TW201107389A - Inorganic microparticle dispersion paste - Google Patents

Inorganic microparticle dispersion paste Download PDF

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TW201107389A
TW201107389A TW099125839A TW99125839A TW201107389A TW 201107389 A TW201107389 A TW 201107389A TW 099125839 A TW099125839 A TW 099125839A TW 99125839 A TW99125839 A TW 99125839A TW 201107389 A TW201107389 A TW 201107389A
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Taiwan
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inorganic fine
fine particle
paste
weight
group
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TW099125839A
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Chinese (zh)
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TWI483977B (en
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Kenji Yamauchi
Hiroko Miyazaki
Takahiro Asao
Daihei Sugita
Hideyuki Takahashi
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Sekisui Chemical Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
    • C03C8/14—Glass frit mixtures having non-frit additions, e.g. opacifiers, colorants, mill-additions
    • C03C8/16—Glass frit mixtures having non-frit additions, e.g. opacifiers, colorants, mill-additions with vehicle or suspending agents, e.g. slip
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F120/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
    • C08F120/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F120/10—Esters
    • C08F120/12—Esters of monohydric alcohols or phenols
    • C08F120/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F120/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • 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
    • C08K3/40—Glass
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
    • C08L1/08—Cellulose derivatives
    • C08L1/26—Cellulose ethers
    • C08L1/28—Alkyl ethers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L29/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical; Compositions of hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Compositions of derivatives of such polymers
    • C08L29/14—Homopolymers or copolymers of acetals or ketals obtained by polymerisation of unsaturated acetals or ketals or by after-treatment of polymers of unsaturated alcohols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
    • C08L33/08—Homopolymers or copolymers of acrylic acid esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Materials Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Inorganic Insulating Materials (AREA)

Abstract

Provided is an inorganic microparticle dispersion paste that can form a sintered layer having excellent surface smoothness. Said inorganic microparticle dispersion paste contains: at least one species chosen from a group comprising ethyl cellulose, (meth)acryl resins, and polyvinyl acetal resins; an organic compound; inorganic microparticles; and an organic solvent. The organic compound has one or more hydroxyl groups, is solid at room temperature, and has a boiling point of less than 300 DEG C.

Description

201107389 發明說明： 【發明所屬之技術領域】 本發明係關於-種可形成表面平滑性優異之 無機微粒子分散糊。 σ曰 【先前技術】 =年來，Α了獲得各種形狀之燒結體，而—直利用將 ，粉末、陶竞粉末等無機微粒子分散於黏合樹脂中而 機微粒子分散糊。尤其是作為無機微粒子而將榮光 2政於黏合樹脂中而成之榮光體糊、或分散低炼點玻璃 而f之玻螭糊被應用於電漿顯示面板等，且近年來需求不 斷高羅。 又’將鈦酸鋇或氧化料為無機微粒子分散於黏合樹 而成之陶瓷糊係成形為生片，用於積層型之電子零 件’例如積層陶瓷電容器。 退而，太陽電池板 -月田电桠通常係藉由M網欣叩 等來塗佈分散有紹粉之糊並加以乾燥，然後進行炮燒而 成0 ，例如，電漿顯示面板之介電質層係藉由如下方式而形 成：於玻璃基板上印刷玻璃糊後，利用在爐内循環排氣之 送風供箱乾燥溶劑’繼而制高溫之㈣進行脫脂、锻燒。 作為用以形成介電質層之玻璃糊，例如專利文獻（中揭示 有-種介電質層用組成物、及藉由將該介電質層用組成物 塗佈於支持體上，然後加以乾燥而獲得之生#，上述介電質 層用組成物係電聚顯示面板之介電質層用組成物，並且含 201107389 有至少含玻璃成分之玻璃料'分散劑'熱解黏合劑及溶劑， 上述分散劑為聚緩酸系高分子化合物。 專利文獻1中揭示，於該文獻所揭示之介電質層用組 成物中’玻璃料之分散狀態有效地提昇。 為了形成均勻之燒結層，使燒結層之特性不產生偏 差’如上所述之無機微粒子之分散性之改善十分重要。然 而，燒結層由於係經由無機微粒子分散糊之印刷、乾燥、 脫脂 '煅燒步驟方可形成，因此僅改善糊狀態之均勻性、 即無機微粒子之分散性難以充分確保最終形成之燒結層之 均勻性。 又，亦研究如專利文獻1所揭示之生片般，將無機微 粒子分散糊預先加工成片狀，使用所得之生片從而形成岣 勻之燒結層，但使用生片之情況下，存在生片對基板之密 接性不充分之問題。 專利文獻1 :日本特開2004-002164號公報 【發明内容】 本發明之目的在於提供一種可形成表面平滑性優異之 燒結層之無機微粒子分散糊。 本發明係一種無機微粒子分散糊，其含有：選自由乙 基纖維素、（甲基）丙烯酸樹脂及聚乙烯縮醛樹脂所組成之群 中的至少一種、有機化合物 '無機微粒子以及有機溶劑； 並且上述有機化合物具有丨個以上之羥基，且於常溫下為 固體’沸點低於30(TC。 以下對本發明加以詳述。 4 ⑧ 201107389 通常，用以形成燒結層之無機微粒 高滞點溶劑以確保印刷性。進而，為了高效：掬中係使用 點溶劑而使生產性提昇，於印刷後之乾：步騍：乾燥高滞 送風供箱。本發明人等發現，供箱内之送風使用 =子刀放糊之塗佈層產生表面㈣，結果 表、= 滑性下降，燒結層之性能惡化。 ^之表面平 本發明人等發現，除了選自由乙基纖維 酸樹脂及聚乙烯縮醛樹脂所組成之群中的至小—土)丙烯 微粒子以及有機溶劑以外，進而含有具有！個^=機 且於常溫下為固體’沸點低於3峨之有 Μ基’ 粒子分散糊於印刷後之乾燥步驟中可：的：機微 烘箱中乾燥時，可抑制因在烘箱内受到送風二致：;： 粗糖，而^不會產生㈣脂交聯所致之結皮現^ 糊而形成之燒41表二 用該無機微粒子分散 士一層之表面平滑性優異，從而完成了本發明。 發明之無機微粒子分散糊含有選自由乙基纖維素 (甲基）丙烯酸樹脂及聚乙稀縮链樹脂所組成之群中的至，,、 一種。 ' 上述乙基纖維素並無特別限定，只要根據所得之 =子分散糊之印刷方法、目標燒結層之厚度等而適； 擇專級即可。