic acid, followed by saponification may be used. alcohol.

於將上述聚乙烯醇共聚合時，上述α-烯烴之含量之較佳下限為1莫耳%，較佳上限為20莫耳%。若上述α-烯烴之含量低於1莫耳%，則有時無法獲得添加上述α-烯烴之效果。若上述α-烯烴之含量超過20莫耳%，則有時因上述聚乙烯醇對於水之溶解性下降，故變得難以進行縮醛化反應，或者所獲得之聚乙烯縮醛樹脂之疏水性變得過強，而對於有機溶劑之溶解性下降。When the polyvinyl alcohol is copolymerized, a preferred lower limit of the content of the above α-olefin is 1 mol%, and a preferred upper limit is 20 mol%. When the content of the above α-olefin is less than 1 mol%, the effect of adding the above α-olefin may not be obtained. When the content of the above α-olefin exceeds 20 mol%, the solubility of the polyvinyl alcohol in water may be lowered, so that it may be difficult to carry out the acetalization reaction or the hydrophobicity of the obtained polyvinyl acetal resin. It becomes too strong, and the solubility to an organic solvent decreases.

於本發明之金屬氧化物微粒子分散糊料中，上述黏合劑樹脂之含量之較佳下限為1重量%，較佳上限為20重量%。若上述黏合劑樹脂之含量低於1重量%，則有時無法獲得充分的由添加黏合劑樹脂所得之增黏效果。若上述黏合劑樹脂之含量超過20重量%，則有時燒結後之殘留碳變多。上述黏合劑樹脂之含量之更佳下限為3重量%，更佳上限為15重量%。In the metal oxide fine particle dispersion paste of the present invention, a preferred lower limit of the content of the above binder resin is 1% by weight, and a preferred upper limit is 20% by weight. When the content of the above binder resin is less than 1% by weight, a sufficient viscosity-increasing effect by the addition of the binder resin may not be obtained. When the content of the above binder resin exceeds 20% by weight, the residual carbon after sintering may increase. A more preferred lower limit of the content of the above binder resin is 3% by weight, and a more preferred upper limit is 15% by weight.

又，於本發明之金屬氧化物微粒子分散糊料中，在如上所述之沸點為140℃以上之其他有機溶劑之中，最佳為使用二乙二醇單***乙酸酯、乙二醇單丁醚乙酸酯、乙二醇單***乙酸酯、二乙二醇單丁醚乙酸酯、二氫松油醇乙酸酯、松油醇乙酸酯、乙酸2-丁氧基乙酯、乙酸2-乙氧基乙酯、乙酸2-甲氧基乙酯、2-苯氧基乙醇、2-(甲氧基甲氧基)乙醇、三乙二醇單甲醚、三乙二醇、二乙二醇單丁基乙酸酯、二乙二醇單丁醚乙酸酯、苯氧基乙酸酯、苯氧基乙基乙酸酯、乙二醇單苯醚、二乙二醇單苯醚、乙二醇單苄醚、二乙二醇單苄醚、丙二醇單苯醚、苄基乙二醇、苯基乙酸甲酯、苯基乙酸乙酯、苯甲酸乙酯、苯甲酸甲酯等。上述多元醇雖存在對於上述(甲基)丙烯酸樹脂等黏合劑樹脂之溶解性較低之情形，但藉由與該等有機溶劑併用，可於維持金屬氧化物微粒子之分散性之狀態下改善對於黏合劑樹脂之溶解性。Further, in the metal oxide fine particle-dispersed paste of the present invention, among other organic solvents having a boiling point of 140 ° C or higher as described above, it is preferred to use diethylene glycol monoethyl ether acetate or ethylene glycol. Butyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, dihydroterpineol acetate, terpineol acetate, 2-butoxyethyl acetate , 2-ethoxyethyl acetate, 2-methoxyethyl acetate, 2-phenoxyethanol, 2-(methoxymethoxy)ethanol, triethylene glycol monomethyl ether, triethylene glycol , diethylene glycol monobutyl acetate, diethylene glycol monobutyl ether acetate, phenoxy acetate, phenoxyethyl acetate, ethylene glycol monophenyl ether, diethylene glycol Monophenyl ether, ethylene glycol monobenzyl ether, diethylene glycol monobenzyl ether, propylene glycol monophenyl ether, benzyl glycol, methyl phenyl acetate, ethyl phenylacetate, ethyl benzoate, benzoic acid Ester and the like. The polyol may have a low solubility in a binder resin such as the above (meth)acrylic resin, but it can be used in combination with the organic solvent to maintain the dispersibility of the metal oxide fine particles. Solubility of the binder resin.

本發明之金屬氧化物微粒子分散糊料於23℃、10rpm之探針轉速下使用B型黏度計進行測定所得之黏度之較佳下限為6Pa‧s，較佳上限為40Pa‧s。若上述黏度低於6Pa‧s，則有時上述金屬氧化物微粒子沈澱，分散性變低。若上述黏度超過40Pa‧s，則有時使用金屬氧化物微粒子分散糊料進行網版印刷時產生拉絲。The preferred lower limit of the viscosity of the metal oxide fine particle-dispersed paste of the present invention measured at 23 ° C and a probe rotation speed of 10 rpm using a B-type viscometer is 6 Pa s, and the upper limit is preferably 40 Pa ‧ . When the viscosity is less than 6 Pa‧s, the metal oxide fine particles may precipitate and the dispersibility may be lowered. When the viscosity is more than 40 Pa s, the wire drawing may be generated when screen printing is performed using the metal oxide fine particle dispersion paste.

製造本發明之金屬氧化物微粒子分散糊料之方法並無特別限定，例如可列舉對本發明之金屬氧化物微粒子分散漿料中添加上述黏合劑樹脂及各種添加劑，使用三輥研磨機等進一步進行分散處理的方法。又，亦可使用珠磨機、球磨機、摻合研磨機、三輥研磨機等混合機，將上述金屬氧化物微粒子、上述有機溶劑及上述高分子陰離子系分散劑加以混合後，進而添加上述黏合劑樹脂並利用上述混合機進行混合。The method of producing the metal oxide fine particle-dispersed paste of the present invention is not particularly limited. For example, the above-mentioned binder resin and various additives are added to the metal oxide fine particle dispersion slurry of the present invention, and further dispersed by using a three-roll mill or the like. The method of processing. Further, the metal oxide fine particles, the organic solvent, and the polymer anionic dispersant may be mixed by using a mixer such as a bead mill, a ball mill, a blending mill, or a three-roll mill, and then the above-mentioned bonding may be further added. The resin was mixed using the above mixer.

本發明之金屬氧化物微粒子分散漿料及本發明之金屬氧化物微粒子分散糊料之用途並無特別限定，例如較佳為用作用於製造金屬氧化物薄膜之材料，上述金屬氧化物薄膜係形成為電漿顯示器面板、液晶顯示器面板、太陽電池、鋰離子電池等之透明電極者。The use of the metal oxide fine particle dispersion slurry of the present invention and the metal oxide fine particle dispersion paste of the present invention is not particularly limited. For example, it is preferably used as a material for producing a metal oxide thin film, and the above metal oxide thin film is formed. It is a transparent electrode for plasma display panels, liquid crystal display panels, solar cells, lithium ion batteries, and the like.

作為上述金屬氧化物薄膜之製造方法，例如可列舉如下方法：使用網版印刷、凹版膠印、輥塗機、刮塗機等的各種印刷方法，將本發明之金屬氧化物微粒子分散漿料或本發明之金屬氧化物微粒子分散糊料塗佈於基板上後，進行溶劑乾燥或燒結。Examples of the method for producing the metal oxide thin film include a method of dispersing a metal oxide fine particle dispersion slurry of the present invention by various printing methods such as screen printing, gravure offset printing, a roll coater, and a knife coater. The metal oxide fine particle dispersion paste of the invention is applied onto a substrate, and then dried or sintered by a solvent.

包括利用網版印刷來塗佈本發明之金屬氧化物微粒子分散漿料或本發明之金屬氧化物微粒子分散糊料之步驟的金屬氧化物薄膜之製造方法亦為本發明之一。The method for producing a metal oxide film comprising the step of coating the metal oxide fine particle dispersion slurry of the present invention or the metal oxide fine particle dispersion paste of the present invention by screen printing is also one of the inventions.

使用本發明之金屬氧化物薄膜之製造方法所獲得之金屬氧化物薄膜亦為本發明之一。進而，於使用氧化鎂微粒子分散糊料作為本發明之金屬氧化物微粒子分散糊料之情形時，可獲得氧化鎂薄膜。The metal oxide film obtained by the method for producing a metal oxide film of the present invention is also one of the inventions. Further, when a magnesium oxide fine particle-dispersed paste is used as the metal oxide fine particle-dispersed paste of the present invention, a magnesium oxide thin film can be obtained.

於將以上述方式所獲得之氧化鎂薄膜用作電漿顯示器之電介質體保護層的情形時，可獲得電漿顯示器用前面板。此種電漿顯示器用前面板亦為本發明之一。When the magnesium oxide film obtained in the above manner is used as a dielectric protective layer of a plasma display, a front panel for a plasma display can be obtained. The front panel for such a plasma display is also one of the inventions.

於本發明之金屬氧化物薄膜為氧化鎂薄膜之情形時，將氧化鎂薄膜於450℃下燒成30分鐘後之殘留碳之較佳上限為1重量%。若氧化鎂之殘留碳超過1重量%，則有時燒成後之殘留碳變多，電漿顯示器面板之壽命變短。將上述氧化鎂薄膜於450℃下燒成30分鐘後之殘留碳之更佳上限為0.5重量%。又，製造上述金屬氧化物微粒子之方法並無特別限定，就可減少本發明之金屬氧化物薄膜中燒成後之殘留碳之量的方面而言，較佳為例如於微粒子化之過程中利用金屬氧化物之組成中不含碳之氣相氧化反應法來製造。In the case where the metal oxide film of the present invention is a magnesium oxide film, a preferred upper limit of the residual carbon after firing the magnesium oxide film at 450 ° C for 30 minutes is 1% by weight. When the residual carbon of the magnesium oxide exceeds 1% by weight, the residual carbon after firing may increase, and the life of the plasma display panel may become short. A more preferable upper limit of residual carbon after firing the above magnesium oxide film at 450 ° C for 30 minutes is 0.5% by weight. Further, the method for producing the metal oxide fine particles is not particularly limited, and the amount of residual carbon after firing in the metal oxide thin film of the present invention can be reduced, and it is preferably used, for example, in the process of pulverization. It is produced by a gas phase oxidation reaction method in which the composition of the metal oxide does not contain carbon.

於本發明之電漿顯示器用前面板中，當形成氧化鎂薄膜時，必需將上述氧化鎂微粒子分散糊料印刷於電漿顯示器用前面板之透明電介質體層上，並進行燒成。於本發明中，可於由通常所使用之鈉鈣玻璃、硼矽酸玻璃、鋁矽酸鹽玻璃、鋇鍶玻璃、由硼酸與氧化鉍-氧化鉬-鹼金屬氧化物構成之玻璃等所構成的透明電介質體層上良好地印刷氧化鎂微粒子分散糊料，並進行燒成。In the front panel for a plasma display of the present invention, when a magnesium oxide film is formed, it is necessary to print the above-mentioned magnesium oxide fine particle dispersion paste on a transparent dielectric body layer of a front panel for a plasma display and to perform firing. In the present invention, it may be composed of soda lime glass, borosilicate glass, aluminosilicate glass, bismuth glass, glass composed of boric acid and cerium oxide-molybdenum oxide-alkali metal oxide. The magnesium oxide fine particle-dispersed paste is well printed on the transparent dielectric body layer and fired.

根據本發明，可提供一種藉由改善金屬氧化物微粒子之分散性而實現優異之網版印刷性的金屬氧化物微粒子分散漿料。進而，根據本發明，可提供一種含有該金屬氧化物微粒子分散漿料之金屬氧化物微粒子分散糊料、使用該金屬氧化物微粒子分散漿料或該金屬氧化物微粒子分散糊料之金屬氧化物薄膜之製造方法、以及利用該金屬氧化物薄膜之製造方法所獲得之金屬氧化物薄膜。According to the present invention, it is possible to provide a metal oxide fine particle-dispersed slurry which achieves excellent screen printing properties by improving the dispersibility of metal oxide fine particles. Further, according to the present invention, a metal oxide fine particle-dispersed paste containing the metal oxide fine particle-dispersed slurry, a metal oxide thin film using the metal oxide fine particle-dispersed slurry or the metal oxide fine particle-dispersed paste can be provided. A manufacturing method and a metal oxide thin film obtained by the method for producing a metal oxide thin film.

以下，列舉實施例來更詳細地說明本發明，但本發明並非僅限定於該等實施例。Hereinafter, the present invention will be described in more detail by way of examples, but the invention is not limited to the examples.

(實施例1)(Example 1)

(黏合劑樹脂之製造)(Manufacture of adhesive resin)

於具備攪拌機、冷卻器、溫度計、熱水浴及氮氣導入口之2L可分離式燒瓶中，混合100重量份之作為(甲基)丙烯酸單體之甲基丙烯酸甲酯、1.5重量份之作為鏈轉移劑之硫醇基琥珀酸、以及100重量份之作為有機溶劑之丙酮，從而獲得單體混合液。100 parts by weight of methyl methacrylate as a (meth)acrylic monomer and 1.5 parts by weight as a chain in a 2 L separable flask equipped with a stirrer, a cooler, a thermometer, a hot water bath, and a nitrogen inlet The thiol succinic acid of the transfer agent and 100 parts by weight of acetone as an organic solvent are used to obtain a monomer mixture.

對於所獲得之單體混合液，藉由使用氮氣起泡20分鐘而去除溶氧後，將可分離式燒瓶系統內以氮氣進行置換，一面攪拌一面升溫至熱水浴沸騰為止。繼而，添加將聚合起始劑(日油公司製造之「PERHEXA H」)以丙酮稀釋而得之溶液。又，於聚合過程中添加數次含有聚合起始劑之丙酮溶液。自聚合開始起7小時後，藉由冷卻至室溫而結束聚合，從而獲得聚甲基丙烯酸甲酯之丙酮溶液。對於所獲得之聚甲基丙烯酸甲酯，使用SHOKO公司製造之管柱LF-804作為管柱，進行利用凝膠滲透層析法(GPC)之分析，結果由聚苯乙烯換算之重量平均分子量為2萬。After the dissolved oxygen was removed by bubbling nitrogen gas for 20 minutes with the obtained monomer mixture, the separable flask system was replaced with nitrogen, and the mixture was heated while stirring until the hot water bath boiled. Then, a solution obtained by diluting a polymerization initiator ("PERHEXA H" manufactured by NOF Corporation) with acetone was added. Further, an acetone solution containing a polymerization initiator was added several times during the polymerization. After 7 hours from the start of the polymerization, the polymerization was terminated by cooling to room temperature, thereby obtaining a solution of polymethyl methacrylate in acetone. With respect to the obtained polymethyl methacrylate, the column LF-804 manufactured by SHOKO Co., Ltd. was used as a column, and analysis by gel permeation chromatography (GPC) was carried out, and the weight average molecular weight in terms of polystyrene was 20000.

(金屬氧化物微粒子分散糊料之製造)(Manufacture of metal oxide fine particle dispersion paste)

以最終達到表1中所記載之金屬氧化物微粒子分散糊料之組成比的方式，對調配有2,2,4-三甲基-1,3-戊二醇單異丁酸酯、丙二醇單苯醚、以及1,6-己二醇(碳原子數相對於羥基數之比=3，常溫下為固體)之媒液(vehicle)中，添加高分子陰離子系分散劑(BYK Chemie公司製造之「DISPERBYK-111」)、以及ITO粒子(C. I. Kasei公司製造，平均粒徑為30nm)，使用珠磨機(AIMEX公司製造之「RMB-08」)及作為介質之粒徑為1mm之氧化鋯粒子進行6小時珠磨機處理。繼而，以使樹脂固體成分達到17重量%之方式添加上述(黏合劑樹脂之製造)中所獲得之聚甲基丙烯酸甲酯之丙酮溶液，利用真空去溶劑處理去除丙酮而獲得金屬氧化物微粒子分散糊料。2,2,4-trimethyl-1,3-pentanediol monoisobutyrate, propylene glycol single was prepared in such a manner as to finally reach the composition ratio of the metal oxide fine particle dispersion paste described in Table 1. A polymer anionic dispersant (by BYK Chemie Co., Ltd.) is added to a vehicle containing phenyl ether and 1,6-hexanediol (the ratio of the number of carbon atoms to the number of hydroxyl groups = 3, which is solid at normal temperature). "DISPERBYK-111") and ITO particles (manufactured by CI Kasei Co., Ltd., average particle size: 30 nm), using a bead mill ("RMB-08" manufactured by AIMEX Corporation) and zirconia particles having a particle size of 1 mm as a medium A 6-hour bead mill process was performed. Then, the acetone solution of the polymethyl methacrylate obtained in the above (manufacture of a binder resin) is added in such a manner that the solid content of the resin is 17% by weight, and acetone is removed by vacuum desolvation treatment to obtain dispersion of metal oxide fine particles. Paste.

(實施例2)(Example 2)

(黏合劑樹脂之製造)(Manufacture of adhesive resin)

以與實施例1相同之方式獲得聚甲基丙烯酸甲酯之丙酮溶液。A solution of polymethyl methacrylate in acetone was obtained in the same manner as in Example 1.