其中’於進行網版印刷之情形時，通常以呈 有觸變性之乙基纖維素為佳，故較佳^ std 45、咖1〇〇 等之等級之乙基纖維素。又，於要獲得較厚之燒結層之情 形夺m要·揭無機微粒子分散糊中之無機微粒子之組成 r-» 5 201107389 比，無機微粒子分散糊之黏度容易變高，故較佳為STD4、 STD10等低黏度規格之等級之乙基纖維素。 上述（曱基）丙烯酸樹脂只要可於350〜400。(：左右之低 溫下分解，則並無特別限定，較佳為由選自由下述化合物 所組成之群中之至少一種所構成的聚合物，即：（曱基）丙烯 酸曱δ旨、（曱基）丙烯酸乙醋、（甲基）丙烯酸丙g旨、（甲基）内 稀酸正丁醋、（曱基）丙烯酸第三丁酯、（甲基）丙烯酸異丁賴、 (曱基）丙烯酸環己酯、（甲基）丙烯酸_2•乙基己酯 '(甲基）丙 烯酸異冰片酯、（甲基）丙烯酸正硬脂酯 '(甲基）丙烯酸苄酯 及具有聚氧伸烧基結構之（甲基）丙烯酸系單體。此處，例如 (甲基）丙烯酸酯係指丙烯酸酯或甲基丙烯酸酯。 其中，較佳為玻璃轉移溫度（Tg)較高之聚曱基丙稀 酸甲酯（甲基丙烯酸酯之聚合物，Tg為105。〇)，其原因 在於以較少之樹脂量便可獲得較高黏度。而且，聚甲基丙 稀酸酯之低溫脫脂性亦優異。進而，由於本發明之無機微 米立子分散糊含有後述之有機化合物，故（甲基）丙烯酸樹脂較 佳為含有來源於曱基丙烯酸丁酯或曱基丙烯酸異丁酯之成 分的聚合物。 又’上述（曱基）丙稀酸樹脂亦可含有由具有極性基之單 體所構成之片段。 作為上述具有極性基之單體’例如可列舉：甲基丙烯 1-2 -羥基乙酯、曱基丙烯酸羥基丙酯、甲基丙烯酸、曱基 内烯酸縮水甘油酯、甘油單甲基丙烯酸酯等。 於含有來源於上述具有極性基之單體的片段之情形 6 201107389 時’來源於上述具有極性基之單體的片段之含量較佳為20 重量％以下。 若來源於上述具有極性基之單驴 平餵的片段之含量超過20 重量％，則有時會損及低溫下之埶分 ._ 〜…、77解性，或附者於無機微 粒子上之煤灰增多，戋者煻往栌+必/ 曰夕A有現、、'°體之殘留碳增多。上述含量 更佳為10重量份以下。 上述（曱基）丙烯酸樹脂較佳為於分子末端具有親水性 吕月b基。上述親水性官能基並無特別限定，較佳為羰基、 胺基、醯胺基類。 通㊉，於使用在（甲基）丙烯酸系單體之酯取代基上導入 有羰基、胺基、醯胺基等相互作用性較高之官能基的（曱基） 丙烯fee樹知之情形時，於無機微粒子分散糊之锻燒步驟 中，3亥（甲基）丙烯酸樹脂之解聚合受到阻礙而導致熱分解結 束溫度提高，熱分解性嚴重惡化。 相對於此’使用於分子末端具有羰基、胺基、醯胺基 等之（曱基）丙烯酸樹脂之情形時，該（甲基）丙烯酸樹脂之解 聚合不會受到阻礙，而幾乎不會影響熱分解結束溫度。又， 由於玻璃粉末等無機微粒子與羰基、胺基、醯胺基等之相 互作用性較高，故而使用於分子末端具有羰基、胺基、醯 胺基等之（甲基）丙烯酸樹脂之情形時，形成該（甲基）丙烯酸 樹脂之一個分子末端吸附於無機微粒子表面，另一個分子 末端朝有機溶劑側延伸之形態，可防止無機微粒子再凝 聚’使分散穩定性提昇。 上述（甲基）丙烯酸樹脂之由聚苯乙烯換算所得之重量 201107389 平均分子量並無特別限定， 500000 較佳下限為5000,較佳上限為 500000。右上述重量平均 q 子置小於500〇，則有時所得之 無機微粒子分散糊盔法蒋p τ W付； ‘，，、忐獲侍充分之黏度’網版印刷性變 差，而且，有時於印刷後 〜祀琛步驟中，因在烘箱内受 送風所導致之表面粗糙搀 糙增大，由此燒結層之表面平滑性下 降。若上述重量平均分子量超過500000，則所得之|機微 粒子分散糊之㈣力變得過高，有時產生致版 印刷性變差。上述重量平妁八工曰^ 导致，..罔版 篁十均刀子直之較佳上限為1〇〇〇〇〇, 更佳上限為50000。尤#县戈u、+，，m好 凡具疋右上述（甲基）丙烯酸樹脂之由聚 苯乙烯換算所得之重詈早的 " 更1 +均刀子望為10000〜5〇〇〇〇，則網 版印刷時可獲得清晰之圖像，故而較佳。 、， 再者，由聚笨乙烯換算所得之重量平均分子量可藉由 使用例如C〇1_LF_8〇4(昭和電工公司製造）作為管：進 订GPC ( gel permeatl〇n ^。咖❶㈣㈣，凝膠滲透層析） 測定而獲得。 製作上述（甲基）丙烯酸樹脂之方法並無特別限定，例如 可列舉··於具有幾基 '胺基、醯胺基等之聚合起始劑之存 在下’利用自由基聚合法、活性自由基聚合法、引發轉移 、·、止劑聚合法、陰離子聚合法、活性陰離子聚合法等先前 A知之方法使上述（甲基）丙烯酸系單體進行共聚合之方 法，或者，於具有羰基、胺基、醯胺基等之鏈轉移劑之存 在下，利用自由基聚合法、活性自由基聚合法、引發轉移 、·’；止劑聚合法、陰離子聚合法、活性陰離子聚合法等先前 公知之方法使上述（甲基）丙烯酸系單體進行共聚合之方法 8 201107389 等。該等方法可單獨使用，亦可併用兩種以上。 於上述製作（甲基）丙烯酸樹脂之方法中，藉由使用具有 幾基、胺基、醯胺基等之聚合起始劑作為自由基聚合起始 齊J可於更夕之分子末端導入羰基、胺基、醯胺基等。再 者，例如可藉由uc_NMR來確認係僅於上述（甲基）丙烯酸 樹脂之分子末端導入有幾基、胺基、酿胺基等。 上述聚乙烯縮醛樹脂只要與後述有機溶劑之相容性優 異，則並無特別限定，較佳為藉由將息化度& 8〇莫耳％以 上之聚乙稀醇樹脂縮酿化所得，且聚合度為議〜4刪， 縮醛化度為60〜80莫耳％之聚乙烯縮醛樹脂。 上述聚乙烯醇之皂化度較佳為8〇莫耳％以上。若 皂化度小於80莫耳％，目丨丨取7 a ^ 、斗 則t乙稀醇於水中之溶解性蠻罢， 故變得難以進行缩g彳μ Θ „ , 選仃細酪化反應，另外，若羥基量較 時縮醛化反應本身變得困難。 、】有 j述聚乙烯醇之聚合度較佳為1000〜4000。 若上述聚合度小於1〇〇〇，則例如於 料之情形時’有時強度變得不充分。若上述：合= 有時於水中之溶解性下降，或水溶液之黏度;t過 難以進行縮醛化。二。 备 又雙阿’ 降。 ❿且，若溶液黏度變得過高則塗佈性下 再者’上述聚乙烯縮醛之聚合 原料的聚乙烯醇之平“ （用作馮合成時之 ,^之聚合度。X，於混合兩種以上 醇之情形時，係使 I乙烯 用其等之聚合度之平均值。 上述聚乙埽醇传& 糸藉由將乙烯酯之聚合物皂化而獲得。 9 201107389 作為上述乙烯酯，可列舉甲酸乙烯酯、乙酸乙烯酯、 丙酸乙烯酯、三甲基乙酸乙烯酯等，就經濟性方面而言， 較佳為乙酸乙烯酯。 又，上述聚乙烯醇較佳為於主鏈上含有烯烴。 聚乙烯縮醛樹脂之氫鍵結力由於上述α _烯烴之存在而 減弱’故可使黏度之經Β寺穩定性提昇’或可使網版印刷性 提昇。 作為上述α -烯烴，例如可列舉：甲烯、乙烯、丙烯、 異丙稀、丁烯、異丁稀、戊嫦、己稀、環己稀、環己基乙 烯、環己基丙烯等，特佳為乙烯。 作為上述（2-烯烴之含量， 右上述CK -稀煙之含量小於 縮醛樹脂之特性與未經改質之 改變，若超過20莫耳％，則有 下降，故變得難以進行縮醛化 縮醛樹脂之疏水性變得過強， 下降。 車父理想為1〜2〇莫耳％。 1莫耳％，則所得之聚乙烯 聚乙烯縮路樹脂相比無任何 時聚乙稀醇於水中之溶解性 反應，或者所形成之聚乙烯 因而於有機溶劑中之溶解性 上述聚乙烯醇亦可於不損及本發明之效果之範圍内共 聚合有其他乙烯性不飽和單體。 作為此種乙稀性不飽和單體，例如可列舉：丙稀酸、 曱基丙烯酸、鄰苯二甲酸（針）、順丁稀二酸（軒） 康酸（in、丙稀腈、τ基丙稀腈、丙稀醯胺、曱^ 醯胺、（3-丙烯醯胺-3-二曱基丙基）三甲Α 土 土氯化叙、丙嫌酿胳 -2-曱基丙磺酸及其鈉鹽、乙基乙烯基 』& 6»稀基鱗、 10 201107389 N-乙烯基吡咯啶酮、氯乙烯 稀、偏二氟乙烯、四氟乙烯 鈉等。 、乙歸、氟乙歸、偏二氯乙 乙烯基磺酸鈉、烯丙基磺酸 入’耶可使用藉由在 ㈣级丨〜嘅等硫醇化合 ::存：下Η吏乙酸乙稀醋等乙相系單體與乙烯進行共 I ’並將其皂化而獲得之末端改質聚乙稀醇。 上述反應中所使用之經並無特別限定，例如可列舉. 甲酸（包括三聚甲越）、乙媒（包括三聚乙酸）、丙越、 :醛、戊媒、己醛、庚醛、2_乙基己醛、環己醛、糠酸、乙 二醛、戊二醛、苯甲醛' 2_甲基苯甲醛、3_甲基苯甲醛、屯 甲基苯甲酸、對經基酸、間經基酸、苯基乙酸、苯 等。 該些醛可單獨使用亦可併用兩種以上，適合的是 乙酸及/或丁駿。 上述聚乙烯縮醛樹脂可藉由如下方式而獲得：以溫水 將聚乙烯醇樹脂溶解後，於酸觸媒之存在下以達到規定之 縮醛化度的方式添加醛並使其反應後，進行水洗、中和、 乾燥。 作為上述酸觸媒，並無特別規定，有機酸、無機酸均 可使用，例如可列舉：乙酸、對甲苯磺酸、硝酸、硫酸、 鹽酸等。 又，作為中和所用之鹼，例如可列舉：氫氧化納、氣 氧化鉀、氨、乙酸鈉、碳酸鈉、碳酸氫鈉、碳酸鉀等。 本發明中所用之聚乙烯縮醛樹脂之縮醛化度較佳為6〇 11 201107389 〜80莫耳％。若上述縮醛化度小於6〇莫耳％，則有時聚乙 烯縮搭樹脂t氫鍵結性變得過強而無法獲#充分之網版印 刷性。 另一方面，上述縮醛化度超過8〇莫耳％之聚乙烯縮醛 樹脂通常於工業上難以製造。（根據Ρ. τ· FlGry之理論計 算，最大縮醛化度較佳為81.6莫耳％eJ. Am，chem. s〇c 61 1518(1939)) ，， 本發明之無機微粒子分散糊中的上述選自由乙基纖維 素、（甲基）丙烯酸樹脂及聚乙稀縮酸樹脂所組成之群中的至 一種之含量並無特別限定，較佳下限為5重量％，較佳上 限為25重量％。若上述選自由乙基纖維素、（甲基)丙烯酸 樹脂及聚乙烯樹脂戶斤叙成之群中的至少 於5重量％’則有時所得之無機微粒子分散糊無法獲：：分 之黏度，網版印刷性變差，而且，有時於印刷後之乾燥步 驟中，因在供箱内受到送風所導致之表面粗糖增大，由此 燒結層之表面平滑性下降。若上述含量超過25重量％，則 有時所得之無機微粒子分散糊之黏度、黏著力變得過高， 網版印刷性變差。 本發明之無機微粒子分散糊含有具有1個以上之羥 土且於常溫下為固體，滞點低於3〇(TC之有機化合物。 八上述有機化合物於常溫下為固體。藉由使上述有機化 -物,常溫下為固體，所得之無機微粒子分散糊於印刷後 燥步驟中因在供箱内受到送風所導致之表面粗链可得 p制’燒結層之表面平滑性優異。 201107389 —再者，雖上述有機化合物於常溫下為固體，但 :解於後述之有機溶劑中而獲得糊狀之無機微粒心散 =者，上述有機化合物與後述之有機溶劑為不同物質。 藉由添加上述具有丨個以上之羥基，且於常溫 體，沸點低於300。(：之有機化a物妒 、 為固 慮如下。 有機化。物而乾燥性提昇之機制可考 添加至無機微粒子分散糊中之無機 性非當古# »^ J〜衣m馮極 通常之L / /具有吸引高極性之官能基的作用。於 在無機微粒子分散糊中添加且—、 的有機材料之情形時，溶劑 ；^ ’f生之g能基 心劑中U粒子彼此凝聚而產生沈, 因此’若添加具有丨個 广我。 