(金屬氧化物微粒子分散糊料之製造)(Manufacture of metal oxide fine particle dispersion paste)

以最終達到表1中所記載之金屬氧化物微粒子分散糊料之組成比的方式，對調配有α-松油醇、二乙二醇單丁醚乙酸酯、1,4-丁二醇(碳原子數相對於羥基數之比=2，常溫下之黏度為128mPa‧s)、以及2,2,4-三甲基-1,3-戊二醇單異丁酸酯之媒液中，添加高分子陰離子系分散劑(花王公司製造之「RHEODOL L-95」)、以及SnO2粒子(JEMCO公司製造之「S-2000」，平均粒徑為30nm)，使用珠磨機(AIMEX公司製造之「RMB-08」)及作為介質之粒徑為1mm之氧化鋯粒子進行6小時珠磨機處理。繼而，以使樹脂固體成分達到17重量%之方式添加上述(黏合劑樹脂之製造)中所獲得之聚甲基丙烯酸甲酯之丙酮溶液，利用真空去溶劑處理去除丙酮而獲得金屬氧化物微粒子分散糊料。The α-terpineol, diethylene glycol monobutyl ether acetate, and 1,4-butanediol were formulated in such a manner that the composition ratio of the metal oxide fine particle-dispersed paste described in Table 1 was finally achieved. The ratio of the number of carbon atoms to the number of hydroxyl groups = 2, the viscosity at room temperature is 128 mPa ‧ s), and the medium of 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate A polymer anionic dispersant ("RHEODOL L-95" manufactured by Kao Corporation) and SnO 2 particles ("S-2000" manufactured by JEMCO Co., Ltd., average particle diameter: 30 nm) were added, and a bead mill (manufactured by AIMEX Co., Ltd.) was used. The "RMB-08" and the zirconia particles having a particle diameter of 1 mm as a medium were subjected to a 6-hour bead mill treatment. Then, the acetone solution of the polymethyl methacrylate obtained in the above (manufacture of a binder resin) is added in such a manner that the solid content of the resin is 17% by weight, and acetone is removed by vacuum desolvation treatment to obtain dispersion of metal oxide fine particles. Paste.

(實施例3)(Example 3)

(黏合劑樹脂之製造)(Manufacture of adhesive resin)

以與實施例1相同之方式獲得聚甲基丙烯酸甲酯之丙酮溶液。A solution of polymethyl methacrylate in acetone was obtained in the same manner as in Example 1.

(金屬氧化物微粒子分散糊料之製造)(Manufacture of metal oxide fine particle dispersion paste)

以最終達到表1中所記載之金屬氧化物微粒子分散糊料之組成比的方式，對調配有2,2,4-三甲基-1,3-戊二醇單異丁酸酯、3-甲基-1,5-戊二醇(碳原子數相對於羥基數之比=3，常溫下之黏度為173mPa‧s)、以及丙二醇單苯醚之媒液中，添加高分子陰離子系分散劑(東邦化學公司製造之「RS-710」)、以及TiO2粒子(日本AEROSIL公司製造之「P-25」，平均粒徑為20nm)，使用珠磨機(AIMEX公司製造之「RMB-08」)及作為介質之粒徑為1mm之氧化鋯粒子進行6小時珠磨機處理。繼而，以使樹脂固體成分達到13重量%之方式添加上述(黏合劑樹脂之製造)中所獲得之聚甲基丙烯酸甲酯之丙酮溶液，利用真空去溶劑處理去除丙酮而獲得金屬氧化物微粒子分散糊料。The 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate was prepared in such a manner that the composition ratio of the metal oxide fine particle-dispersed paste described in Table 1 was finally achieved. Methyl-1,5-pentanediol (the ratio of the number of carbon atoms to the number of hydroxyl groups = 3, the viscosity at room temperature is 173 mPa ‧ s), and the polymer liquid of propylene glycol monophenyl ether is added with a polymer anionic dispersant ("RS-710" manufactured by Toho Chemical Co., Ltd.) and TiO 2 particles ("P-25" manufactured by AEROSIL, Japan, average particle size: 20 nm), using a bead mill ("RMB-08" manufactured by AIMEX Corporation) And a zirconia particle having a particle diameter of 1 mm as a medium was subjected to a 6-hour bead mill treatment. Then, the acetone solution of the polymethyl methacrylate obtained in the above (manufacture of a binder resin) is added in such a manner that the solid content of the resin is 13% by weight, and acetone is removed by vacuum desolvation treatment to obtain dispersion of metal oxide fine particles. Paste.

(實施例4)(Example 4)

(黏合劑樹脂之製造)(Manufacture of adhesive resin)

以與實施例1相同之方式獲得聚甲基丙烯酸甲酯之丙酮溶液。A solution of polymethyl methacrylate in acetone was obtained in the same manner as in Example 1.

(金屬氧化物微粒子分散糊料之製造)(Manufacture of metal oxide fine particle dispersion paste)

以最終達到表1中所記載之金屬氧化物微粒子分散糊料之組成比的方式，對調配有2,2,4-三甲基-1,3-戊二醇單異丁酸酯、2,4-二乙基-1,5-戊二醇(碳原子數相對於羥基數之比=4.5，常溫下之黏度為1650mPa‧s)、以及丙二醇單苯醚之媒液中，添加高分子陰離子系分散劑(楠本化成公司製造之「ED-216」)、以及MgO粒子(UBE MATERIALS公司製造之「MAGNESIA」，平均粒徑為50nm)，使用珠磨機(AIMEX公司製造之「RMB-08」)及作為介質之粒徑為1mm之氧化鋯粒子進行6小時珠磨機處理。繼而，以使樹脂固體成分達到13重量%之方式添加上述(黏合劑樹脂之製造)中所獲得之聚甲基丙烯酸甲酯之丙酮溶液，利用真空去溶劑處理去除丙酮而獲得金屬氧化物微粒子分散糊料。2,2,4-trimethyl-1,3-pentanediol monoisobutyrate, 2, was prepared in such a manner as to finally reach the composition ratio of the metal oxide fine particle-dispersed paste described in Table 1. 4-Diethyl-1,5-pentanediol (ratio of the number of carbon atoms to the number of hydroxyl groups = 4.5, viscosity at room temperature of 1650 mPa ‧ s), and a polymer anion of propylene glycol monophenyl ether A dispersant ("ED-216" manufactured by Kusumoto Kasei Co., Ltd.) and MgO particles ("MAGNESIA" manufactured by UBE MATERIALS Co., Ltd., average particle size: 50 nm), and a bead mill ("RMB-08" manufactured by AIMEX Corporation) was used. And a zirconia particle having a particle diameter of 1 mm as a medium was subjected to a 6-hour bead mill treatment. Then, the acetone solution of the polymethyl methacrylate obtained in the above (manufacture of a binder resin) is added in such a manner that the solid content of the resin is 13% by weight, and acetone is removed by vacuum desolvation treatment to obtain dispersion of metal oxide fine particles. Paste.

(實施例5)(Example 5)

(黏合劑樹脂之製造)(Manufacture of adhesive resin)

於具備攪拌機、冷卻器、溫度計、熱水浴及氮氣導入口之2L可分離式燒瓶中，混合100重量份之作為(甲基)丙烯酸單體之甲基丙烯酸甲酯、0.4重量份之作為鏈轉移劑之硫醇基琥珀酸、以及100重量份之作為有機溶劑之乙酸乙酯，從而獲得單體混合液。100 parts by weight of methyl methacrylate (meth)acrylic acid monomer and 0.4 parts by weight as a chain in a 2 L separable flask equipped with a stirrer, a cooler, a thermometer, a hot water bath, and a nitrogen gas inlet The thiol succinic acid of the transfer agent and 100 parts by weight of ethyl acetate as an organic solvent were used to obtain a monomer mixture.

對於所獲得之單體混合液，藉由使用氮氣起泡20分鐘而去除溶氧後，將可分離式燒瓶系統內以氮氣進行置換，並一面攪拌一面升溫至熱水浴沸騰為止。繼而，添加將聚合起始劑(日油公司製造之「PERHEXA H」)以乙酸乙酯稀釋而得之溶液。又，於聚合過程中添加數次含有聚合起始劑之乙酸乙酯溶液。After the dissolved oxygen was removed by bubbling nitrogen gas for 20 minutes with the obtained monomer mixture, the separable flask system was replaced with nitrogen, and the mixture was heated while stirring until the hot water bath boiled. Then, a solution obtained by diluting a polymerization initiator ("PERHEXA H" manufactured by NOF Corporation) with ethyl acetate was added. Further, an ethyl acetate solution containing a polymerization initiator was added several times during the polymerization.

自聚合開始起7小時後，藉由冷卻至室溫而結束聚合，從而獲得聚甲基丙烯酸甲酯之乙酸乙酯溶液。對於所獲得之聚甲基丙烯酸甲酯，使用SHOKO公司製造之管柱LF-804作為管柱，進行利用凝膠滲透層析法(GPC)之分析，結果由聚苯乙烯換算之重量平均分子量為5萬。After 7 hours from the start of the polymerization, the polymerization was terminated by cooling to room temperature, thereby obtaining an ethyl acetate solution of polymethyl methacrylate. With respect to the obtained polymethyl methacrylate, the column LF-804 manufactured by SHOKO Co., Ltd. was used as a column, and analysis by gel permeation chromatography (GPC) was carried out, and the weight average molecular weight in terms of polystyrene was 50000.

(金屬氧化物微粒子分散糊料之製造)(Manufacture of metal oxide fine particle dispersion paste)

以最終達到表1中所記載之金屬氧化物微粒子分散糊料之組成比的方式，利用松油醇乙酸酯、以及2,2,4-三甲基-1,3-戊二醇單異丁酸酯對所獲得之聚甲基丙烯酸甲酯之乙酸乙酯溶液進行溶劑取代，使用高速分散機使聚甲基丙烯酸甲酯分散而獲得媒液。Using terpineol acetate and 2,2,4-trimethyl-1,3-pentanediol monoiso, in such a manner as to finally reach the composition ratio of the metal oxide fine particle-dispersed paste described in Table 1. The butyric acid ester was subjected to solvent substitution with the obtained ethyl methacrylate solution of the methyl methacrylate, and the polymethyl methacrylate was dispersed using a high-speed disperser to obtain a vehicle liquid.

以最終達到表1中所記載之金屬氧化物微粒子分散糊料之組成比的方式，將甘油(碳原子數相對於羥基數之比=1，常溫下之黏度為1412mPa‧s)、高分子陰離子系分散劑(第一工業藥品公司製造之「SHALLOL AH」)、以及ZnO粒子(堺化學公司製造之「50A」，平均粒徑為20nm)利用高速分散器進行混練，從而獲得高黏度金屬氧化物微粒子分散漿料。藉由利用三輥研磨機將所獲得之高黏度金屬氧化物微粒子分散漿料進行混練而使其低黏度化後，將其與上述媒液混合，使用高速攪拌裝置充分混練後，使用三輥研磨機進一步進行處理，從而獲得金屬氧化物微粒子分散糊料。Glycerol (ratio of the number of carbon atoms to the number of hydroxyl groups = 1, the viscosity at room temperature is 1412 mPa ‧ s), and the polymer anion, in such a manner as to finally reach the composition ratio of the metal oxide fine particle-dispersed paste described in Table 1. A dispersant ("SHALLOL AH" manufactured by Daiichi Kogyo Co., Ltd.) and ZnO particles ("50A" manufactured by Seiko Chemical Co., Ltd., average particle diameter of 20 nm) were kneaded by a high-speed disperser to obtain a high-viscosity metal oxide. The microparticles disperse the slurry. The obtained high-viscosity metal oxide fine particle dispersion slurry is kneaded by a three-roll mill to have a low viscosity, and then mixed with the above-mentioned vehicle liquid, and kneaded thoroughly using a high-speed stirring device, and then used three-roll grinding. The machine is further processed to obtain a metal oxide fine particle-dispersed paste.

(比較例1)(Comparative Example 1)

(金屬氧化物微粒子分散糊料之製造)(Manufacture of metal oxide fine particle dispersion paste)

以最終達到表1中所記載之金屬氧化物微粒子分散糊料之組成比的方式，調配α-松油醇、高分子陰離子系分散劑(BYK Chemie公司製造之「DISPERBYK-111」)、以及ITO粒子(C. I. Kasei公司製造，平均粒徑為30nm)，使用珠磨機(AIMEX公司製造之「RMB-08」)及作為介質之粒徑為1mm之氧化鋯粒子進行6小時珠磨機處理。繼而，以達到3重量%之方式添加乙基纖維素(STD100，重量平均分子量為9萬)，使用高速分散機使乙基纖維素分散，使用高速攪拌裝置充分混練後，使用三輥研磨機進行處理，從而獲得金屬氧化物微粒子分散糊料。A-terpineol, a polymer anionic dispersant ("DISPERBYK-111" manufactured by BYK Chemie Co., Ltd.), and ITO were prepared so as to finally reach the composition ratio of the metal oxide fine particle-dispersed paste described in Table 1. The particles (manufactured by CI Kasei Co., Ltd., average particle diameter: 30 nm) were subjected to a 6-hour bead mill treatment using a bead mill ("RMB-08" manufactured by AIMEX Co., Ltd.) and zirconia particles having a particle diameter of 1 mm as a medium. Then, ethyl cellulose (STD100, weight average molecular weight: 90,000) was added so as to be 3% by weight, and ethyl cellulose was dispersed using a high-speed disperser, and after thorough kneading using a high-speed stirring device, a three-roll mill was used. The treatment is performed to obtain a metal oxide fine particle-dispersed paste.

(比較例2)(Comparative Example 2)

(金屬氧化物微粒子分散糊料之製造)(Manufacture of metal oxide fine particle dispersion paste)

以最終達到表1中所記載之金屬氧化物微粒子分散糊料之組成比的方式，使用高分子陰離子分散劑(花王公司製造之「L-95」)、以及SnO2粒子(JEMCO公司製造之「S-2000」，平均粒徑為30nm)，除此以外，以與比較例1相同之方式獲得金屬氧化物微粒子分散糊料。A polymer anionic dispersant ("L-95" manufactured by Kao Corporation) and SnO 2 particles (manufactured by JEMCO Co., Ltd.) were used to finally achieve the composition ratio of the metal oxide fine particle-dispersed paste described in Table 1. A metal oxide fine particle-dispersed paste was obtained in the same manner as in Comparative Example 1, except that the average particle diameter was 30 nm.

(比較例3)(Comparative Example 3)

(金屬氧化物微粒子分散糊料之製造)(Manufacture of metal oxide fine particle dispersion paste)

以最終達到表1中所記載之金屬氧化物微粒子分散糊料之組成比的方式，使用α-松油醇、高分子陰離子系分散劑(東邦化學公司製造之「RS710」)、以及TiO2粒子(日本AEROSIL公司製造之「P-25」，平均粒徑為20nm)，除此以外，以與比較例1相同之方式獲得金屬氧化物微粒子分散糊料。Α-terpineol, a polymer anionic dispersant ("RS710" manufactured by Toho Chemical Co., Ltd.), and TiO 2 particles were used so as to finally reach the composition ratio of the metal oxide fine particle-dispersed paste described in Table 1. A metal oxide fine particle-dispersed paste was obtained in the same manner as in Comparative Example 1, except that "P-25" manufactured by AEROSIL Co., Ltd., having an average particle diameter of 20 nm).

(比較例4)(Comparative Example 4)

(金屬氧化物微粒子分散糊料之製造)(Manufacture of metal oxide fine particle dispersion paste)

以最終達到表1中所記載之金屬氧化物微粒子分散糊料之組成比的方式，使用α-松油醇、高分子陰離子系分散劑(楠本化成公司製造之「ED-216」)、以及MgO粒子(UBE MATERIALS公司製造之「MAGNESIA」，平均粒徑為50nm)，除此以外，以與比較例1相同之方式獲得金屬氧化物微粒子分散糊料。Α-terpineol, a polymer anionic dispersant ("ED-216" manufactured by Nanben Chemical Co., Ltd.), and MgO are used so as to finally reach the composition ratio of the metal oxide fine particle-dispersed paste described in Table 1. A metal oxide fine particle-dispersed paste was obtained in the same manner as in Comparative Example 1, except that the particles ("MAGNESIA" manufactured by UBE MATERIALS Co., Ltd., having an average particle diameter of 50 nm).

(比較例5)(Comparative Example 5)

(金屬氧化物微粒子分散糊料之製造)(Manufacture of metal oxide fine particle dispersion paste)

以最終達到表1中所記載之金屬氧化物微粒子分散糊料之組成比的方式，使用α-松油醇、高分子陰離子系分散劑(第一工業藥品公司製造之「SHALLOL AH」)、以及ZnO粒子(堺化學公司製造之「50A」，平均粒徑為20nm)，除此以外，以與比較例1相同之方式獲得金屬氧化物微粒子分散糊料。Α-terpineol and a polymer anionic dispersant ("SHALLOL AH" manufactured by Dai-ichi Kogyo Co., Ltd.), and, as a result, the composition ratio of the metal oxide fine particle-dispersed paste of the first embodiment is used. A metal oxide fine particle-dispersed paste was obtained in the same manner as in Comparative Example 1, except that ZnO particles ("50A" manufactured by Seiko Chemical Co., Ltd., average particle diameter: 20 nm) were used.

＜評價＞<evaluation>

對於實施例1～5及比較例1～5中所獲得之金屬氧化物微粒子分散糊料進行以下之評價。將結果示於表1及表2中。The metal oxide fine particle dispersion pastes obtained in Examples 1 to 5 and Comparative Examples 1 to 5 were evaluated as follows. The results are shown in Tables 1 and 2.

(1)網版印刷性(1) Screen printing

使用金屬氧化物微粒子分散糊料，利用網版印刷機(MICROTEK公司製造之「MT-320TV」，間隙=2.0mm，刮漿板速度=50mm/s，刮漿刀速度=50mm/s，刮漿板壓=0.25MPa，刮漿刀壓=0.17MPa，背壓=0.10MPa)、網版製版(Tokyo Process Service公司製造之「SX230」，20μm之乳劑，320mm×320mm之網框)、印刷基板(150mm×150mm之鈉玻璃，厚度為15mm)、印刷圖像(線寬/間隙(Line/Space)=50μm/150μm)，於溫度為23℃、濕度為50%之環境下進行網版印刷。連續印刷10片，利用立體顯微鏡對所獲得之第10片之印刷圖像進行觀察，且以如下方式進行評價。Using metal oxide fine particles to disperse the paste, using a screen printing machine ("MT-320TV" manufactured by MICROTEK Co., Ltd., gap = 2.0 mm, squeegee speed = 50 mm/s, doctor blade speed = 50 mm/s, squeegee Plate pressure = 0.25 MPa, squeegee pressure = 0.17 MPa, back pressure = 0.110 MPa), screen plate making ("SX230" manufactured by Tokyo Process Service, 20 μm emulsion, 320 mm × 320 mm frame), printed circuit board ( 150 mm × 150 mm soda glass, thickness 15 mm), printed image (line/space = 50 μm / 150 μm), screen printing at a temperature of 23 ° C and a humidity of 50%. Ten sheets were continuously printed, and the printed image of the obtained tenth sheet was observed with a stereo microscope, and evaluated in the following manner.

○印刷圖像之粗細度並無不均。○ There is no unevenness in the thickness of the printed image.

△印刷圖像之粗細度存在不均，或者印刷圖像非常薄。△The thickness of the printed image is uneven, or the printed image is very thin.

×因堵塞而導致油墨未塗佈於印刷基板上。× The ink was not applied to the printed substrate due to clogging.

(2)燒結性(2) Sinterability

使用設定成5密耳(mil)之塗覆器，將金屬氧化物微粒子分散糊料塗佈於玻璃基板上，利用150℃之送風烘箱乾燥30分鐘後，於450℃之電爐中燒成30分鐘。利用堀場製作所製造之碳硫分析裝置來測定殘留碳(ppm)。又，以目視確認燒成顏色，並以如下方式進行評價。The metal oxide fine particle dispersion paste was applied onto a glass substrate using an applicator set to 5 mils, dried in a 150 ° C air oven for 30 minutes, and then fired in an electric furnace at 450 ° C for 30 minutes. . The residual carbon (ppm) was measured using a carbon-sulfur analyzer manufactured by Horiba, Ltd. Moreover, the baking color was visually confirmed, and it evaluated by the following.

○無色。○ colorless.

△成為淡黃色。△ becomes pale yellow.

×附有茶色之燒成顏色。×The color of the burnt brown is attached.

(3)儲藏穩定性(3) Storage stability

將金屬氧化物微粒子分散糊料於23℃之恆溫室中靜置2週後，以目視確認糊料之狀態，並以如下方式進行評價。After the metal oxide fine particle dispersion paste was allowed to stand in a constant temperature room at 23 ° C for 2 weeks, the state of the paste was visually confirmed and evaluated as follows.

○既未觀察到層分離，亦未觀察到金屬氧化物微粒子之沈澱。○ No layer separation was observed, and precipitation of metal oxide fine particles was not observed.

△透明之溶液滲出，但可再分散。△ The transparent solution oozes, but can be redispersed.

×分離成兩層，且金屬氧化物微粒子沈澱。× separated into two layers, and metal oxide fine particles were precipitated.

(實施例6)(Example 6)

調配12重量份之1,6-己二醇(碳原子數相對於羥基數之比=3，常溫下為固體)、5重量份之丙二醇、1重量份之界面活性劑(Nikko Chemical公司製造之「BL25」)、以及2重量份之高分子陰離子系分散劑(BYK Chemie公司製造之「DISPERBYK-111」)，使用高速分散機進行混合後，添加20重量份之ITO粒子(C. I. Kasei公司製造，平均粒徑為30nm)，並利用三輥研磨機進行處理，直至黏度變低且變得平滑為止。繼而，添加30重量份之1,6-己二醇及30重量份之丙二醇單苯醚，並利用高速攪拌機進行攪拌而獲得金屬氧化物微粒子分散漿料。12 parts by weight of 1,6-hexanediol (ratio of carbon number to hydroxyl number = 3, solid at normal temperature), 5 parts by weight of propylene glycol, and 1 part by weight of a surfactant (manufactured by Nikko Chemical Co., Ltd.) "BL25") and 2 parts by weight of a polymer anionic dispersant ("DISPERBYK-111" manufactured by BYK Chemie Co., Ltd.) were mixed with a high-speed disperser, and then 20 parts by weight of ITO particles (manufactured by CI Kasei Co., Ltd.) were added. The average particle diameter was 30 nm), and it was processed by a three-roll mill until the viscosity became low and it became smooth. Then, 30 parts by weight of 1,6-hexanediol and 30 parts by weight of propylene glycol monophenyl ether were added, and the mixture was stirred with a high speed mixer to obtain a metal oxide fine particle dispersion slurry.

(實施例7)(Example 7)

添加12重量份之2-乙基-1,3-己二醇(碳原子數相對於羥基數之比=4，常溫下之黏度為323mPa‧s)、1重量份之界面活性劑(Nikko Chemical公司製造之「BL25」)、2重量份之高分子陰離子分散劑(花王公司製造之「L-95」)、以及20重量份之SnO2粒子(JEMCO公司製造之「S-2000」，平均粒徑為30nm)，利用三輥研磨機進行處理，直至黏度變低且變得平滑為止。繼而，添加53重量份之2-乙基-1,3-己二醇及7重量份之苯甲酸乙酯，利用高速攪拌機進行攪拌而獲得金屬氧化物微粒子分散漿料。12 parts by weight of 2-ethyl-1,3-hexanediol (ratio of carbon number to hydroxyl number = 4, viscosity at normal temperature of 323 mPa ‧ s), 1 part by weight of surfactant (Nikko Chemical) "BL25" manufactured by the company, 2 parts by weight of a polymer anionic dispersant ("L-95" manufactured by Kao Corporation), and 20 parts by weight of SnO 2 particles ("S-2000" manufactured by JEMCO Corporation, average particle size) The diameter was 30 nm), and it was processed by a three-roll mill until the viscosity became low and it became smooth. Then, 53 parts by weight of 2-ethyl-1,3-hexanediol and 7 parts by weight of ethyl benzoate were added, and the mixture was stirred by a high-speed stirrer to obtain a metal oxide fine particle-dispersed slurry.

(實施例8)(Example 8)

添加30重量份之3-甲基-1,5-戊二醇(碳原子數相對於羥基數之比=3，常溫下之黏度為173mPa‧s)、1重量份之界面活性劑(Nikko Chemical公司製造之「BL25」)、2重量份之高分子陰離子系分散劑(東邦化學公司製造之「RS710」)、以及40重量份之TiO2粒子(日本AEROSIL公司製造之「P-25」，平均粒徑為20nm)，利用三輥研磨機進行處理，直至黏度變低且變得平滑為止。繼而，添加12重量份之3-甲基-1,5-戊二醇及15重量份之乙二醇單苯醚，利用高速攪拌機進行攪拌而獲得金屬氧化物微粒子分散漿料。30 parts by weight of 3-methyl-1,5-pentanediol (ratio of carbon number to hydroxyl number = 3, viscosity at normal temperature of 173 mPa ‧ s), and 1 part by weight of surfactant (Nikko Chemical) "BL25" manufactured by the company, 2 parts by weight of a polymer anionic dispersant ("RS710" manufactured by Toho Chemical Co., Ltd.), and 40 parts by weight of TiO 2 particles ("P-25" manufactured by AEROSIL, Japan), average The particle size was 20 nm), and the treatment was carried out by a three-roll mill until the viscosity became low and it became smooth. Then, 12 parts by weight of 3-methyl-1,5-pentanediol and 15 parts by weight of ethylene glycol monophenyl ether were added, and the mixture was stirred by a high-speed stirrer to obtain a metal oxide fine particle-dispersed slurry.

(實施例9)(Example 9)

添加20重量份之2,4-二乙基-1,5-戊二醇(碳原子數相對於羥基數之比=4.5，常溫下之黏度為1650mPa‧s)、1重量份之界面活性劑(Nikko Chemical公司製造之「BL25」)、2重量份之高分子陰離子系分散劑(楠本化成公司製造之「ED-216」)、以及30重量份之MgO粒子(UBE MATERIALS公司製造之「MAGNESIA」，平均粒徑為50nm)，利用三輥研磨機進行處理，直至黏度變低且變得平滑為止。繼而，添加33重量份之2,4-二乙基-1,5-戊二醇及20重量份之丙二醇單苯醚，利用高速攪拌機進行攪拌而獲得金屬氧化物微粒子分散漿料。20 parts by weight of 2,4-diethyl-1,5-pentanediol (ratio of carbon number to hydroxyl number = 4.5, viscosity at room temperature of 1650 mPa ‧ s), 1 part by weight of surfactant ("BL25" manufactured by Nikko Chemical Co., Ltd.), 2 parts by weight of a polymer anionic dispersant ("ED-216" manufactured by Kusumoto Kasei Co., Ltd.), and 30 parts by weight of MgO particles ("MAGNESIA" manufactured by UBE MATERIALS) The average particle diameter was 50 nm), and the treatment was performed by a three-roll mill until the viscosity became low and it became smooth. Then, 33 parts by weight of 2,4-diethyl-1,5-pentanediol and 20 parts by weight of propylene glycol monophenyl ether were added, and the mixture was stirred by a high-speed stirrer to obtain a metal oxide fine particle-dispersed slurry.

(實施例10)(Embodiment 10)

添加6重量份之甘油(碳原子數相對於羥基數之比=1，常溫下之黏度為1412mPa‧s)、20重量份之α-松油醇、1重量份之界面活性劑(Nikko Chemical公司製造之「BL25」)、2重量份之高分子陰離子系分散劑(第一工業藥品公司製造之「SHALLOL AH」)、以及30重量份之ZnO粒子(堺化學公司製造之「50A」，平均粒徑為20nm)，利用三輥研磨機進行處理，直至黏度變低且變得平滑為止。繼而，添加21重量份之α-松油醇及20重量份之松油醇乙酸酯，利用高速攪拌機進行攪拌而獲得金屬氧化物微粒子分散漿料。6 parts by weight of glycerin (ratio of the number of carbon atoms to the number of hydroxyl groups = 1, the viscosity at room temperature is 1412 mPa ‧ s), 20 parts by weight of α-terpineol, and 1 part by weight of a surfactant (Nikko Chemical Co., Ltd.) Manufactured "BL25"), 2 parts by weight of a polymer anionic dispersant ("SHALLOL AH" manufactured by Daiichi Kogyo Co., Ltd.), and 30 parts by weight of ZnO particles ("50A" manufactured by Sigma Chemical Co., Ltd., average granules) The diameter was 20 nm), and the treatment was performed by a three-roll mill until the viscosity became low and it became smooth. Then, 21 parts by weight of α-terpineol and 20 parts by weight of terpineol acetate were added, and the mixture was stirred by a high-speed stirrer to obtain a metal oxide fine particle-dispersed slurry.

＜評價＞<evaluation>

對於實施例6～10中所獲得之金屬氧化物微粒子分散漿料進行以下之評價。將結果示於表3及表4中。The following evaluations were performed on the metal oxide fine particle-dispersed slurry obtained in Examples 6 to 10. The results are shown in Tables 3 and 4.

(1)網版印刷性(1) Screen printing

使用金屬氧化物微粒子分散漿料，利用網版印刷機(MICROTEK公司製造之「MT-320TV」，間隙=2.0mm，刮漿板速度=50mm/s，刮漿刀速度=50mm/s，刮漿板壓=0.25MPa，刮漿刀壓=0.17MPa，背壓=0.10MPa)、網版製版(Tokyo Process Service公司製造之「ST500CAL」，2μm之乳劑，320mm×320mm之網框)、印刷基板(150mm×150mm之鈉玻璃，厚度為15mm)、印刷圖像(線/間隙=50μm/150μm)，於溫度為23℃、濕度為50%之環境下進行網版印刷。連續印刷10片，利用立體顯微鏡對所獲得之第10片之印刷圖像進行觀察，且以如下方式進行評價。Using a metal oxide fine particle dispersion slurry, using a screen printing machine ("MT-320TV" manufactured by MICROTEK Co., Ltd., gap = 2.0 mm, squeegee speed = 50 mm/s, doctor blade speed = 50 mm/s, squeegee) Plate pressure = 0.25 MPa, squeegee pressure = 0.17 MPa, back pressure = 0.110 MPa), screen plate making ("ST500CAL" manufactured by Tokyo Process Service, 2 μm emulsion, 320 mm × 320 mm frame), printed circuit board ( 150 mm × 150 mm soda glass, thickness 15 mm), printed image (line/gap = 50 μm / 150 μm), screen printing at a temperature of 23 ° C and a humidity of 50%. Ten sheets were continuously printed, and the printed image of the obtained tenth sheet was observed with a stereo microscope, and evaluated in the following manner.

○印刷圖像之粗細度並無不均。○ There is no unevenness in the thickness of the printed image.

△印刷圖像之粗細度存在不均，或者印刷圖像非常薄。△The thickness of the printed image is uneven, or the printed image is very thin.

×因堵塞而導致油墨未塗佈於印刷基板上。× The ink was not applied to the printed substrate due to clogging.

(2)燒結性(2) Sinterability

使用設定成5密耳之塗覆器，將金屬氧化物微粒子分散漿料塗佈於玻璃基板上，利用150℃之送風烘箱乾燥30分鐘後，於450℃之電爐中燒成30分鐘。利用堀場製作所製造之碳硫分析裝置來測定殘留碳(ppm)。又，以目視確認燒成顏色，並以如下方式進行評價。The metal oxide fine particle dispersion slurry was applied onto a glass substrate using an applicator set at 5 mils, dried in a blowing oven at 150 ° C for 30 minutes, and then fired in an electric furnace at 450 ° C for 30 minutes. The residual carbon (ppm) was measured using a carbon-sulfur analyzer manufactured by Horiba, Ltd. Moreover, the baking color was visually confirmed, and it evaluated by the following.

○無色。○ colorless.

△成為淡黃色。△ becomes pale yellow.

×附有茶色之燒成顏色。×The color of the burnt brown is attached.

(3)儲藏穩定性(3) Storage stability

將金屬氧化物徽粒子分散漿料於23℃之恆溫室中靜置2週後，以目視確認漿料之狀態，並以如下方式進行評價。After the metal oxide-particle-dispersing slurry was allowed to stand in a thermostatic chamber at 23 ° C for 2 weeks, the state of the slurry was visually confirmed and evaluated as follows.

○既未觀察到層分離，亦未觀察到金屬氧化物微粒子之沈澱。○ No layer separation was observed, and precipitation of metal oxide fine particles was not observed.

△透明之溶液浸出，但可再分散。△ The transparent solution is leached, but can be redispersed.

×分離成兩層，且金屬氧化物微粒子沈澱。× separated into two layers, and metal oxide fine particles were precipitated.

(實施例11)(Example 11)

調配12重量份之2,4-二乙基-1,5-戊二醇(碳原子數相對於羥基數之比=4.5，常溫下之黏度為1650mPa‧s)、1重量份之界面活性劑(Nikko Chemical公司製造之「BL25」)、以及2重量份之高分子陰離子系分散劑(BYK Chemie公司製造之「DISPERBYK-111」)，使用高速分散機進行混合後，添加20重量份之ITO粒子(C. I. Kasei公司製造，平均粒徑為30nm)，利用三輥研磨機進行處理，直至黏度變低且變得平滑為止。繼而，以成為表5之樹脂固體成分之方式添加預先溶解於2,4-二乙基-1,5-戊二醇、丙二醇單苯醚之1：1混合溶液中之乙基纖維素(STD10，WAKO Chemical公司製造)，進一步添加2,4-二乙基-1,5-戊二醇、丙二醇單苯醚，利用高速攪拌機進行攪拌而獲得金屬氧化物微粒子分散糊料。12 parts by weight of 2,4-diethyl-1,5-pentanediol (ratio of carbon number to hydroxyl number = 4.5, viscosity at room temperature of 1650 mPa ‧ s), 1 part by weight of surfactant ("BL25" manufactured by Nikko Chemical Co., Ltd.) and 2 parts by weight of a polymer anionic dispersant ("DISPERBYK-111" manufactured by BYK Chemie Co., Ltd.), and mixed with a high-speed disperser to add 20 parts by weight of ITO particles. (manufactured by CI Kasei Co., Ltd., having an average particle diameter of 30 nm), it was treated by a three-roll mill until the viscosity became low and it became smooth. Then, ethyl cellulose (STD10) previously dissolved in a 1:1 mixed solution of 2,4-diethyl-1,5-pentanediol and propylene glycol monophenyl ether was added as a solid component of the resin of Table 5. Further, 2,4-diethyl-1,5-pentanediol and propylene glycol monophenyl ether were further added by a high-speed stirrer to obtain a metal oxide fine particle-dispersed paste.