體，彿點低於赠之有機化^ 基’且於常溫下為固 微粒子分散_巾& ° 則4有機化合物於無機 卞刀政糊中與有機溶劑混合而 先吸附於無機;h i 成Ί夜狀，故而可優 #機微拉子之表面，而形成在 微粒子之周圍可蒸發之層。 ”於無機 及聚:稀=樹::W由乙基纖維素、(甲基)丙稀酸樹脂 分子量之群中的至少-種黏合樹脂為高 微粒子分散糊表面逐漸===有機溶劑自無機 樹脂層。 ’、 發生結皮，形成較薄之 此種與乾燥相伴而形成之表 依存於乾燥條件，若在送風條株了曰層非节不均勾，且 成更不均勻之層 ’、之強乾燥條件下則會形 層因此’存在於結皮之樹脂層下的有機溶 13 201107389 劑難以蒸發，而容易於塗膜表面產生凹凸。 相對於此，於無機微粒子 表面形成層的上述有機化 =於乾燥條件下蒸發，而形成使内部之有機溶劑蒸發的 :，此’可減少因樹脂結皮所致的有機溶劑之乾燥不 =二’即便於乾燥不充分之情形時，亦由於該有機化 — 易作為塑化劑而發揮作用，從 而谷易維持平滑性。 上述有機化合物之沸點低於遍。c。若上述有機化合物 :點為取以上’則所得之無機微粒子分散糊於印刷後 之乾燦步驟中之乾燥性下降，燒結層之表面平滑性下降。 上述有機化合物較佳為彿點低於·。C，更佳為低於260。〇 杜或又’上述有機化合物之沸點之下限並無特別限定，較 點2 16(TC以上1上述有機化合物之沸點低於⑽ ’則所得之無機微粒子分散糊容易在印刷過程中乾燥， =於長時間之連續印刷之情形時有時會發生不良狀況。 再者，上述沸點係指常壓下之沸點。 、上述有機化合物具有1個以上之經基。藉由具有"固 =亡之上述經基’可提高所得之無機微粒子分散糊之儲存 〜、疋性，又’藉由羥基與樹脂及有機溶劑之相互作用，可 提高無機微粒子分散糊之勒度，從而可獲得適合於網版印 刷專之黏度。 下二有機化合物只要具有1個以上之經基，且於常溫 :為固體’冻點低於30(rc則並無特別限定，較佳為由碳數 二5 Μ上且小於2G之脂肪鏈構成之醇系有機化合物。 14 201107389 =延醇系有機化合物並無特別限定，例如可列舉：1心 己二醇、丨，8-辛二醇、u〇·癸二 牛， 一田I 叶』且寇知、鯨蠟醇、2,2- T I · 1，3 -丙二辱、22-一广其 17 名―λ*»* 哔，2 —乙基·1，3-丙一醇、2_ 丁基_2乙基 ，3_丙二醇、三羥甲基丙烷、季戊四醇等。 其中，羥基相對於碳數之比例較高的2,2_二甲基_1，3_ 丙一醇、2,2-一乙基_1，3 -丙二醇、2 -丁美2 7甘 衧ζ Ί I·2-乙基_1，3-丙二醇 由於沸點為20(TC左右，軟化點Α 為20 C以上，故可適合地 用作網版印刷中所使用之無機微粒子分散糊。 旦本發明之無機微粒子分散糊中的上述有機化合物之含 里並無特別限定，較佳下限或1壬曰。/ 曰 卜限為1重罝/〇，較佳上限為30重 若上述有機化合物之含量小W重量％，則有時所得 ‘.、、機微粒子分散糊於印㈣之㈣步驟中乾燥性下降， 或因在烘箱内受到送風 7導致之表面粗糖增大，或者產生 :樹知乂聯所致之結皮現象’由此燒結層之表面平滑性下 降。若上述有機化合物之含量超過3〇重量％，則有時所得 之無機微粒子分散糊之儲存穩定性變差。 本發明之無機微粒子分散糊含有有機溶劑。 上述有機溶劑並無特別限定，例如可列舉：乙二醇乙 喊、乙二醇單丁醚、乙_ —%早乙醚乙酸酯、二乙二醇單乙 喊、二乙二醇單甲Μ、- πβ —乙二醇單異丁鍵、三曱基戊二醇 早異丁酸酯、丁基卡必醇、 ^ _ 丁基卡必醇乙酸酉旨、Texanol、 異佛爾酮、乳酸丁酯、鄰 鄰本二甲酸二辛酯、己二酸二辛酯、 卞醇、苯基丙二醇、甲祕上 ,v ^ 断、松脂醇、松脂醇乙酸酯、二氫 A月日醇、一氣松脂醇乙酸狀 曰、丙鲷、甲基乙基酮、曱醇、[Technical Field] The present invention relates to an inorganic fine particle-dispersed paste which is excellent in surface smoothness.曰 曰 [Prior Art] = In the past years, the sintered bodies of various shapes have been obtained, and the inorganic fine particles such as powder and ceramic powder have been dispersed in the adhesive resin to disperse the fine particles. In particular, as a fine particle, a glory paste obtained by glory in a binder resin or a glass paste in which a low-refining glass is dispersed and used as a plasma display panel has been demanded in recent years. Further, a ceramic paste obtained by dispersing barium titanate or an oxidized material as an inorganic fine particle in a bonded tree is formed into a green sheet, and is used for a laminated electronic part such as a laminated ceramic capacitor. Retreat, the solar panel - the moonfield electric raft is usually coated with the paste of the powder and dried by M mesh Xin Yan, etc., and then fired into a gun, for example, the dielectric of the plasma display panel The quality layer is formed by printing a glass paste on a glass substrate, and then drying the solvent by a supply air supply box that circulates and exhausts in the furnace, and then performing high-temperature (four) degreasing and calcination. As a glass paste for forming a dielectric layer, for example, a patent document (a composition for a dielectric layer is disclosed, and a composition for a dielectric layer is applied onto a support, and then applied) By drying, the composition for the dielectric layer is a composition for the dielectric layer of the electropolymer display panel, and contains a glass frit 'dispersant' pyrolysis adhesive and solvent containing at least glass component in 201107389 The dispersing agent is a polyamic acid-based polymer compound. Patent Document 1 discloses that the dispersion state of the glass frit is effectively improved in the composition for a dielectric layer disclosed in the document. In order to form a uniform sintered layer, It is important to improve the dispersibility of the inorganic fine particles as described above. However, since the sintered layer is formed by the printing, drying, and degreasing 'calcining steps of the inorganic fine particle-dispersing paste, it is only improved. The uniformity of the paste state, that is, the dispersibility of the inorganic fine particles, is difficult to sufficiently ensure the uniformity of the sintered layer finally formed. Further, the green sheet disclosed in Patent Document 1 is also studied. The inorganic fine particle-dispersed paste is preliminarily processed into a sheet shape, and the obtained green sheet is used to form a sintered layer. However, when a green sheet is used, there is a problem that the adhesion of the green sheet to the substrate is insufficient. Patent Document 1: Japan JP-A-2004-002164 SUMMARY OF THE INVENTION An object of the present invention is to provide an inorganic fine particle-dispersed paste which can form a sintered layer having excellent surface smoothness. The present invention is an inorganic fine particle-dispersed paste comprising: selected from ethyl fibers At least one of a group consisting of a (meth)acrylic resin and a polyvinyl acetal resin, an organic compound 'inorganic fine particles and an organic solvent; and the above organic compound has more than one hydroxyl group and is solid at normal temperature' The boiling point is less than 30 (TC. The following is a detailed description of the present invention. 