(實施例12)(Embodiment 12)

添加12重量份之3-甲基-1,5-戊二醇(碳原子數相對於羥基數之比=3，常溫下之黏度為250mPa‧s)、1重量份之界面活性劑(Nikko Chemical公司製造之「BL25」)、2重量份之高分子陰離子分散劑(花王公司製造之「L-95」)、以及20重量份之SnO2粒子(JEMCO公司製造之「S-2000」，平均粒徑為30nm)，利用三輥研磨機進行處理，直至黏度變低且變得平滑為止。繼而，以成為表5之樹脂固體成分之方式添加預先溶解於3-甲基-1,5-戊二醇、丙二醇單苯醚之1：1混合溶液中之乙基纖維素(STD10，WAKO Chemical公司製造)，進一步添加3-甲基-1,5-戊二醇、丙二醇單苯醚溶液，利用高速攪拌機進行攪拌而獲得金屬氧化物微粒子分散糊料。Add 12 parts by weight of 3-methyl-1,5-pentanediol (ratio of carbon number to hydroxyl number = 3, viscosity at room temperature: 250 mPa ‧ s), 1 part by weight of surfactant (Nikko Chemical "BL25" manufactured by the company, 2 parts by weight of a polymer anionic dispersant ("L-95" manufactured by Kao Corporation), and 20 parts by weight of SnO 2 particles ("S-2000" manufactured by JEMCO Corporation, average particle size) The diameter was 30 nm), and it was processed by a three-roll mill until the viscosity became low and it became smooth. Then, ethyl cellulose (STD10, WAKO Chemical) previously dissolved in a 1:1 mixed solution of 3-methyl-1,5-pentanediol and propylene glycol monophenyl ether was added as a solid component of the resin of Table 5. Further, a solution of 3-methyl-1,5-pentanediol and propylene glycol monophenyl ether was added, and the mixture was stirred by a high-speed stirrer to obtain a metal oxide fine particle-dispersed paste.

(實施例13)(Example 13)

添加30重量份之2-乙基-1,3-己二醇(碳原子數相對於羥基數之比=4，常溫下之黏度為323mPa‧s)、1重量份之界面活性劑(Nikko Chemical公司製造之「BL25」)、2重量份之高分子陰離子系分散劑(東邦化學公司製造之「RS710」)、以及60重量份之TiO2粒子(日本AEROSIL公司製造之「P-25」，平均粒徑為20nm)，利用三輥研磨機進行處理，直至黏度變低且變得平滑為止。繼而，以成為表5之樹脂固體成分之方式添加預先溶解於2-乙基-1,3-己二醇溶液中之乙基纖維素(STD10，WAKO Chemical公司製造)，進一步添加2-乙基-1,3-己二醇溶液，利用高速攪拌機進行攪拌而獲得金屬氧化物微粒子分散糊料。30 parts by weight of 2-ethyl-1,3-hexanediol (ratio of carbon number to hydroxyl number = 4, viscosity at normal temperature of 323 mPa ‧), and 1 part by weight of surfactant (Nikko Chemical) "BL25" manufactured by the company, 2 parts by weight of a polymer anionic dispersant ("RS710" manufactured by Toho Chemical Co., Ltd.), and 60 parts by weight of TiO 2 particles ("P-25" manufactured by AEROSIL, Japan, average) The particle size was 20 nm), and the treatment was carried out by a three-roll mill until the viscosity became low and it became smooth. Then, ethyl cellulose (STD10, manufactured by WAKO Chemical Co., Ltd.) previously dissolved in a 2-ethyl-1,3-hexanediol solution was added as a solid component of the resin of Table 5, and 2-ethyl group was further added. The -1,3-hexanediol solution was stirred by a high speed mixer to obtain a metal oxide fine particle dispersion paste.

(實施例14)(Example 14)

添加20重量份之2-乙基-1,3-己二醇(碳原子數相對於羥基數之比=4，常溫下之黏度為323mPa‧s)、1重量份之界面活性劑(Nikko Chemical公司製造之「BL25」)、2重量份之高分子陰離子系分散劑(楠本化成公司製造之「ED-216」)、以及40重量份之MgO粒子(UBE MATERIALS公司製造之「MAGNESIA」，平均粒徑為50nm)，利用三輥研磨機進行處理，直至黏度變低且變得平滑為止。繼而，以成為表5之樹脂固體成分之方式添加預先溶解於2-乙基-1,3-己二醇溶液中之乙基纖維素(STD10，WAKO Chemical公司製造)，進一步添加2-乙基-1,3-己二醇溶液，並利用高速攪拌機進行攪拌而獲得金屬氧化物微粒子分散糊料。20 parts by weight of 2-ethyl-1,3-hexanediol (ratio of carbon number to hydroxyl number = 4, viscosity at normal temperature of 323 mPa ‧ s), 1 part by weight of surfactant (Nikko Chemical) "BL25" manufactured by the company, 2 parts by weight of a polymer anionic dispersant ("ED-216" manufactured by Kusumoto Kasei Co., Ltd.), and 40 parts by weight of MgO particles ("MAGNESIA" manufactured by UBE MATERIALS Co., Ltd.) The diameter was 50 nm), and the treatment was performed by a three-roll mill until the viscosity became low and it became smooth. Then, ethyl cellulose (STD10, manufactured by WAKO Chemical Co., Ltd.) previously dissolved in a 2-ethyl-1,3-hexanediol solution was added as a solid component of the resin of Table 5, and 2-ethyl group was further added. A -1,3-hexanediol solution was stirred with a high-speed stirrer to obtain a metal oxide fine particle-dispersed paste.

(實施例15)(Example 15)

添加20重量份之2-乙基-1,3-己二醇(碳原子數相對於羥基數之比=4，常溫下之黏度為323mPa‧s)、1重量份之界面活性劑(Nikko Chemical公司製造之「BL25」)、2重量份之高分子陰離子系分散劑(第一工業藥品公司製造之「SHALLOL AH」)、以及40重量份之ZnO粒子(堺化學公司製造之「50A」，平均粒徑為20nm)，利用三輥研磨機進行處理，直至黏度變低且變得平滑為止。繼而，以成為表5之樹脂固體成分之方式添加預先溶解於2-乙基-1,3-己二醇、乙二醇單苯醚之1：1混合溶液中之乙基纖維素(STD10，WAKO Chemical公司製造)，進一步添加2-乙基-1,3-己二醇、乙二醇單苯醚，利用高速攪拌機進行攪拌而獲得金屬氧化物微粒子分散糊料。20 parts by weight of 2-ethyl-1,3-hexanediol (ratio of carbon number to hydroxyl number = 4, viscosity at normal temperature of 323 mPa ‧ s), 1 part by weight of surfactant (Nikko Chemical) "BL25" manufactured by the company, 2 parts by weight of a polymer anionic dispersant ("SHALLOL AH" manufactured by Daiichi Kogyo Co., Ltd.), and 40 parts by weight of ZnO particles ("50A" manufactured by Seiko Chemical Co., Ltd.) The particle size was 20 nm), and the treatment was carried out by a three-roll mill until the viscosity became low and it became smooth. Then, ethyl cellulose (STD10, previously dissolved in a 1:1 mixed solution of 2-ethyl-1,3-hexanediol or ethylene glycol monophenyl ether) was added as a solid component of the resin of Table 5. Further, 2-ethyl-1,3-hexanediol and ethylene glycol monophenyl ether were added, and the mixture was stirred by a high-speed stirrer to obtain a metal oxide fine particle-dispersed paste.

(實施例16)(Embodiment 16)

(黏合劑樹脂之製造)(Manufacture of adhesive resin)

於具備攪拌機、冷卻器、溫度計、熱水浴及氮氣導入口之2L可分離式燒瓶中，混合60重量份之作為(甲基)丙烯酸單體之甲基丙烯酸異丁酯(IBMA，三菱麗陽公司製造)、10重量份之甲基丙烯酸甲酯(MMA，三菱麗陽公司製造)、30重量份之具有聚乙烯鏈之甲基丙烯酸酯單體(PEOMA，日油公司製造之「PME-1000」)、1.5重量份之作為鏈轉移劑之硫醇基琥珀酸、以及100重量份之作為有機溶劑之丙酮，從而獲得單體混合液。60 parts by weight of isobutyl methacrylate as a (meth)acrylic monomer (IBMA, Mitsubishi Rayon) was mixed in a 2 L separable flask equipped with a stirrer, a cooler, a thermometer, a hot water bath, and a nitrogen inlet. 10 parts by weight of methyl methacrylate (MMA, manufactured by Mitsubishi Rayon Co., Ltd.), 30 parts by weight of methacrylate monomer having a polyethylene chain (PEOMA, "PME-1000" manufactured by Nippon Oil Co., Ltd. And 1.5 parts by weight of thiol succinic acid as a chain transfer agent, and 100 parts by weight of acetone as an organic solvent, thereby obtaining a monomer mixture.

對於所獲得之單體混合液，藉由使用氮氣起泡20分鐘而去除溶氧後，將可分離式燒瓶系統內以氮氣進行置換，一面攪拌一面升溫至熱水浴沸騰為止。繼而，添加將聚合起始劑(日油公司製造之「PERHEXA H」)以丙酮稀釋而得之溶液。又，於聚合過程中添加數次含有聚合起始劑之丙酮溶液。自聚合開始起7小時後，藉由冷卻至室溫而結束聚合，從而獲得(甲基)丙烯酸樹脂之丙酮溶液。對於所獲得之聚(甲基)丙烯酸甲酯，使用SHOKO公司製造之管柱LF-804作為管柱，進行利用凝膠滲透層析法(GPC)之分析，結果由聚苯乙烯換算之重量平均分子量為2萬。After the dissolved oxygen was removed by bubbling nitrogen gas for 20 minutes with the obtained monomer mixture, the separable flask system was replaced with nitrogen, and the mixture was heated while stirring until the hot water bath boiled. Then, a solution obtained by diluting a polymerization initiator ("PERHEXA H" manufactured by NOF Corporation) with acetone was added. Further, an acetone solution containing a polymerization initiator was added several times during the polymerization. After 7 hours from the start of the polymerization, the polymerization was terminated by cooling to room temperature, thereby obtaining an acetone solution of a (meth)acrylic resin. For the obtained poly(methyl) acrylate, a column LF-804 manufactured by SHOKO Co., Ltd. was used as a column, and analysis by gel permeation chromatography (GPC) was carried out, and the weight average was calculated by polystyrene. The molecular weight is 20,000.

(金屬氧化物微粒子分散糊料之製造)(Manufacture of metal oxide fine particle dispersion paste)

以最終達到表5中所記載之金屬氧化物微粒子分散糊料之組成比的方式，對調配有2,4-二乙基-1,5-戊二醇(碳原子數相對於羥基數之比=4.5，常溫下之黏度為1650mPa‧s)、丙二醇單苯醚之媒液中，添加0.5重量份之界面活性劑(Nikko Chemical公司製造之「BL25」)、高分子陰離子系分散劑(BYK Chemie公司製造之「DISPERBYK-111」)、以及ITO粒子(C. I. Kasei公司製造，平均粒徑為30nm)，使用珠磨機(AIMEX公司製造之「RMB-08」)及作為介質之粒徑為1mm之氧化鋯粒子進行6小時珠磨機處理。繼而，以使樹脂固體成分達到17重量%之方式添加上述(黏合劑樹脂之製造)中所獲得之(甲基)丙烯酸樹脂之丙酮溶液，利用真空去溶劑處理去除丙酮而獲得金屬氧化物微粒子分散糊料。2,4-diethyl-1,5-pentanediol (the ratio of the number of carbon atoms to the number of hydroxyl groups) was prepared in such a manner that the composition ratio of the metal oxide fine particle-dispersed paste described in Table 5 was finally achieved. = 4.5, viscosity at room temperature: 1650 mPa ‧ s), 0.5 parts by weight of a surfactant ("BL25" manufactured by Nikko Chemical Co., Ltd.) and a polymer anionic dispersant (BYK Chemie) in a vehicle containing propylene glycol monophenyl ether "DISPERBYK-111" manufactured by the company, and ITO particles (manufactured by CI Kasei Co., Ltd., average particle size: 30 nm), using a bead mill ("RMB-08" manufactured by AIMEX Corporation) and a particle size of 1 mm as a medium. The zirconia particles were subjected to a 6 hour bead mill treatment. Then, the acetone solution of the (meth)acrylic resin obtained in the above (manufacture of a binder resin) is added in such a manner that the solid content of the resin is 17% by weight, and acetone is removed by vacuum desolvation treatment to obtain dispersion of metal oxide fine particles. Paste.

(實施例17)(Example 17)

(黏合劑樹脂之製造)(Manufacture of adhesive resin)

以與實施例16相同之方式獲得(甲基)丙烯酸樹脂之丙酮溶液。An acetone solution of a (meth)acrylic resin was obtained in the same manner as in Example 16.

(金屬氧化物微粒子分散糊料之製造)(Manufacture of metal oxide fine particle dispersion paste)

以最終達到表5中所記載之金屬氧化物微粒子分散糊料之組成比的方式，對調配有2-乙基-1,3-己二醇(碳原子數相對於羥基數之比=4，常溫下之黏度為323mPa‧s)、以及乙二醇單苯醚之媒液中，添加0.5重量份之界面活性劑(Nikko Chemical公司製造之「BL25」)、高分子陰離子系分散劑(花王公司製造之「RHEODOL L-95」)、以及SnO2粒子(JEMCO公司製造之「S-2000」，平均粒徑為30nm)，使用珠磨機(AIMEX公司製造之「RMB-08」)及作為介質之粒徑為1mm之氧化鋯粒子進行6小時珠磨機處理。繼而，以使樹脂固體成分達到17重量%之方式添加上述(黏合劑樹脂之製造)中所獲得之(甲基)丙烯酸樹脂之丙酮溶液，利用真空去溶劑處理去除丙酮而獲得金屬氧化物微粒子分散糊料。2-ethyl-1,3-hexanediol (the ratio of the number of carbon atoms to the number of hydroxyl groups = 4, in such a manner as to finally reach the composition ratio of the metal oxide fine particle-dispersed paste described in Table 5 0.5 parts by weight of a surfactant ("BL25" manufactured by Nikko Chemical Co., Ltd.) and a polymer anionic dispersant (Kao Corporation) in a medium having a viscosity of 323 mPa·s at room temperature and ethylene glycol monophenyl ether "RHEODOL L-95" manufactured by the company and SnO 2 particles ("S-2000" manufactured by JEMCO Co., Ltd., average particle size: 30 nm), using a bead mill ("RMB-08" manufactured by AIMEX Corporation) and as a medium The zirconia particles having a particle diameter of 1 mm were subjected to a 6-hour bead mill treatment. Then, the acetone solution of the (meth)acrylic resin obtained in the above (manufacture of a binder resin) is added in such a manner that the solid content of the resin is 17% by weight, and acetone is removed by vacuum desolvation treatment to obtain dispersion of metal oxide fine particles. Paste.

(實施例18)(Embodiment 18)

(黏合劑樹脂之製造)(Manufacture of adhesive resin)

以與實施例16相同之方式獲得(甲基)丙烯酸樹脂之丙酮溶液。An acetone solution of a (meth)acrylic resin was obtained in the same manner as in Example 16.

(金屬氧化物微粒子分散糊料之製造)(Manufacture of metal oxide fine particle dispersion paste)

以最終達到表5中所記載之金屬氧化物微粒子分散糊料之組成比的方式，對調配有2-乙基-1,3-己二醇(碳原子數相對於羥基數之比=4，常溫下之黏度為323mPa‧s)之媒液中，添加0.5重量份之界面活性劑(Nikko Chemical公司製造之「BL25」)、高分子陰離子系分散劑(東邦化學公司製造之「RS-710」)、以及TiO2粒子(日本AEROSIL公司製造之「P-25」，平均粒徑為20nm)，使用珠磨機(AIMEX公司製造之「RMB-08」)及作為介質之粒徑為1mm之氧化鋯粒子進行6小時珠磨機處理。繼而，以使樹脂固體成分達到13重量%之方式添加上述(黏合劑樹脂之製造)中所獲得之(甲基)丙烯酸樹脂之丙酮溶液，利用真空去溶劑處理去除丙酮而獲得金屬氧化物微粒子分散糊料。2-ethyl-1,3-hexanediol (the ratio of the number of carbon atoms to the number of hydroxyl groups = 4, in such a manner as to finally reach the composition ratio of the metal oxide fine particle-dispersed paste described in Table 5 0.5 parts by weight of a surfactant ("BL25" manufactured by Nikko Chemical Co., Ltd.) and a polymer anionic dispersant ("RS-710" manufactured by Toho Chemical Co., Ltd.) in a vehicle having a viscosity of 323 mPa·s at room temperature And TiO 2 particles ("P-25" manufactured by AEROSIL Co., Ltd., average particle size: 20 nm), using a bead mill ("RMB-08" manufactured by AIMEX Corporation) and an oxidation particle size of 1 mm as a medium. The zirconium particles were treated with a 6 hour bead mill. Then, the acetone solution of the (meth)acrylic resin obtained in the above (manufacture of a binder resin) is added in such a manner that the solid content of the resin is 13% by weight, and acetone is removed by vacuum desolvation treatment to obtain dispersion of metal oxide fine particles. Paste.

(實施例19)(Embodiment 19)

(黏合劑樹脂之製造)(Manufacture of adhesive resin)

以與實施例16相同之方式獲得(甲基)丙烯酸樹脂之丙酮溶液。An acetone solution of a (meth)acrylic resin was obtained in the same manner as in Example 16.