4 8 201107389 Usually, the inorganic fine particles of the sintered layer are used to ensure the printability. Further, in order to achieve high efficiency, the production is carried out by using a point solvent in the crucible. Sexual improvement, after printing: Step: dry and high stagnation air supply box. The inventors found that the inside of the box The use of the air supply = the coating layer of the sub-blade paste produces the surface (4), and as a result, the slip property is lowered, and the performance of the sintered layer is deteriorated. ^ The surface of the inventors found that, in addition to being selected from the group consisting of ethyl cellulose resin and poly The propylene microparticles and the organic solvent in the group consisting of the ethylene acetal resin further contain a sulfhydryl group-dispersing paste having a constant value at room temperature and having a boiling point of less than 3 Å. In the drying step after printing: in the machine micro-drying oven, it can suppress the air supply in the oven:;: raw sugar, and ^ will not produce (four) fat-crossing caused by the crust The present invention has been completed by using the inorganic fine particle dispersion layer to have excellent surface smoothness. The inorganic fine particle dispersion paste of the invention contains an ethyl cellulose (meth)acrylic resin and a polyethylene chain. To, in, one of the group consisting of resins. The ethyl cellulose is not particularly limited as long as it is based on the printing method of the obtained sub-dispersion paste, the thickness of the target sintered layer, and the like; Among them, in the case of screen printing, ethyl cellulose having a thixotropic property is preferred, and ethyl cellulose of a grade such as std 45 or coffee is preferred. Further, in order to obtain a thick sintered layer, the composition of the inorganic fine particles in the inorganic fine particle dispersion paste is r-» 5 201107389, and the viscosity of the inorganic fine particle dispersed paste is easily increased, so STD4 is preferable. Ethyl cellulose of low viscosity grade such as STD10. The above (fluorenyl) acrylic resin may be used in the range of 350 to 400. (It is not particularly limited as long as it decomposes at a low temperature, and is preferably a polymer composed of at least one selected from the group consisting of: (mercapto)acrylic acid 曱δ, (曱Ethyl acrylate, (meth)acrylic acid, (methyl) dilute acid n-butyl vinegar, (butyl) methacrylate, butyl (meth) acrylate, (meth) acrylate Cyclohexyl ester, (meth)acrylic acid 2·ethylhexyl ester 'isobornyl (meth)acrylate, n-stearyl (meth) acrylate 'benzyl (meth) acrylate and polyoxyalkylene A (meth)acrylic monomer having a structure. Here, for example, (meth)acrylate means an acrylate or a methacrylate. Among them, a polyacrylonitrile having a high glass transition temperature (Tg) is preferred. Methyl ester (polymer of methacrylate, Tg is 105. 〇), because the higher viscosity can be obtained with a smaller amount of resin. Moreover, the low-temperature degreasing property of polymethyl acrylate is also excellent. Further, since the inorganic micron dispersion paste of the present invention contains organic substances described later The (meth)acrylic resin is preferably a polymer containing a component derived from butyl methacrylate or isobutyl methacrylate. The above (mercapto) acrylic resin may also contain A fragment composed of a monomer having a polar group. Examples of the monomer having a polar group include, for example, 1-2-hydroxyethyl methacrylate, hydroxypropyl methacrylate, methacrylic acid, and decyl enoic acid. Glycidyl ester, glycerol monomethacrylate, etc. In the case of a fragment containing a monomer derived from the above-mentioned polar group, the content of the fragment derived from the above-mentioned monomer having a polar group is preferably 20% by weight. In the following, if the content of the fragment derived from the above-mentioned monoterpenoid having a polar group exceeds 20% by weight, the fraction at a low temperature may be damaged. _ ~..., 77 is decomposable, or attached to the inorganic fine particles. The amount of coal ash is increased, and the latter is 栌+必/ 曰 A A, and the residual carbon of the '° body is increased. The above content is more preferably 10 parts by weight or less. The above (fluorenyl) acrylic resin is preferably a molecule. Hydrophilic at the end The hydrophilic functional group is not particularly limited, and is preferably a carbonyl group, an amine group or a guanamine group. The carbonyl group is introduced on an ester substituent of a (meth)acrylic monomer. When a (mercapto) propylene feel tree having a higher functional group such as an amine group or a guanamine group is known, in the calcination step of the inorganic fine particle dispersion paste, the depolymerization of 3 meth (meth)acrylic resin When it is hindered, the temperature at the end of thermal decomposition is increased, and the thermal decomposition property is seriously deteriorated. In contrast, when it is used in the case of a (fluorenyl) acrylic resin having a carbonyl group, an amine group, a guanamine group or the like at the molecular terminal, the (meth) group is used. The depolymerization of the acrylic resin is not hindered, and the thermal decomposition end temperature is hardly affected. Further, since inorganic fine particles such as glass powder have high interaction with a carbonyl group, an amine group, a mercapto group or the like, they are used at the molecular end. In the case of a (meth)acrylic resin having a carbonyl group, an amine group, a guanamine group, etc., one molecular end of the (meth)acrylic resin is adsorbed on the surface of the inorganic fine particles, and the other Shape extending towards the molecular terminal side of the organic solvent, and then inorganic fine particles can be prevented cohesion 'to enhance the dispersion stability. The weight of the above (meth)acrylic resin converted from polystyrene 201107389 The average molecular weight is not particularly limited, and the preferred lower limit of 500000 is 5,000, and the upper limit is preferably 500000. When the above weight average q sub-set is less than 500 〇, the resulting inorganic fine particles are scattered, and the viscosity of the screen is poor, and sometimes In the post-printing step, the surface roughness and roughness caused by the air blown in the oven are increased, whereby the surface smoothness of the sintered layer is lowered. When the weight average molecular weight exceeds 500,000, the (4) force of the obtained machine-particle-dispersing paste becomes too high, and the plate-printing property may be deteriorated. The above-mentioned weight is flat, and the upper limit of the 篁 均 均 均 knife is 1 〇〇〇〇〇, and the upper limit is 50,000.尤#县戈u,+,,m 凡有有有有有有有有有有有; , it is better to obtain a clear image when printing on the screen. Further, the weight average molecular weight obtained by converting polystyrene can be used as a tube by using, for example, C〇1_LF_8〇4 (manufactured by Showa Denko Co., Ltd.): GPC (gel permeatl〇n ^. curry (four) (four), gel permeation Obtained by chromatography. The method for producing the above (meth)acrylic resin is not particularly limited, and examples thereof include the use of a radical polymerization method or a living radical in the presence of a polymerization initiator having a few groups of an amine group or a guanamine group. a method of copolymerizing the above (meth)acrylic monomer by a method such as a polymerization method, an initiating transfer, a stopper polymerization method, an anion polymerization method, a living anionic polymerization method, or the like, or a carbonyl group or an amine group. In the presence of a chain transfer agent such as a guanamine group, a conventionally known method such as a radical polymerization method, a living radical polymerization method, an initiating transfer, a 'stopping polymerization method, an anionic polymerization method, or a living anionic polymerization method is used. The method of copolymerizing the above (meth)acrylic monomer is 8 201107389 and the like. These methods may be used singly or in combination of two or more. In the above method for producing a (meth)acrylic resin, a carbonyl group can be introduced at the end of the molecule of the molecule by using a polymerization initiator having a group, an amine group, a guanamine group or the like as a radical polymerization initiator. Amine group, guanamine group and the like. Further, for example, it can be confirmed by uc_NMR that a