(金屬氧化物微粒子分散糊料之製造)(Manufacture of metal oxide fine particle dispersion paste)

以最終達到表5中所記載之金屬氧化物微粒子分散糊料之組成比的方式，對調配有2-乙基-1,3-己二醇(碳原子數相對於羥基數之比=4，常溫下之黏度為323mPa‧s)之媒液中，添加0.5重量份之界面活性劑(Nikko Chemical公司製造之「BL25」)、高分子陰離子系分散劑(楠本化成公司製造之「ED-216」)、以及MgO粒子(UBE MATERIALS公司製造之「MAGNESIA」，平均粒徑為50nm)，使用珠磨機(AIMEX公司製造之「RMB-08」)及作為介質之粒徑為1mm之氧化鋯粒子進行6小時珠磨機處理。繼而，以使樹脂固體成分達到13重量%之方式添加上述(黏合劑樹脂之製造)中所獲得之(甲基)丙烯酸樹脂之丙酮溶液，利用真空去溶劑處理去除丙酮而獲得金屬氧化物微粒子分散糊料。2-ethyl-1,3-hexanediol (the ratio of the number of carbon atoms to the number of hydroxyl groups = 4, in such a manner as to finally reach the composition ratio of the metal oxide fine particle-dispersed paste described in Table 5 0.5 parts by weight of a surfactant ("BL25" manufactured by Nikko Chemical Co., Ltd.) and a polymer anionic dispersant ("ED-216" manufactured by Nanben Chemical Co., Ltd.) in a vehicle having a viscosity of 323 mPa·s at room temperature And MgO particles ("MAGNESIA" manufactured by UBE MATERIALS Co., Ltd., average particle diameter: 50 nm), using a bead mill ("RMB-08" manufactured by AIMEX Corporation) and zirconia particles having a particle diameter of 1 mm as a medium. 6-hour bead mill treatment. Then, the acetone solution of the (meth)acrylic resin obtained in the above (manufacture of a binder resin) is added in such a manner that the solid content of the resin is 13% by weight, and acetone is removed by vacuum desolvation treatment to obtain dispersion of metal oxide fine particles. Paste.

(實施例20)(Embodiment 20)

(黏合劑樹脂之製造)(Manufacture of adhesive resin)

以與實施例16相同之方式獲得(甲基)丙烯酸樹脂之丙酮溶液。An acetone solution of a (meth)acrylic resin was obtained in the same manner as in Example 16.

(金屬氧化物微粒子分散糊料之製造)(Manufacture of metal oxide fine particle dispersion paste)

以最終達到表5中所記載之金屬氧化物微粒子分散糊料之組成比的方式，對調配有3-甲基-1,5-戊二醇(碳原子數相對於羥基數之比=3，常溫下之黏度為250mPa‧s)、以及丙二醇單苯醚之媒液中，添加0.5重量份之界面活性劑(Nikko Chemical公司製造之「BL25」)、高分子陰離子系分散劑(第一工業藥品公司製造之「SHALLOL AH」)、以及ZnO粒子(堺化學公司製造之「50A」，平均粒徑為20nm)，使用珠磨機(AIMEX公司製造之「RMB-08」)及作為介質之粒徑為1mm之氧化鋯粒子進行6小時珠磨機處理。繼而，以使樹脂固體成分達到13重量%之方式添加上述(黏合劑樹脂之製造)中所獲得之(甲基)丙烯酸樹脂之丙酮溶液，利用真空去溶劑處理去除丙酮而獲得金屬氧化物微粒子分散糊料。The ratio of the number of carbon atoms to the number of hydroxyl groups = 3 was formulated in such a manner that the composition ratio of the metal oxide fine particle-dispersed paste described in Table 5 was finally achieved. 0.5 parts by weight of a surfactant ("BL25" manufactured by Nikko Chemical Co., Ltd.) and a polymer anionic dispersant (first industrial drug) in a vehicle having a viscosity of 250 mPa·s at room temperature and propylene glycol monophenyl ether "SHALLOL AH" manufactured by the company, and ZnO particles ("50A" manufactured by Suga Chemical Co., Ltd., average particle size: 20 nm), using a bead mill ("RMB-08" manufactured by AIMEX Corporation) and a particle size as a medium The 1 mm zirconia particles were subjected to a 6 hour bead mill treatment. Then, the acetone solution of the (meth)acrylic resin obtained in the above (manufacture of a binder resin) is added in such a manner that the solid content of the resin is 13% by weight, and acetone is removed by vacuum desolvation treatment to obtain dispersion of metal oxide fine particles. Paste.

＜評價＞<evaluation>

對於實施例11～20中所獲得之金屬氧化物微粒子分散糊料進行以下之評價。將結果示於表5及表6中。The following evaluations were performed on the metal oxide fine particle-dispersed pastes obtained in Examples 11 to 20. The results are shown in Tables 5 and 6.

(1)網版印刷性(1) Screen printing

使用金屬氧化物微粒子分散糊料，利用網版印刷機(MICROTEK公司製造之「MT-320TV」，間隙=2.0mm，刮漿板速度=50mm/s，刮漿刀速度=50mm/s，刮漿板壓=0.25MPa，刮漿刀壓=0.17MPa，背壓=0.10MPa)、網版製版(Tokyo Process Service公司製造之「ST500CAL」，2μm之乳劑，320mm×320mm之網框)、印刷基板(150mm×150mm之鈉玻璃，厚度為15mm)、印刷圖像(線/間隙=50μm/150μm)，於溫度為23℃、濕度為50%之環境下進行網版印刷。連續印刷10片，利用立體顯微鏡對所獲得之第10片之印刷圖像進行觀察，且以如下方式進行評價。Using metal oxide fine particles to disperse the paste, using a screen printing machine ("MT-320TV" manufactured by MICROTEK Co., Ltd., gap = 2.0 mm, squeegee speed = 50 mm/s, doctor blade speed = 50 mm/s, squeegee Plate pressure = 0.25 MPa, squeegee pressure = 0.17 MPa, back pressure = 0.110 MPa), screen plate making ("ST500CAL" manufactured by Tokyo Process Service, 2 μm emulsion, 320 mm × 320 mm frame), printed circuit board ( 150 mm × 150 mm soda glass, thickness 15 mm), printed image (line/gap = 50 μm / 150 μm), screen printing at a temperature of 23 ° C and a humidity of 50%. Ten sheets were continuously printed, and the printed image of the obtained tenth sheet was observed with a stereo microscope, and evaluated in the following manner.

○印刷圖像之粗細度並無不均。○ There is no unevenness in the thickness of the printed image.

△印刷圖像之粗細度存在不均，或者印刷圖像非常薄。△The thickness of the printed image is uneven, or the printed image is very thin.

×因堵塞而導致油墨未塗佈於印刷基板上。× The ink was not applied to the printed substrate due to clogging.

(2)燒結性(2) Sinterability

使用設定成5密耳之塗覆器，將金屬氧化物微粒子分散糊料塗佈於玻璃基板上，利用150℃之送風烘箱乾燥30分鐘後，於450℃之電爐中燒成30分鐘。利用堀場製作所製造之碳硫分析裝置來測定殘留碳(ppm)。又，以目視確認燒成顏色，並以如下方式進行評價。The metal oxide fine particle dispersion paste was applied onto a glass substrate using an applicator set at 5 mils, dried in a blowing oven at 150 ° C for 30 minutes, and then fired in an electric furnace at 450 ° C for 30 minutes. The residual carbon (ppm) was measured using a carbon-sulfur analyzer manufactured by Horiba, Ltd. Moreover, the baking color was visually confirmed, and it evaluated by the following.

○無色。○ colorless.

△成為淡黃色。△ becomes pale yellow.

×附有茶色之燒成顏色。×The color of the burnt brown is attached.

(3)儲藏穩定性(3) Storage stability

將金屬氧化物微粒子分散糊料於23℃之恆溫室中靜置2週後，以目視確認糊料之狀態，並以如下方式進行評價。After the metal oxide fine particle dispersion paste was allowed to stand in a constant temperature room at 23 ° C for 2 weeks, the state of the paste was visually confirmed and evaluated as follows.

○既未觀察到層分離，亦未觀察到金屬氧化物微粒子之沈澱。○ No layer separation was observed, and precipitation of metal oxide fine particles was not observed.

△透明之溶液滲出，但可再分散。△ The transparent solution oozes, but can be redispersed.

×分離成兩層，且金屬氧化物微粒子沈澱。× separated into two layers, and metal oxide fine particles were precipitated.

(實施例21)(Example 21)

(黏合劑樹脂之製造)(Manufacture of adhesive resin)

除將實施例1中所添加之鏈轉移劑之量設為1.2重量份以外，以與實施例1相同之方式獲得(甲基)丙烯酸樹脂(聚甲基丙烯酸甲酯)之丙酮溶液。對所獲得之溶液中加入2-乙基-1,3-己二醇，進行真空去溶劑處理，藉此獲得聚甲基丙烯酸甲酯之2-乙基-1,3-己二醇溶液。An acetone solution of a (meth)acrylic resin (polymethyl methacrylate) was obtained in the same manner as in Example 1 except that the amount of the chain transfer agent added in Example 1 was 1.2 parts by weight. To the obtained solution, 2-ethyl-1,3-hexanediol was added, and vacuum desolvation treatment was carried out, whereby a solution of polymethyl methacrylate in 2-ethyl-1,3-hexanediol was obtained.

(金屬氧化物微粒子分散糊料之製造)(Manufacture of metal oxide fine particle dispersion paste)

以最終達到表7中所記載之金屬氧化物微粒子分散糊料之組成比的方式，將2-乙基-1,3-己二醇(碳原子數相對於羥基數之比=4，常溫下之黏度為323mPa‧s)、界面活性劑(Nikko Chemical公司製造之「BL25」)、高分子陰離子系分散劑(楠本化成公司製造之「ED-216」)、以及MgO粒子(UBE MATERIALS公司製造之「MAGNESIA」，平均粒徑為50nm)加以混合，使用珠磨機(AIMEX公司製造之「RMB-08」)及作為介質之粒徑為1mm之氧化鋯粒子進行6小時珠磨機處理。2-ethyl-1,3-hexanediol (the ratio of the number of carbon atoms to the number of hydroxyl groups = 4, at room temperature, in such a manner as to finally reach the composition ratio of the metal oxide fine particle-dispersed paste described in Table 7 The viscosity is 323 mPa·s), the surfactant ("BL25" manufactured by Nikko Chemical Co., Ltd.), the polymer anionic dispersant ("ED-216" manufactured by Nanben Chemical Co., Ltd.), and the MgO particles (manufactured by UBE MATERIALS). "MAGNESIA" (average particle diameter: 50 nm) was mixed, and a bead mill ("RMB-08" manufactured by AIMEX Co., Ltd.) and zirconia particles having a particle diameter of 1 mm as a medium were subjected to a 6-hour bead mill treatment.

繼而，以使樹脂固體成分達到表7中所記載之量之方式添加上述(黏合劑樹脂之製造)中所獲得之聚甲基丙烯酸甲酯之2-乙基-1,3-己二醇溶液，從而獲得金屬氧化物徽粒子分散糊料。Then, the polyethyl methacrylate 2-ethyl-1,3-hexanediol solution obtained in the above (manufacture of a binder resin) was added in such a manner that the resin solid content reached the amount described in Table 7. Thereby obtaining a metal oxide emblem particle dispersion paste.

(實施例22)(Example 22)

(黏合劑樹脂之製造)(Manufacture of adhesive resin)

除了使用甲基丙烯酸異丁酯(IBMA，三菱麗陽公司製造)代替甲基丙烯酸甲酯來作為(甲基)丙烯酸單體以外，以與實施例21相同之方式獲得(甲基)丙烯酸樹脂之2-乙基-1,3-己二醇溶液。(Meth)acrylic resin was obtained in the same manner as in Example 21 except that isobutyl methacrylate (IBMA, manufactured by Mitsubishi Rayon Co., Ltd.) was used instead of methyl methacrylate as the (meth)acrylic monomer. 2-ethyl-1,3-hexanediol solution.

(金屬氧化物微粒子分散糊料之製造)(Manufacture of metal oxide fine particle dispersion paste)

以最終達到表7中所記載之金屬氧化物微粒子分散糊料之組成比的方式，將2-乙基-1,3-己二醇(碳原子數相對於羥基數之比=4，常溫下之黏度為323mPa‧s)、界面活性劑(Nikko Chemical公司製造之「BL25」)、以及MgO粒子(UBE MATERIALS公司製造之「MAGNESIA」，平均粒徑為50nm)、上述(黏合劑樹脂之製造)中所獲得之(甲基)丙烯酸樹脂之2-乙基-1,3-己二醇溶液加以混合，使用珠磨機(AIMEX公司製造之「RMB-08」)及作為介質之粒徑為1mm之氧化鋯粒子進行6小時珠磨機處理，從而獲得金屬氧化物微粒子分散糊料。2-ethyl-1,3-hexanediol (the ratio of the number of carbon atoms to the number of hydroxyl groups = 4, at room temperature, in such a manner as to finally reach the composition ratio of the metal oxide fine particle-dispersed paste described in Table 7 The viscosity is 323 mPa·s), the surfactant ("BL25" manufactured by Nikko Chemical Co., Ltd.), and the MgO particles ("MAGNESIA" manufactured by UBE MATERIALS Co., Ltd., average particle diameter: 50 nm), and the above (manufacture of the binder resin) The 2-ethyl-1,3-hexanediol solution of the (meth)acrylic resin obtained in the mixture was mixed, and a bead mill ("RMB-08" manufactured by AIMEX Co., Ltd.) and a particle diameter of 1 mm as a medium were used. The zirconia particles were subjected to a 6-hour bead mill treatment to obtain a metal oxide fine particle-dispersed paste.

(實施例23)(Example 23)

(黏合劑樹脂之製造)(Manufacture of adhesive resin)

除使用60重量份之甲基丙烯酸異丁酯(IBMA，三菱麗陽公司製造)、10重量份之甲基丙烯酸甲酯(MMA，三菱麗陽公司製造)、30重量份之具有聚乙烯鏈之甲基丙烯酸酯單體(PEOMA，日油公司製造之「PME-1000」)作為(甲基)丙烯酸單體以外，以與實施例21相同之方式獲得(甲基)丙烯酸樹脂之2-乙基-1,3-己二醇溶液。In addition to 60 parts by weight of isobutyl methacrylate (IBMA, manufactured by Mitsubishi Rayon Co., Ltd.), 10 parts by weight of methyl methacrylate (MMA, manufactured by Mitsubishi Rayon Co., Ltd.), and 30 parts by weight of a polyethylene chain A 2-ethyl group of a (meth)acrylic resin was obtained in the same manner as in Example 21 except that a methacrylate monomer (PEOMA, "PME-1000" manufactured by Nippon Oil Co., Ltd.) was used as the (meth)acrylic monomer. - 1,3-hexanediol solution.

(金屬氧化物微粒子分散糊料之製造)(Manufacture of metal oxide fine particle dispersion paste)

以最終達到表7中所記載之金屬氧化物微粒子分散糊料之組成比的方式，將2-乙基-1,3-己二醇(碳原子數相對於羥基數之比=4，常溫下之黏度為323mPa‧s)、界面活性劑(Nikko Chemical公司製造之「BL25」)、以及MgO粒子(UBE MATERIALS公司製造之「MAGNESIA」，平均粒徑為50nm)、上述(黏合劑樹脂之製造)中所獲得之(甲基)丙烯酸樹脂之2-乙基-1,3-己二醇溶液加以混合，使用珠磨機(AIMEX公司製造之「RMB-08」)及作為介質之粒徑為1mm之氧化鋯粒子進行6小時珠磨機處理，從而獲得金屬氧化物微粒子分散糊料。2-ethyl-1,3-hexanediol (the ratio of the number of carbon atoms to the number of hydroxyl groups = 4, at room temperature, in such a manner as to finally reach the composition ratio of the metal oxide fine particle-dispersed paste described in Table 7 The viscosity is 323 mPa·s), the surfactant ("BL25" manufactured by Nikko Chemical Co., Ltd.), and the MgO particles ("MAGNESIA" manufactured by UBE MATERIALS Co., Ltd., average particle diameter: 50 nm), and the above (manufacture of the binder resin) The 2-ethyl-1,3-hexanediol solution of the (meth)acrylic resin obtained in the mixture was mixed, and a bead mill ("RMB-08" manufactured by AIMEX Co., Ltd.) and a particle diameter of 1 mm as a medium were used. The zirconia particles were subjected to a 6-hour bead mill treatment to obtain a metal oxide fine particle-dispersed paste.

(實施例24)(Example 24)

添加50重量份之2-乙基-1,3-己二醇(碳原子數相對於羥基數之比=4，常溫下之黏度為323mPa‧s)、1重量份之界面活性劑(Nikko Chemical公司製造之「BL25」)、2重量份之高分子陰離子系分散劑(BYK Chemie公司製造之「DISPERBYK-111」、以及30重量份之MgO粒子(UBE MATERIALS公司製造之「MAGNESIA」，平均粒徑為50nm)，使用珠磨機(AIMEX公司製造之「RMB-08」)及作為介質之粒徑為1mm之氧化鋯粒子進行6小時珠磨機處理，從而獲得金屬氧化物微粒子分散溶液。50 parts by weight of 2-ethyl-1,3-hexanediol (ratio of carbon number to hydroxyl number = 4, viscosity at normal temperature of 323 mPa ‧ s), 1 part by weight of surfactant (Nikko Chemical) "BL25" manufactured by the company, 2 parts by weight of a polymer anionic dispersant ("DISPERBYK-111" manufactured by BYK Chemie Co., Ltd., and 30 parts by weight of MgO particles ("MAGNESIA" manufactured by UBE MATERIALS), average particle diameter In the case of 50 nm), a bead mill ("RMB-08" manufactured by AIMEX Co., Ltd.) and zirconia particles having a particle diameter of 1 mm as a medium were subjected to a 6-hour bead mill treatment to obtain a metal oxide fine particle dispersion solution.