few groups, an amine group, an amine group, and the like are introduced only at the molecular terminal of the above (meth)acrylic resin. The polyvinyl acetal resin is not particularly limited as long as it has excellent compatibility with an organic solvent to be described later, and it is preferably obtained by condensing a polyethylene glycol resin having a degree of reproducibility of 8 mol% or more. And the degree of polymerization is a polyethylene acetal resin having a degree of acetalization of 60 to 80 mol%. The degree of saponification of the above polyvinyl alcohol is preferably 8 〇 mol% or more. If the degree of saponification is less than 80 mol%, the solubility of 7 a ^ and the solvent of t-diethyl alcohol in water is quite good, so it becomes difficult to carry out the shrinkage reaction. Further, when the amount of the hydroxyl group is relatively small, the acetalization reaction itself becomes difficult. The degree of polymerization of the polyvinyl alcohol is preferably from 1,000 to 4,000. If the degree of polymerization is less than 1 Torr, for example, in the case of a material. At the time, sometimes the strength is insufficient. If the above: combined = sometimes the solubility in water decreases, or the viscosity of the aqueous solution; t is too difficult to carry out acetalization. 2. Prepare and double A ' drop. When the viscosity of the solution becomes too high, the coating property is further referred to as the "polyvinyl alcohol of the polymerization raw material of the above polyvinyl acetal" (used as a polymerization degree in the case of von synthesis. X, in the case of mixing two or more kinds of alcohols) In the case of I, the average degree of polymerization of I ethylene is used. The above-mentioned polyethylene glycol is obtained by saponifying a polymer of vinyl ester. 9 201107389 As the vinyl ester, vinyl formate can be mentioned. Ester, vinyl acetate, vinyl propionate, trimethyl vinyl acetate, etc. In terms of economical properties, vinyl acetate is preferred. Further, the polyvinyl alcohol preferably contains an olefin in the main chain. The hydrogen bonding force of the polyvinyl acetal resin is weakened by the presence of the above α-olefin. The stability of the viscosity of the temple can be improved or the screen printing property can be improved. As the above α-olefin, for example, methylene, ethylene, propylene, isopropyl, butene, isobutylene, pentylene can be mentioned. , dilute, cyclohexene, cyclohexylethylene, cyclohexyl propylene, etc., particularly preferably ethylene. As the above (2-olefin content, the content of the above CK-smoke is less than that of the acetal resin and has not been modified. If the change exceeds 20 mol%, the viscosity is lowered, so that it becomes difficult to carry out the acetalization of the acetal resin, and the hydrophobicity is too strong and lowered. The car father is ideally 1 to 2 mol%. %, the obtained polyethylene polyethylene shrinkage resin does not have any solubility reaction of polyethylene glycol in water, or the solubility of the formed polyethylene in an organic solvent. Copolymerization within the range that impairs the effects of the present invention There are other ethylenically unsaturated monomers. Examples of such ethylenically unsaturated monomers include acrylic acid, mercaptoacrylic acid, phthalic acid (needle), and cis-butyl diacid (Xuan) acid. (in, acrylonitrile, τ-acrylonitrile, acrylamide, decylamine, (3-propenylamine-3-dimercaptopropyl) trimethyl hydrazine, chlorinated, arsenic -2-mercaptopropanesulfonic acid and its sodium salt, ethyl vinyl 』& 6» diluted base scale, 10 201107389 N-vinylpyrrolidone, vinyl chloride dilute, vinylidene fluoride, sodium tetrafluoroethylene, etc. , 乙归, 氟乙归, sodium dichloroethylene vinyl sulfonate, allyl sulfonic acid into the 'Ye can use thiol in the (four) grade 慨 ~ generence:: deposit: Η吏 acetic acid A terminally modified polyethylene glycol obtained by synthesizing and saponifying a phase B monomer such as dilute vinegar with ethylene. The above-mentioned reaction is not particularly limited, and examples thereof include formic acid (including trimeric methine), ethyl phthalate (including tripolyacetic acid), propylene, aldehyde, pentane, hexanal, heptaldehyde, and 2 _Ethylhexanal, cyclohexanal, decanoic acid, glyoxal, glutaraldehyde, benzaldehyde '2-methylbenzaldehyde, 3-methylbenzaldehyde, hydrazine methylbenzoic acid, p-basic acid, between By base acid, phenylacetic acid, benzene, and the like. These aldehydes may be used singly or in combination of two