對所獲得之金屬氧化物微粒子分散溶液中，添加預先將3重量份之乙基纖維素(STD100，WAKO Chemical公司製造)溶解於14重量份之2-乙基-1,3-己二醇中而成的乙基纖維素之2-乙基-1,3-己二醇溶液，利用高速攪拌機進行攪拌而獲得金屬氧化物微粒子分散糊料。To the obtained metal oxide fine particle dispersion solution, 3 parts by weight of ethyl cellulose (STD100, manufactured by WAKO Chemical Co., Ltd.) was previously dissolved in 14 parts by weight of 2-ethyl-1,3-hexanediol. The 2-ethyl-1,3-hexanediol solution of ethyl cellulose obtained was stirred by a high-speed stirrer to obtain a metal oxide fine particle-dispersed paste.

(比較例6)(Comparative Example 6)

除了使用α-松油醇代替2-乙基-1,3-己二醇來作為有機溶劑以外，以與實施例21相同之方式獲得表7中所記載之金屬氧化物微粒子分散糊料。The metal oxide fine particle-dispersed paste described in Table 7 was obtained in the same manner as in Example 21 except that α-terpineol was used instead of 2-ethyl-1,3-hexanediol as the organic solvent.

(比較例7)(Comparative Example 7)

除了使用α-松油醇代替2-乙基-1,3-己二醇來作為有機溶劑以外，以與實施例22相同之方式獲得表7中所記載之金屬氧化物微粒子分散糊料。The metal oxide fine particle dispersion paste described in Table 7 was obtained in the same manner as in Example 22 except that α-terpineol was used instead of 2-ethyl-1,3-hexanediol as the organic solvent.

(比較例8)(Comparative Example 8)

除了使用α-松油醇代替2-乙基-1,3-己二醇來作為有機溶劑以外，以與實施例23相同之方式獲得表7中所記載之金屬氧化物微粒子分散糊料。The metal oxide fine particle dispersion paste described in Table 7 was obtained in the same manner as in Example 23 except that α-terpineol was used instead of 2-ethyl-1,3-hexanediol as the organic solvent.

(比較例9)(Comparative Example 9)

除了使用α-松油醇代替2-乙基-1,3-己二醇來作為有機溶劑以外，以與實施例24相同之方式獲得表7中所記載之金屬氧化物微粒子分散糊料。The metal oxide fine particle-dispersed paste described in Table 7 was obtained in the same manner as in Example 24 except that α-terpineol was used instead of 2-ethyl-1,3-hexanediol as the organic solvent.

＜評價＞<evaluation>

通常之電漿顯示器用前面板係藉由於基板玻璃上積層由透明電極(ITO)或匯流電極(銀)所構成之透明電介質體層，進而印刷金屬氧化物微粒子分散糊料並加以燒成而獲得，因此於本評價中，作為替代，對在基板玻璃上積層有透明電介質體層之積層體上印刷金屬氧化物微粒子分散糊料並燒成而成之試樣進行評價，藉此作為電漿顯示器用前面板之性能試驗。In general, a front panel for a plasma display is obtained by laminating a transparent dielectric body layer made of a transparent electrode (ITO) or a bus electrode (silver) on a substrate glass, and printing a metal oxide fine particle-dispersed paste and firing it. Therefore, in this evaluation, a sample obtained by printing a metal oxide fine particle-dispersed paste on a laminated body in which a transparent dielectric body layer is laminated on a substrate glass and firing it is evaluated, and this is used as a plasma display. Panel performance test.

(粒度分布)(Particle size distribution)

將所獲得之金屬氧化物微粒子分散糊料以乙醇溶液進行稀釋，利用粒度分布計(堀場製作所製造之LA-910)來測定粒度分布。The obtained metal oxide fine particle dispersion paste was diluted with an ethanol solution, and the particle size distribution was measured by a particle size distribution meter (LA-910 manufactured by Horiba, Ltd.).

將Dmax為0.5μm以下之情形判定為◎，將D90為0.5μm以下之情形判定為○，將D90超過0.5μm之情形判定為×。The case where D max was 0.5 μm or less was judged as ◎, the case where D90 was 0.5 μm or less was judged as ○, and the case where D90 exceeded 0.5 μm was judged as ×.

(透光率)(Transmittance)

＜透明電介質體層之製作＞<Production of Transparent Dielectric Body Layer>

使用刮塗法將含有以B2O3、Li2O、Bi2O3及MoO3為主成分之玻璃粉末、乙基纖維素、松油醇的玻璃糊料塗佈於基板玻璃上，於100℃、30分鐘之條件下使其乾燥，然後於軟化點+10℃之溫度下燒成10分鐘，藉此形成厚度為30μm之透明電介質體層。Applying a glass paste containing a glass powder containing B 2 O 3 , Li 2 O, Bi 2 O 3 and MoO 3 as a main component, ethyl cellulose, terpineol to a substrate glass by a doctor blade method, It was dried at 100 ° C for 30 minutes, and then fired at a softening point of +10 ° C for 10 minutes, thereby forming a transparent dielectric body layer having a thickness of 30 μm.

＜金屬氧化物微粒子燒結膜之製作＞<Production of Metal Oxide Fine Particle Sintered Film>

使用實施例21～24及比較例6～9中所獲得之金屬氧化物微粒子分散糊料，以下述條件進行利用網版印刷機(MICROTEK公司製造之「MT-320TV」)之印刷，從而於積層有＜透明電介質體層之製作＞中所獲得之透明電介質體層之基板玻璃上獲得10cm×10cm之金屬氧化物微粒子分散糊料之乾燥膜。Using the metal oxide fine particle-dispersed pastes obtained in the examples 21 to 24 and the comparative examples 6 to 9, the printing was carried out by a screen printing machine ("MT-320TV" manufactured by MICROTEK Co., Ltd.) under the following conditions. A dried film of a metal oxide fine particle dispersion paste of 10 cm × 10 cm was obtained on the substrate glass of the transparent dielectric body layer obtained in <Production of Transparent Dielectric Body Layer>.

＜印刷條件＞<Printing conditions>

間隙：2.0mm，刮漿板速度：50mm/s，刮漿刀速度：50mm/s，刮漿板壓：0.25MPa，刮漿刀壓：0.17MPa，背壓：0.10MPa，網版製版(Tokyo Process Service公司製造之「ST500CAL」，2μm之乳劑，320mm×320mm之網框)，印刷基板(150mm×150mm之鈉玻璃，厚度為15mm)，溫度：23℃，濕度：50%，乾燥條件：150℃×10分鐘。Clearance: 2.0mm, squeegee speed: 50mm/s, squeegee speed: 50mm/s, squeegee pressure: 0.25MPa, squeegee pressure: 0.17MPa, back pressure: 0.10MPa, screen plate making (Tokyo Process Service company "ST500CAL", 2μm emulsion, 320mm × 320mm frame), printed substrate (150mm × 150mm soda glass, thickness 15mm), temperature: 23 ° C, humidity: 50%, drying conditions: 150 °C × 10 minutes.

使用蒙烰爐(Advantech公司製造，FUW230PA)，以10℃/分鐘之升溫速度將所獲得之乾燥膜升溫至400℃為止，保持30分鐘後，放置冷卻而獲得金屬氧化物微粒子之燒結膜。The obtained dried film was heated to 400 ° C at a temperature increase rate of 10 ° C /min using a mash furnace (FUW230PA, manufactured by Advantech Co., Ltd.), and after standing for 30 minutes, it was left to cool to obtain a sintered film of metal oxide fine particles.

再者，於使用實施例24及比較例9中所獲得之金屬氧化物微粒子分散糊料之情形時，升溫至500℃為止。In the case of using the metal oxide fine particle-dispersed paste obtained in Example 24 and Comparative Example 9, the temperature was raised to 500 °C.

使用觸針儀(P-16，KLA-tencor公司製造)測定所得燒結膜之厚度。繼而，使用霧度計(TC-H3DPK，東京電色公司製造)，以根據JIS K 6714、JIS K 6718之方法測定總透光率(n=3)。將所獲得之值為90%以上之情形判定為◎，將低於90%且88%以上之情形判定為○，將低於88%且85%以上之情形判定為△，將低於85%之情形判定為×。再者，於基板玻璃上形成有透明電介質體層之狀態下之總透光率為91%。The thickness of the obtained sintered film was measured using a stylus instrument (P-16, manufactured by KLA-tencor Co., Ltd.). Then, a haze meter (TC-H3DPK, manufactured by Tokyo Denshoku Co., Ltd.) was used to measure the total light transmittance (n = 3) in accordance with the method of JIS K 6714 and JIS K 6718. The case where the obtained value is 90% or more is judged as ◎, the case where it is less than 90% and 88% or more is judged as ○, and the case where it is less than 88% and 85% or more is judged as Δ, and will be less than 85%. The case is judged as ×. Further, the total light transmittance in the state in which the transparent dielectric body layer was formed on the substrate glass was 91%.

(細密性)(fineness)

對於所獲得之金屬氧化物微粒子燒結膜之SEM(Scanning Electron Microscope，掃描電子顯微鏡)照片(20000倍)，以全部5個視野的方式確認視野(6μm×5μm)中所見到之粒子間之間隙。With respect to the SEM (Scanning Electron Microscope) photograph (20000 times) of the obtained metal oxide fine particle sintered film, the gap between the particles seen in the visual field (6 μm × 5 μm) was confirmed in all five fields of view.

將未確認到100nm以上之間隙之情形判定為○，將確認到100nm以上之間隙之情形判定為×。The case where the gap of 100 nm or more was not confirmed was judged as ○, and the case where the gap of 100 nm or more was confirmed was judged as ×.

(分散性)(dispersion)

對於所獲得之金屬氧化物微粒子燒結膜之SEM照片(5000倍)，以全部5個視野的方式確認視野(24μm×20μm)中是否存在凝聚之氧化鎂。將未確認到凝聚體之情形判定為○，將確認到凝聚體之情形判定為×。With respect to the SEM photograph (5000 times) of the obtained metal oxide fine particle sintered film, whether or not agglomerated magnesium oxide was present in the visual field (24 μm × 20 μm) was confirmed in all five fields of view. The case where the aggregate was not confirmed was judged as ○, and the case where the aggregate was confirmed was judged as ×.

(實施例25)(Embodiment 25)

添加70重量份之2-乙基-1,3-己二醇(碳原子數相對於羥基數之比=4，常溫下之黏度為323mPa‧s)、30重量份之MgO粒子(UBE MATERIALS公司製造之「MAGNESIA」，平均粒徑為50nm)，使用珠磨機(AIMEX公司製造之「RMB-08」)及作為介質之粒徑為1mm之氧化鋯粒子進行6小時珠磨機處理，從而獲得金屬氧化物微粒子分散漿料。70 parts by weight of 2-ethyl-1,3-hexanediol (ratio of carbon number to hydroxyl number = 4, viscosity at normal temperature: 323 mPa ‧ s), and 30 parts by weight of MgO particles (UBE MATERIALS) The "MAGNESIA" manufactured by the company has an average particle diameter of 50 nm), and is subjected to a 6-hour bead mill treatment using a bead mill ("RMB-08" manufactured by AIMEX Co., Ltd.) and zirconia particles having a particle diameter of 1 mm as a medium. The metal oxide fine particles disperse the slurry.

(實施例26)(Example 26)

添加70重量份之乙醇、30重量份之MgO粒子(UBE MATERIALS公司製造之「MAGNESIA」，平均粒徑為50nm)，使用珠磨機(AIMEX公司製造之「RMB-08」)及作為介質之粒徑為1mm之氧化鋯粒子進行6小時珠磨機處理，從而獲得金屬氧化物微粒子分散漿料。70 parts by weight of ethanol and 30 parts by weight of MgO particles ("MAGNESIA" manufactured by UBE MATERIALS Co., Ltd., average particle diameter: 50 nm) were added, and a bead mill ("RMB-08" manufactured by AIMEX Co., Ltd.) and a medium as a medium were used. The zirconia particles having a diameter of 1 mm were subjected to a 6-hour bead mill treatment to obtain a metal oxide fine particle-dispersed slurry.

對所獲得之漿料溶液中加入70重量份之2-乙基-1,3-己二醇(碳原子數相對於羥基數之比=4，常溫下之黏度為323mPa‧s)，利用真空去溶劑處理去除乙醇而獲得金屬氧化物微粒子分散漿料。70 parts by weight of 2-ethyl-1,3-hexanediol (the ratio of the number of carbon atoms to the number of hydroxyl groups = 4, and the viscosity at normal temperature was 323 mPa ‧) was added to the obtained slurry solution, and vacuum was used. The solvent removal treatment removes ethanol to obtain a metal oxide fine particle dispersion slurry.

(實施例27)(Example 27)

添加70重量份之乙醇、30重量份之TiO2粒子(日本AEROSIL公司製造之「P-25」，平均粒徑為20nm)，使用珠磨機(AIMEX公司製造之「RMB-08」)及作為介質之粒徑為1mm之氧化鋯粒子進行6小時珠磨機處理，從而獲得金屬氧化物微粒子分散漿料。70 parts by weight of ethanol and 30 parts by weight of TiO 2 particles ("P-25" manufactured by AEROSIL Co., Ltd., average particle diameter of 20 nm) were added, and a bead mill ("RMB-08" manufactured by AIMEX Co., Ltd.) was used as a The zirconia particles having a particle diameter of 1 mm were subjected to a 6-hour bead mill treatment to obtain a metal oxide fine particle-dispersed slurry.

對所獲得之漿料溶液中加入70重量份之2-乙基-1,3-己二醇(碳原子數相對於羥基數之比=4，常溫下之黏度為323mPa‧s)，利用真空去溶劑處理去除乙醇而獲得金屬氧化物微粒子分散漿料。70 parts by weight of 2-ethyl-1,3-hexanediol (the ratio of the number of carbon atoms to the number of hydroxyl groups = 4, and the viscosity at normal temperature was 323 mPa ‧) was added to the obtained slurry solution, and vacuum was used. The solvent removal treatment removes ethanol to obtain a metal oxide fine particle dispersion slurry.

(實施例28)(Embodiment 28)

除了使用2,4-二乙基-1,5-戊二醇代替2-乙基-1,3-己二醇來作為有機溶劑以外，以與實施例26相同之方式獲得表9中所記載之金屬氧化物微粒子分散漿料。Table 2 was obtained in the same manner as in Example 26 except that 2,4-diethyl-1,5-pentanediol was used instead of 2-ethyl-1,3-hexanediol as the organic solvent. The metal oxide fine particles disperse the slurry.

(實施例29)(Example 29)

除了使用1,4-丁二醇代替2-乙基-1,3-己二醇來作為有機溶劑以外，以與實施例26相同之方式獲得表9中所記載之金屬氧化物微粒子分散漿料。The metal oxide fine particle dispersion slurry described in Table 9 was obtained in the same manner as in Example 26 except that 1,4-butanediol was used instead of 2-ethyl-1,3-hexanediol as the organic solvent. .

(實施例30)(Embodiment 30)

添加70重量份之乙醇、30重量份之MgO粒子(UBE MATERIALS公司製造之「MAGNESIA」，平均粒徑為50nm)，使用珠磨機(AIMEX公司製造之「RMB-08」)及作為介質之粒徑為1mm之氧化鋯粒子進行6小時珠磨機處理，從而獲得金屬氧化物微粒子分散漿料。70 parts by weight of ethanol and 30 parts by weight of MgO particles ("MAGNESIA" manufactured by UBE MATERIALS Co., Ltd., average particle diameter: 50 nm) were added, and a bead mill ("RMB-08" manufactured by AIMEX Co., Ltd.) and a medium as a medium were used. The zirconia particles having a diameter of 1 mm were subjected to a 6-hour bead mill treatment to obtain a metal oxide fine particle-dispersed slurry.

對所獲得之漿料溶液中加入40重量份之2-乙基-1,3-己二醇(碳原子數相對於羥基數之比=4，常溫下之黏度為323mPa‧s)、30重量份之異莰基環已醇，利用真空去溶劑處理去除乙醇而獲得金屬氧化物微粒子分散漿料。To the obtained slurry solution, 40 parts by weight of 2-ethyl-1,3-hexanediol (ratio of the number of carbon atoms to the number of hydroxyl groups = 4, viscosity at normal temperature of 323 mPa ‧ s), 30 weights were added The isodecylcyclohexanol is removed by a vacuum desolvation treatment to obtain a metal oxide fine particle dispersion slurry.

(實施例31)(Example 31)

除了使用50重量份之2,4-二乙基-1,5-戊二醇、20重量份之異莰基環己醇代替40重量份之2-乙基-1,3-己二醇、30重量份之異莰基環己醇，來作為有機溶劑以外，以與實施例30相同之方式獲得表9中所記載之金屬氧化物微粒子分散漿料。In place of 50 parts by weight of 2,4-diethyl-1,5-pentanediol, 20 parts by weight of isodecylcyclohexanol instead of 40 parts by weight of 2-ethyl-1,3-hexanediol, The metal oxide fine particle-dispersed slurry described in Table 9 was obtained in the same manner as in Example 30 except that 30 parts by weight of isodecylcyclohexanol was used as the organic solvent.