or more kinds, and are preferably acetic acid and/or butyl. The polyvinyl acetal resin can be obtained by dissolving a polyvinyl alcohol resin in warm water and then adding an aldehyde to a predetermined degree of acetalization in the presence of an acid catalyst, and then reacting the aldehyde. Wash, neutralize, and dry. The acid catalyst is not particularly limited, and any of an organic acid and an inorganic acid may be used. Examples thereof include acetic acid, p-toluenesulfonic acid, nitric acid, sulfuric acid, and hydrochloric acid. Further, examples of the base to be used for the neutralization include sodium hydroxide, potassium oxychloride, ammonia, sodium acetate, sodium carbonate, sodium hydrogencarbonate, and potassium carbonate. The degree of acetalization of the polyvinyl acetal resin used in the present invention is preferably from 6 〇 11 201107389 to 80 mol%. When the degree of acetalization is less than 6 〇 mol%, the hydrogen bonding property of the polyethylene shrink resin may become too strong to obtain sufficient screen printing property. On the other hand, the above polyvinyl acetal resin having a degree of acetalization of more than 8 〇 mol% is generally industrially difficult to manufacture. (The maximum acetalization degree is preferably 81.6 mol% eJ. According to the theory of τ. τ·FlGry. Am, chem. s〇c 61 1518 (1939)), the above-mentioned inorganic fine particle dispersion paste of the present invention The content of one selected from the group consisting of ethyl cellulose, (meth)acrylic resin, and polyacetic acid resin is not particularly limited, and a preferred lower limit is 5% by weight, and a preferred upper limit is 25% by weight. . If the above-mentioned inorganic fine particle-dispersed paste which is selected from the group consisting of ethyl cellulose, (meth)acrylic resin, and polyethylene resin is at least 5% by weight', the obtained inorganic fine particle-dispersed paste may not be obtained: The screen printing property is deteriorated, and in some cases, in the drying step after printing, the surface coarseness due to the air blowing in the supply box is increased, whereby the surface smoothness of the sintered layer is lowered. When the content is more than 25% by weight, the viscosity and the adhesive force of the obtained inorganic fine particle-dispersed paste may become too high, and the screen printing property may be deteriorated. The inorganic fine particle-dispersed paste of the present invention contains an organic compound having one or more kinds of hydroxyline and being solid at a normal temperature and having a hysteresis of less than 3 Å (TC). The above organic compound is a solid at normal temperature. - The material is solid at normal temperature, and the obtained inorganic fine particle dispersion paste is excellent in surface smoothness of the sintered layer due to the surface thick chain caused by the air supply in the supply box after the printing drying step. 201107389 - Again The organic compound is solid at room temperature, but is obtained by dissolving it in an organic solvent to be described later to obtain a paste-like inorganic particle core dispersion. The organic compound is different from the organic solvent described later. More than one hydroxyl group, and at a normal temperature, the boiling point is less than 300. (: The organic a substance is determined as follows. The mechanism of organic matter. The drying property is improved and added to the inorganic fine particle dispersion paste. Sexual non-traditional # »^ J~ clothing m von very general L / / has the function of attracting highly polar functional groups. Adding organic materials in the inorganic microparticle dispersion paste When the solvent is used, the U particles in the core agent can agglomerate and form a sinking, so if the addition has a wide area, the body is lower than the organic layer of the gift and at room temperature. For the solid particles dispersion _ towel & ° then 4 organic compounds in the inorganic squeegee paste mixed with the organic solvent and first adsorbed to the inorganic; hi into the night, so the excellent surface of the micro-pull, formed in the micro-particles The layer that can be evaporated around it. "Inorganic and poly: thin = tree:: W from ethyl cellulose, at least one kind of binder resin in the molecular weight of (meth) acrylate resin is the surface of the high-fine particle dispersion paste gradually ===Organic solvent from the inorganic resin layer. ', the occurrence of skinning, the formation of thinner such as the