(實施例32)(Example 32)

除了使用1,4-丁二醇代替2-乙基-1,3-己二醇來作為有機溶劑以外，以與實施例30相同之方式獲得表9中所記載之金屬氧化物微粒子分散漿料。The metal oxide fine particle dispersion slurry described in Table 9 was obtained in the same manner as in Example 30 except that 1,4-butanediol was used instead of 2-ethyl-1,3-hexanediol as the organic solvent. .

(實施例33)(Example 33)

添加85重量份之乙醇、15重量份之MgO粒子(UBE MATERIALS公司製造之「MAGNESIA」，平均粒徑為50nm)，使用珠磨機(AIMEX公司製造之「RMB-08」)及作為介質之粒徑為1mm之氧化鋯粒子進行6小時珠磨機處理，從而獲得金屬氧化物微粒子分散漿料。85 parts by weight of ethanol and 15 parts by weight of MgO particles ("MAGNESIA" manufactured by UBE MATERIALS Co., Ltd., average particle diameter: 50 nm) were added, and a bead mill ("RMB-08" manufactured by AIMEX Co., Ltd.) and a medium as a medium were used. The zirconia particles having a diameter of 1 mm were subjected to a 6-hour bead mill treatment to obtain a metal oxide fine particle-dispersed slurry.

對所獲得之漿料溶液中加入60重量份之2,4-二乙基-1,5-戊二醇(碳原子數相對於羥基數之比=4.5，常溫下之黏度為1650mPa‧s)、25重量份之異莰基環已醇，利用真空去溶劑處理去除乙醇而獲得金屬氧化物微粒子分散漿料。60 parts by weight of 2,4-diethyl-1,5-pentanediol (the ratio of the number of carbon atoms to the number of hydroxyl groups = 4.5, and the viscosity at room temperature was 1,650 mPa ‧) was added to the obtained slurry solution. 25 parts by weight of isodecylcyclohexanol was removed by vacuum desolvation treatment to obtain a metal oxide fine particle dispersion slurry.

(實施例34)(Example 34)

除了使用粒徑為0.3mm之氧化鋯粒子作為珠磨機之介質以外，以與實施例25相同之方式獲得表9中所記載之金屬氧化物微粒子分散漿料。The metal oxide fine particle-dispersed slurry described in Table 9 was obtained in the same manner as in Example 25, except that zirconia particles having a particle diameter of 0.3 mm were used as the medium of the bead mill.

(比較例10～11)(Comparative Examples 10 to 11)

除了使用表9中所記載之有機溶劑代替2-乙基-1,3-己二醇來作為有機溶劑以外，以與實施例26相同之方式獲得金屬氧化物微粒子分散漿料。A metal oxide fine particle-dispersed slurry was obtained in the same manner as in Example 26 except that the organic solvent described in Table 9 was used instead of 2-ethyl-1,3-hexanediol as the organic solvent.

(比較例12)(Comparative Example 12)

除了使用丁基卡必醇代替2-乙基-1,3-己二醇來作為有機溶劑以外，以與實施例30相同之方式獲得表9中所記載之金屬氧化物微粒子分散漿料。The metal oxide fine particle dispersion slurry described in Table 9 was obtained in the same manner as in Example 30 except that butyl carbitol was used instead of 2-ethyl-1,3-hexanediol as the organic solvent.

＜評價＞<evaluation>

對於實施例25～34、比較例10～12中所獲得之金屬氧化物微粒子分散漿料進行以下之評價。將結果示於表9及表10中。The metal oxide fine particle dispersion slurry obtained in Examples 25 to 34 and Comparative Examples 10 to 12 was evaluated as follows. The results are shown in Tables 9 and 10.

(粒度分布)(Particle size distribution)

將所獲得之金屬氧化物微粒子分散漿料以乙醇溶液進行稀釋，利用粒度分布計(堀場製作所製造之LA-910)來測定粒度分布。The obtained metal oxide fine particle dispersion slurry was diluted with an ethanol solution, and the particle size distribution was measured by a particle size distribution meter (LA-910 manufactured by Horiba, Ltd.).

將Dmax為0.5μm以下之情形判定為◎，將D90為0.5μm以下之情形判定為○，將D90超過0.5μm之情形判定為×。The case where D max was 0.5 μm or less was judged as ◎, the case where D90 was 0.5 μm or less was judged as ○, and the case where D90 exceeded 0.5 μm was judged as ×.

(儲藏穩定性)(storage stability)

將金屬氧化物微粒子分散漿料於23℃之恆溫室中靜置2週後，以目視確認漿料之狀態，並以如下方式進行評價。After the metal oxide fine particle-dispersed slurry was allowed to stand in a constant temperature room at 23 ° C for 2 weeks, the state of the slurry was visually confirmed and evaluated as follows.

○既未觀察到層分離，亦未觀察到金屬氧化物微粒子之沈澱。○ No layer separation was observed, and precipitation of metal oxide fine particles was not observed.

△透明之溶液滲出，但可再分散。△ The transparent solution oozes, but can be redispersed.

×分離成兩層，且金屬氧化物微粒子沈澱。× separated into two layers, and metal oxide fine particles were precipitated.

(網版印刷性)(screen printing)

使用金屬氧化物微粒子分散漿料，利用網版印刷機(MICROTEK公司製造之「MT-320TV」，間隙=2.0mm，刮漿板速度=50mm/s，刮漿刀速度=50mm/s，刮漿板壓=0.25MPa，刮漿刀壓=0.17MPa，背壓=0.10MPa)、網版製版(Tokyo Process Service公司製造之「ST500CAL」，2μm之乳劑，320mm×320mm之網框)、印刷基板(150mm×150mm之鈉玻璃，厚度為15mm)、印刷圖像(線/間隙=50μm/150μm)，於溫度為23℃、濕度為50%之環境下進行網版印刷。連續印刷10片，利用立體顯微鏡對所獲得之第10片之印刷圖像進行觀察，且以如下方式進行評價。又，利用觸針儀(P-16，KLA-tencor公司製造)測定以如下所述之方式所獲得之燒結膜之厚度。Using a metal oxide fine particle dispersion slurry, using a screen printing machine ("MT-320TV" manufactured by MICROTEK Co., Ltd., gap = 2.0 mm, squeegee speed = 50 mm/s, doctor blade speed = 50 mm/s, squeegee) Plate pressure = 0.25 MPa, squeegee pressure = 0.17 MPa, back pressure = 0.110 MPa), screen plate making ("ST500CAL" manufactured by Tokyo Process Service, 2 μm emulsion, 320 mm × 320 mm frame), printed circuit board ( 150 mm × 150 mm soda glass, thickness 15 mm), printed image (line/gap = 50 μm / 150 μm), screen printing at a temperature of 23 ° C and a humidity of 50%. Ten sheets were continuously printed, and the printed image of the obtained tenth sheet was observed with a stereo microscope, and evaluated in the following manner. Further, the thickness of the sintered film obtained in the manner described below was measured by a stylus instrument (P-16, manufactured by KLA-tencor Co., Ltd.).

○印刷圖像之粗細度並無不均。○ There is no unevenness in the thickness of the printed image.

△印刷圖像之粗細度存在不均。△ There is unevenness in the thickness of the printed image.

×因堵塞而導致油墨未塗佈於印刷基板上。× The ink was not applied to the printed substrate due to clogging.

(燒結性)(sinterability)

使用設定成5密耳之塗覆器，將金屬氧化物微粒子分散漿料塗佈於玻璃基板上，利用150℃之送風烘箱乾燥30分鐘後，於450℃之電爐中燒成30分鐘，藉此形成金屬氧化物燒結膜。其後，利用碳硫分析裝置(堀場製作所製造)測定燒結膜之殘留碳(ppm)。又，以目視確認燒成顏色，並以如下方式進行評價。The metal oxide fine particle dispersion slurry was applied onto a glass substrate using an applicator set at 5 mils, dried in a blowing oven at 150 ° C for 30 minutes, and then baked in an electric furnace at 450 ° C for 30 minutes. A metal oxide sintered film is formed. Thereafter, residual carbon (ppm) of the sintered film was measured by a carbon sulfur analyzer (manufactured by Horiba, Ltd.). Moreover, the baking color was visually confirmed, and it evaluated by the following.

○無色。○ colorless.

△成為淡黃色。△ becomes pale yellow.

×附有茶色之燒成顏色。×The color of the burnt brown is attached.

(透光率)(Transmittance)

對於所獲得之金屬氧化物燒結膜，使用霧度計(TC-H3DPK，東京電色公司製造)，以根據JIS K 6714、JIS K 6718之方法測定總透光率(n=3)。將所獲得之值為90%以上之情形判定為◎，將低於90%且88%以上之情形判定為○，將低於88%且85%以上%之情形判定為△，將低於85%低於之情形判定為×。For the obtained metal oxide sintered film, a haze meter (TC-H3DPK, manufactured by Tokyo Denshoku Co., Ltd.) was used to measure the total light transmittance (n = 3) in accordance with the method of JIS K 6714 and JIS K 6718. The case where the obtained value is 90% or more is judged as ◎, the case where it is less than 90% and 88% or more is judged as ○, and the case where it is less than 88% and 85% or more is judged as Δ, and will be lower than 85. The case where % is lower is judged as ×.

(細密性)(fineness)

對於所獲得之金屬氧化物微粒子燒結膜之SEM照片(20000倍)，以全部5個視野的方式確認視野(6μm×5μm)中所見到之粒子間之間隙。將未確認到100nm以上之間隙之情形判定為○，將確認到100nm以上之間隙之情形判定為×。With respect to the SEM photograph (20000 times) of the obtained metal oxide fine particle sintered film, the gap between the particles seen in the visual field (6 μm × 5 μm) was confirmed in all five fields of view. The case where the gap of 100 nm or more was not confirmed was judged as ○, and the case where the gap of 100 nm or more was confirmed was judged as ×.

(分散性)(dispersion)

對於所獲得之金屬氧化物微粒子燒結膜之SEM照片(5000倍)，以全部5個視野的方式確認視野(24μm×20μm)中是否存在凝聚之氧化鎂。With respect to the SEM photograph (5000 times) of the obtained metal oxide fine particle sintered film, whether or not agglomerated magnesium oxide was present in the visual field (24 μm × 20 μm) was confirmed in all five fields of view.

將未確認到凝聚體之情形判定為○，將確認到凝聚體之情形判定為×。The case where the aggregate was not confirmed was judged as ○, and the case where the aggregate was confirmed was judged as ×.

(實施例35)(Example 35)

(黏合劑樹脂之製造)(Manufacture of adhesive resin)

於具備攪拌機、冷卻器、溫度計、熱水浴及氮氣導入口之2L可分離式燒瓶中，混合100重量份之作為(甲基)丙烯酸單體之甲基丙烯酸異丁酯，2.5重量份之作為鏈轉移劑之硫醇基琥珀酸、以及100重量份之作為有機溶劑之乙醇，從而獲得單體混合液。In a 2 L separable flask equipped with a stirrer, a cooler, a thermometer, a hot water bath, and a nitrogen inlet, 100 parts by weight of isobutyl methacrylate as a (meth)acrylic monomer was mixed, and 2.5 parts by weight was used. The thiol succinic acid of the chain transfer agent and 100 parts by weight of ethanol as an organic solvent are used to obtain a monomer mixture.

對於所獲得之單體混合液，藉由使用氮氣起泡20分鐘而去除溶氧後，將可分離式燒瓶系統內以氮氣進行置換，一面攪拌一面升溫至熱水浴沸騰為止。繼而，添加將聚合起始劑(日油公司製造之「PERHEXA H」)以乙醇稀釋而得之溶液。又，於聚合過程中添加數次含有聚合起始劑之乙醇溶液。自聚合開始起7小時後，藉由冷卻至室溫而結束聚合，從而獲得聚甲基丙烯酸異丁酯之乙醇溶液。對於所獲得之聚甲基丙烯酸異丁酯，使用SHOKO公司製造之管柱LF-804作為管柱，進行利用凝膠滲透層析法(GPC)之分析，結果由聚苯乙烯換算之重量平均分子量為1萬。After the dissolved oxygen was removed by bubbling nitrogen gas for 20 minutes with the obtained monomer mixture, the separable flask system was replaced with nitrogen, and the mixture was heated while stirring until the hot water bath boiled. Then, a solution obtained by diluting a polymerization initiator ("PERHEXA H" manufactured by NOF Corporation) with ethanol was added. Further, an ethanol solution containing a polymerization initiator was added several times during the polymerization. After 7 hours from the start of the polymerization, the polymerization was terminated by cooling to room temperature, thereby obtaining an ethanol solution of polyisobutyl methacrylate. For the obtained polybutyl methacrylate, a column LF-804 manufactured by SHOKO Co., Ltd. was used as a column, and analysis by gel permeation chromatography (GPC) was carried out, and the weight average molecular weight converted from polystyrene was obtained. It is 10,000.

(金屬氧化物微粒子分散糊料之製造)(Manufacture of metal oxide fine particle dispersion paste)

以最終達到表11中所記載之金屬氧化物微粒子分散糊料之組成比的方式，對調配有2-乙基-1,3-己二醇(碳原子數相對於羥基數之比=4，常溫下之黏度為323mPa‧s)、2,2-二甲基-1,3-丙二醇(碳原子數相對於羥基數之比=2.5，常溫下為固體)、苄醇之媒液中，添加TiO2粒子(日本AEROSIL公司製造，平均粒徑為20nm)，使用珠磨機(AIMEX公司製造之「RMB-08」)及作為介質之粒徑為1mm之氧化鋯粒子進行6小時珠磨機處理。繼而，以使樹脂固體成分達到15重量%之方式添加上述(黏合劑樹脂之製造)中所獲得之聚甲基丙烯酸異丁酯之乙醇溶液，利用真空去溶劑處理去除乙醇而獲得金屬氧化物微粒子分散糊料。2-ethyl-1,3-hexanediol (the ratio of the number of carbon atoms to the number of hydroxyl groups = 4, in such a manner as to finally reach the composition ratio of the metal oxide fine particle-dispersed paste described in Table 11 The viscosity at room temperature is 323 mPa·s), 2,2-dimethyl-1,3-propanediol (ratio of the number of carbon atoms to the number of hydroxyl groups = 2.5, solid at room temperature), and the medium of benzyl alcohol is added. TiO 2 particles (manufactured by AEROSIL, Japan, average particle diameter: 20 nm), and subjected to a 6-hour bead mill treatment using a bead mill ("RMB-08" manufactured by AIMEX Corporation) and zirconia particles having a particle size of 1 mm as a medium. . Then, an ethanol solution of polyisobutyl methacrylate obtained in the above (manufacture of a binder resin) is added so as to have a resin solid content of 15% by weight, and ethanol is removed by vacuum desolvation treatment to obtain metal oxide fine particles. Disperse the paste.

(實施例36)(Example 36)

(黏合劑樹脂之製造)(Manufacture of adhesive resin)

於具備攪拌機、冷卻器、溫度計、熱水浴及氮氣導入口之2L可分離式燒瓶中，混合100重量份之作為(甲基)丙烯酸單體之甲基丙烯酸異丁酯、0.5重量份之作為鏈轉移劑之硫醇基琥珀酸、以及100重量份之作為有機溶劑之乙醇，從而獲得單體混合液。In a 2 L separable flask equipped with a stirrer, a cooler, a thermometer, a hot water bath, and a nitrogen gas inlet, 100 parts by weight of isobutyl methacrylate (meth)acrylic acid monomer and 0.5 parts by weight were mixed. The thiol succinic acid of the chain transfer agent and 100 parts by weight of ethanol as an organic solvent are used to obtain a monomer mixture.

對於所獲得之單體混合液，藉由使用氮氣起泡20分鐘而去除溶氧後，將可分離式燒瓶系統內以氮氣進行置換，一面攪拌一面升溫至熱水浴沸騰為止。繼而，添加將聚合起始劑(日油公司製造之「PERHEXA H」)以乙醇稀釋而得之溶液。又，於聚合過程中添加數次含有聚合起始劑之乙醇溶液。自聚合開始起7小時後，藉由冷卻至室溫而結束聚合，從而獲得聚甲基丙烯酸異丁酯之乙醇溶液。對於所獲得之聚甲基丙烯酸異丁酯，使用SHOKO公司製造之管柱LF-804作為管柱，進行利用凝膠滲透層析法(GPC)之分析，結果由聚苯乙烯換算之重量平均分子量為4萬。After the dissolved oxygen was removed by bubbling nitrogen gas for 20 minutes with the obtained monomer mixture, the separable flask system was replaced with nitrogen, and the mixture was heated while stirring until the hot water bath boiled. Then, a solution obtained by diluting a polymerization initiator ("PERHEXA H" manufactured by NOF Corporation) with ethanol was added. Further, an ethanol solution containing a polymerization initiator was added several times during the polymerization. After 7 hours from the start of the polymerization, the polymerization was terminated by cooling to room temperature, thereby obtaining an ethanol solution of polyisobutyl methacrylate. For the obtained polybutyl methacrylate, a column LF-804 manufactured by SHOKO Co., Ltd. was used as a column, and analysis by gel permeation chromatography (GPC) was carried out, and the weight average molecular weight converted from polystyrene was obtained. It is 40,000.

(金屬氧化物微粒子分散糊料之製造)(Manufacture of metal oxide fine particle dispersion paste)

以使樹脂固體成分達到11重量%之方式添加上述(黏合劑樹脂之製造)中所獲得之聚甲基丙烯酸異丁酯之乙醇溶液，除此以外，以與實施例35相同之方式獲得金屬氧化物微粒子分散糊料。The metal oxide was obtained in the same manner as in Example 35 except that the ethanol solution of polybutyl methacrylate obtained in the above (manufacture of a binder resin) was added in such a manner that the solid content of the resin was 11% by weight. The fine particles disperse the paste.

(實施例37)(Example 37)

(矽粒子之製造)(Manufacture of bismuth particles)

對三口燒瓶中加入20mL之二辛醚、500μL之油酸，並於燒瓶內流動Ar氣15分鐘。其後，利用真空泵使燒瓶內為減壓狀態，升溫至100℃而熟化1小時後，利用Ar氣恢復至常壓。使燒瓶內升溫至280℃，加入100mg之碘化矽、1mL之THF(tetrahydrofuran，四氫呋喃)，攪拌30分鐘，然後於Ar氣存在下藉由空氣冷卻而冷卻至常溫，從而獲得平均粒徑為50nm之矽粒子(Si-SiO)。To a three-necked flask, 20 mL of dioctyl ether and 500 μL of oleic acid were added, and Ar gas was allowed to flow in the flask for 15 minutes. Thereafter, the inside of the flask was depressurized by a vacuum pump, and the temperature was raised to 100 ° C to be aged for 1 hour, and then returned to normal pressure with Ar gas. The temperature inside the flask was raised to 280 ° C, 100 mg of cesium iodide, 1 mL of THF (tetrahydrofuran, tetrahydrofuran) was added, and the mixture was stirred for 30 minutes, and then cooled to room temperature by air cooling in the presence of Ar gas, thereby obtaining an average particle diameter of 50 nm. Then the particles (Si-SiO).

對所得矽粒子之醚溶液中添加100mg之2,4-二乙基-1,5-戊二醇(碳原子數相對於羥基數之比=4.5，常溫下之黏度為1650mPa‧s)，攪拌後，利用真空去溶劑處理去除醚而獲得金屬氧化物微粒子分散漿料。To the ether solution of the obtained cerium particles, 100 mg of 2,4-diethyl-1,5-pentanediol (the ratio of the number of carbon atoms to the number of hydroxyl groups = 4.5, and the viscosity at normal temperature was 1,650 mPa ‧ s) was added, and the mixture was stirred. Thereafter, the ether was removed by vacuum desolvation treatment to obtain a metal oxide fine particle-dispersed slurry.

(實施例38)(Example 38)

於製造矽粒子時，使燒瓶內升溫至280℃，加入100mg之碘化矽、1mL之THF，攪拌30分鐘後，於Ar氣存在下添加5mL之1-十二烯，藉此進行抗氧化之表面處理，從而獲得平均粒徑為50nm之矽粒子(Si-SiOCnHm)，除此以外，以與實施例37相同之方式獲得金屬氧化物微粒子分散漿料。In the production of ruthenium particles, the temperature in the flask was raised to 280 ° C, 100 mg of cesium iodide and 1 mL of THF were added, and the mixture was stirred for 30 minutes, and then 5 mL of 1-dodecene was added in the presence of Ar gas, thereby performing oxidation resistance. A metal oxide fine particle-dispersed slurry was obtained in the same manner as in Example 37 except that the surface was treated to obtain a cerium particle (Si-SiOC n H m ) having an average particle diameter of 50 nm.

＜評價＞<evaluation>

對於實施例35～38中所獲得之金屬氧化物微粒子分散糊料或金屬氧化物微粒子分散漿料進行以下之評價。將結果示於表11及12中。The following evaluations were performed on the metal oxide fine particle-dispersed paste or the metal oxide fine particle-dispersed slurry obtained in Examples 35 to 38. The results are shown in Tables 11 and 12.

(1)網版印刷性(1) Screen printing

使用金屬氧化物微粒子分散糊料或金屬氧化物微粒子分散漿料，利用網版印刷機(MICROTEK公司製造之「MT-320TV」，間隙=2.0mm，刮漿板速度=50mm/s，刮漿刀速度=50mm/s，刮漿板壓=0.25MPa，刮漿刀壓=0.17MPa，背壓=0.10MPa)、網版製版(Tokyo Process Service公司製造之「ST500CAL」，2μm之乳劑，320mm×320mm之網框)、印刷基板(150mm×150mm之鈉玻璃，厚度為15mm)、印刷圖像(線/間隙=50μm/150μm)，於溫度為23℃、濕度為50%之環境下進行網版印刷。連續印刷10片，利用立體顯微鏡對所獲得之第10片之印刷圖像進行觀察，且以如下方式進行評價。The metal oxide fine particle dispersion paste or the metal oxide fine particle dispersion slurry is used, and a screen printing machine ("MT-320TV" manufactured by MICROTEK Co., Ltd., gap = 2.0 mm, squeegee speed = 50 mm/s, squeegee) is used. Speed = 50mm / s, squeegee pressure = 0.25MPa, squeegee pressure = 0.17MPa, back pressure = 0.110MPa), screen plate making ("ST500CAL" by Tokyo Process Service, 2μm emulsion, 320mm × 320mm Screen frame, printed substrate (150mm × 150mm soda glass, thickness 15mm), printed image (line / gap = 50μm / 150μm), screen printing in an environment of 23 ° C and humidity of 50% . Ten sheets were continuously printed, and the printed image of the obtained tenth sheet was observed with a stereo microscope, and evaluated in the following manner.

○印刷圖像之粗細度並無不均。○ There is no unevenness in the thickness of the printed image.

△印刷圖像之粗細度存在不均、或者印刷圖像非常薄。△The thickness of the printed image is uneven, or the printed image is very thin.

×因堵塞而導致油墨未塗佈於印刷基板上。× The ink was not applied to the printed substrate due to clogging.

(2)燒結性(2) Sinterability

使用設定成5密耳之塗覆器，將金屬氧化物微粒子分散糊料或金屬氧化物微粒子分散漿料塗佈於玻璃基板上，利用150℃之送風烘箱乾燥30分鐘後，於450℃之電爐中燒成30分鐘。利用堀場製作所製造之碳硫分析裝置來測定殘留碳(ppm)。又，以目視確認燒成顏色，並以如下方式進行評價。The metal oxide fine particle dispersion paste or the metal oxide fine particle dispersion slurry was applied onto a glass substrate using an applicator set to 5 mils, and dried in a blowing oven at 150 ° C for 30 minutes, and then at 450 ° C in an electric furnace. Boil in for 30 minutes. The residual carbon (ppm) was measured using a carbon-sulfur analyzer manufactured by Horiba, Ltd. Moreover, the baking color was visually confirmed, and it evaluated by the following.

○無色。○ colorless.

△成為淡黃色。△ becomes pale yellow.

×附有茶色之燒成顏色。×The color of the burnt brown is attached.

(3)儲藏穩定性(3) Storage stability

將金屬氧化物微粒子分散糊料或金屬氧化物微粒子分散漿料於23℃之恆溫室中靜置2週後，以目視確認糊料或漿料之狀態，並以如下方式進行評價。After the metal oxide fine particle dispersion paste or the metal oxide fine particle dispersion slurry was allowed to stand in a constant temperature room at 23 ° C for 2 weeks, the state of the paste or the slurry was visually confirmed and evaluated as follows.

○既未觀察到層分離，亦未觀察到金屬氧化物微粒子之沈澱。○ No layer separation was observed, and precipitation of metal oxide fine particles was not observed.

△透明之溶液滲出，但可再分散。△ The transparent solution oozes, but can be redispersed.

×分離成兩層，且金屬氧化物微粒子沈澱。× separated into two layers, and metal oxide fine particles were precipitated.

產業上之可利用性Industrial availability

根據本發明，可提供一種藉由改善金屬氧化物微粒子之分散性而實現優異之網版印刷性的金屬氧化物微粒子分散漿料。進而，根據本發明，可提供一種含有該金屬氧化物微粒子分散漿料之金屬氧化物微粒子分散糊料、使用該金屬氧化物微粒子分散漿料或該金屬氧化物微粒子分散糊料之金屬氧化物薄膜之製造方法、以及利用該金屬氧化物薄膜之製造方法所獲得之金屬氧化物薄膜。According to the present invention, it is possible to provide a metal oxide fine particle-dispersed slurry which achieves excellent screen printing properties by improving the dispersibility of metal oxide fine particles. Further, according to the present invention, a metal oxide fine particle-dispersed paste containing the metal oxide fine particle-dispersed slurry, a metal oxide thin film using the metal oxide fine particle-dispersed slurry or the metal oxide fine particle-dispersed paste can be provided. A manufacturing method and a metal oxide thin film obtained by the method for producing a metal oxide thin film.

Claims (7)

一種金屬氧化物微粒子分散糊料，其係含有金屬氧化物微粒子分散漿料及黏合劑樹脂者，該金屬氧化物微粒子分散漿料含有金屬氧化物微粒子及有機溶劑，其特徵在於：該金屬氧化物微粒子之平均粒徑為10~100nm，該有機溶劑含有多元醇，該多元醇係於1分子中具有2個以上之羥基；分子中之碳原子數相對於羥基數之比低於5；且常溫下之黏度為100mPa．s以上；此外，該多元醇係選自由3-甲基-1,5-戊二醇、2,4-二乙基-1,5-戊二醇、以及2-乙基-1,3-己二醇所構成之群中的至少一種；該黏合劑樹脂係選自由(甲基)丙烯酸樹脂及聚乙烯縮醛樹脂所構成之群中的至少一種；該(甲基)丙烯酸樹脂具有源自甲基丙烯酸甲酯之鏈段。 A metal oxide fine particle dispersion paste containing a metal oxide fine particle dispersion slurry containing a metal oxide fine particle and an organic solvent, and an organic solvent, characterized in that the metal oxide The average particle diameter of the microparticles is 10 to 100 nm, and the organic solvent contains a polyhydric alcohol having two or more hydroxyl groups in one molecule; the ratio of the number of carbon atoms in the molecule to the number of hydroxyl groups is less than 5; The viscosity is 100mPa. In addition, the polyol is selected from the group consisting of 3-methyl-1,5-pentanediol, 2,4-diethyl-1,5-pentanediol, and 2-ethyl-1,3- At least one selected from the group consisting of hexanediols; the binder resin is selected from at least one selected from the group consisting of (meth)acrylic resins and polyvinyl acetal resins; the (meth)acrylic resin has Methyl methacrylate segment. 如申請專利範圍第1項之金屬氧化物微粒子分散糊料，其中金屬氧化物微粒子含有選自由氧化鋅、氧化銻、氧化矽、氧化錫、氧化銦、氧化鈦、氧化鐵、氧化鎂以及於該等中摻雜有其他金屬之金屬氧化物所構成之群中的至少一種。 The metal oxide fine particle dispersion paste of claim 1, wherein the metal oxide fine particles are selected from the group consisting of zinc oxide, cerium oxide, cerium oxide, tin oxide, indium oxide, titanium oxide, iron oxide, magnesium oxide, and the like And at least one of the group consisting of metal oxides of other metals. 一種金屬氧化物薄膜之製造方法，其具有藉由網版印刷來塗佈申請專利範圍第1項或第2項之金屬氧化物微粒子分散糊料的步驟。 A method for producing a metal oxide thin film comprising the step of coating a metal oxide fine particle-dispersed paste of the first or second aspect of the patent application by screen printing. 一種金屬氧化物薄膜，其係使用申請專利範圍第3項之金屬氧化物薄膜之製造方法而獲得者。 A metal oxide film obtained by using the method for producing a metal oxide film of the third application of the patent application. 如申請專利範圍第4項之金屬氧化物薄膜，其係氧化鎂薄膜。 A metal oxide film according to item 4 of the patent application, which is a magnesium oxide film. 如申請專利範圍第5項之金屬氧化物薄膜，其於450℃下燒成30分鐘後之殘留碳為1重量%以下。 The metal oxide film according to claim 5, wherein the residual carbon after firing at 450 ° C for 30 minutes is 1% by weight or less. 一種電漿顯示器用前面板，其具有申請專利範圍第5項或第6項之金屬氧化物薄膜作為電介質體保護層。A front panel for a plasma display having a metal oxide film of claim 5 or 6 as a dielectric protective layer.
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Families Citing this family (23)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2011148668A (en) * 2010-01-25 2011-08-04 Jsr Corp Metal oxide particle dispersion, metal oxide particle-containing composition and film formed using the same, and photoelectric conversion element
CN102148081A (en) * 2010-11-11 2011-08-10 深圳顺络电子股份有限公司 Manufacturing method of laminated type ceramic electronic element
JP5942983B2 (en) * 2011-03-24 2016-06-29 旭硝子株式会社 Liquid composition, method for producing the same, and glass article
KR101230235B1 (en) * 2011-09-08 2013-02-06 (주)에이티엠코리아 Ink composition for patterning at light guide plate for back light units and method for producing thereof
TW201331353A (en) * 2012-01-17 2013-08-01 Regal Paper Tech Co Ltd Heat dissipation material, heat dissipation structure, preparation method and use thereof
JP5984451B2 (en) * 2012-03-28 2016-09-06 大阪瓦斯株式会社 Metal oxide paste composition
JP5982243B2 (en) * 2012-03-30 2016-08-31 積水化学工業株式会社 Titanium oxide paste
JP6266981B2 (en) * 2012-11-27 2018-01-24 積水化学工業株式会社 Method for producing porous titanium oxide laminate
JP5953217B2 (en) * 2012-12-07 2016-07-20 宇部マテリアルズ株式会社 Magnesium oxide fine particle dispersion
US20140179049A1 (en) * 2012-12-20 2014-06-26 Nanogram Corporation Silicon/germanium-based nanoparticle pastes with ultra low metal contamination
JP6195719B2 (en) * 2013-03-14 2017-09-13 新日本理化株式会社 Composite resin composition
EP2781562B1 (en) * 2013-03-20 2016-01-20 Agfa-Gevaert A method to prepare a metallic nanoparticle dispersion
WO2014181329A1 (en) * 2013-05-06 2014-11-13 Bar-Ilan University Doped metal oxide nanoparticles of and uses thereof
WO2014189886A1 (en) * 2013-05-24 2014-11-27 Nanogram Corporation Printable inks with silicon/germanium based nanoparticles with high viscosity alcohol solvents
JP6391334B2 (en) * 2013-07-12 2018-09-19 積水化学工業株式会社 Method for producing porous titanium oxide laminate
JP2015193709A (en) * 2014-03-31 2015-11-05 太陽インキ製造株式会社 Conductive resin composition and conductive circuit
KR101994736B1 (en) * 2014-07-16 2019-07-01 삼성전기주식회사 Paste for electrostatic protection and their manufacturing method
CN105621475B (en) * 2014-12-01 2017-12-12 北京化工大学 A kind of metal doped zinc oxide liquid phase transparent dispersion and preparation method
JP6160788B1 (en) 2017-01-13 2017-07-12 千住金属工業株式会社 flux
JP7150005B2 (en) * 2018-03-15 2022-10-07 富士フイルム株式会社 Curable resin composition, cured product, diffractive optical element, multilayer diffractive optical element, and method for producing curable resin composition
JP7355313B2 (en) 2019-03-28 2023-10-03 石川県 Metal paste, electronic components, and electronic component manufacturing method
CN112133467A (en) * 2019-06-24 2020-12-25 南京工业大学 Transparent conductive paste based on metal oxide, preparation method and application thereof
JP2023147930A (en) * 2022-03-30 2023-10-13 日揮触媒化成株式会社 Dispersion liquid of particles and method for producing the same, and production method for coating liquid and film-attached substrate

Family Cites Families (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH09129141A (en) * 1995-11-01 1997-05-16 Shinto Paint Co Ltd Metal oxide thin film forming coating agent
JP2000053444A (en) * 1998-08-07 2000-02-22 Jsr Corp Glass paste composition, transfer film and plasma display panel
US7157788B2 (en) * 2001-02-21 2007-01-02 Showa Denko K.K. Metal oxide dispersion for dye-sensitized solar cells, photoactive electrode and dye-sensitized solar cell
JP2003160313A (en) * 2001-09-06 2003-06-03 Tdk Corp Compound for forming metal oxide thin film, method for producing metal oxide and metal oxide thin film
JP4578100B2 (en) * 2001-12-18 2010-11-10 旭化成イーマテリアルズ株式会社 Metal oxide dispersion
CN1711213A (en) * 2002-11-13 2005-12-21 日本曹达株式会社 Dispersoid having metal-oxygen bond, metal oxide film, and monomolecular film
JP2004351608A (en) * 2003-05-07 2004-12-16 Institute Of Physical & Chemical Research Manufacturing method of nano material, and nano material
JP2006049019A (en) 2004-08-02 2006-02-16 Sumitomo Metal Mining Co Ltd Transparent conductive film and its manufacturing method, and paste for forming transparent conductive film
JP2006096577A (en) * 2004-09-28 2006-04-13 Tokyo Institute Of Technology Metal oxide film, method for producing the same, and formed article
TWI398496B (en) * 2005-03-31 2013-06-11 Sekisui Chemical Co Ltd A binder resin composition, and an inorganic fine particle dispersion paste composition
JP2007197296A (en) * 2005-07-27 2007-08-09 Showa Denko Kk Dispersion of metal oxide fine particle and its manufacturing method
US20070078190A1 (en) * 2005-09-30 2007-04-05 Distefano Frank V Use of 2,3-dihydroxynaphthalene-6-sulfonic acid salts as dispersants
JP4956386B2 (en) * 2006-11-09 2012-06-20 古河電気工業株式会社 Manufacturing method of conductive member
CN100511718C (en) * 2007-01-26 2009-07-08 中国科学院物理研究所 Nanometer oxide porous membrane electrode and preparing method and application thereof

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