accompanying form of drying depends on the drying conditions, if the air supply strain is not uniform, and A more uneven layer', under strong drying conditions, the layer will be so that the organic solvent present under the resin layer of the skin is difficult to evaporate, and it is easy to cause irregularities on the surface of the coating film. The above organication of the surface layer of the microparticles = evaporating under dry conditions to form an internal organic solvent to evaporate: this 'can reduce the drying of the organic solvent caused by the resin crust, not = two' even in the case of insufficient drying, also due to the organic It is easy to function as a plasticizer, so that the grain is easy to maintain smoothness. The boiling point of the above organic compound is lower than that of the above. If the above organic compound: the point is taken above, the obtained inorganic fine particle dispersed paste is printed. The drying property in the dry-drying step is lowered, and the surface smoothness of the sintered layer is lowered. The organic compound is preferably a point lower than · C, more preferably less than 260. The lower limit of the boiling point of the above organic compound It is not particularly limited, and the inorganic fine particle-dispersed paste obtained by the above-mentioned point 2 is more likely to be dried in the printing process than in the case of TC or higher (the above-mentioned organic compound has a boiling point lower than (10)', and sometimes occurs in the case of continuous printing for a long time. Bad condition. Further, the above boiling point means the boiling point at normal pressure. The above organic compound has one or more mesogenic groups. By having the above-mentioned "base of the solid", the storage of the obtained inorganic fine particle-dispersed paste can be improved, and the interaction of the hydroxyl group with the resin and the organic solvent can improve the dispersion of the inorganic fine particles. Degree, so that the viscosity suitable for screen printing can be obtained. The second organic compound has one or more kinds of radicals, and is at a normal temperature: a solid 'freezing point is less than 30 (rc is not particularly limited, and is preferably composed of a fatty chain having a carbon number of 2 Μ and less than 2G). The alcohol-based organic compound is not particularly limited, and examples thereof include 1 hexamethylene glycol, hydrazine, 8-octanediol, u〇·癸二牛, and Ida I leaf.寇, cetyl alcohol, 2,2- TI · 1,3 - propylene dilute, 22-one wide 17 λ*»* 哔, 2-ethyl 1,3-propanol, 2 _ Base 2, ethyl 3-propanediol, trimethylolpropane, pentaerythritol, etc. Among them, 2,2-dimethyl-1,3-propanol, 2,2- having a higher ratio of hydroxyl groups to carbon number Monoethyl-1,3-propanediol, 2-butyrene 2 7-glycan Ί I·2-ethyl-1,3-propanediol has a boiling point of 20 (about TC and a softening point of 20 C or more). The inorganic fine particle-dispersed paste used in the screen printing is suitably used. The content of the above-mentioned organic compound in the inorganic fine particle-dispersed paste of the present invention is not particularly limited, and a preferred lower limit or 1 壬曰 is limited. 1 heavy 罝 / Preferably, the upper limit is 30%. If the content of the organic compound is less than W% by weight, the resulting dryness of the '., the fine particle dispersion paste may be lowered in the step (4) of the printing (4), or may be caused by the supply of air 7 in the oven. The surface of the raw sugar is increased, or the result is: the tree is caused by the crust phenomenon caused by the splicing. The surface smoothness of the sintered layer is lowered. If the content of the above organic compound exceeds 3% by weight, the obtained inorganic fine particles may be dispersed. The inorganic fine particle-dispersing paste of the present invention contains an organic solvent. The organic solvent is not particularly limited, and examples thereof include ethylene glycol, ethylene glycol monobutyl ether, and ethyl ether. Acetate, diethylene glycol monoethyl sulfonate, diethylene glycol monomethyl hydrazine, - πβ-ethylene glycol monoisobutyl bond, tridecyl pentanediol early isobutyrate, butyl carbitol, ^ _ butyl carbitol acetate, Texanol, isophorone, butyl lactate, dioctyl phthalate, dioctyl adipate, decyl alcohol, phenyl propylene glycol, carbamide, v ^ Broken, rosinol, rosin acetate, dihydro A, alcohol, one Gas rosin acetate acetate, acetonide, methyl ethyl ketone, sterol,

S 15 201107389 乙醇、正丙醇、異丙醇、正丁醇、甲笨、二甲苯等。該等 有機溶劑可單獨使用，亦可併用兩種以上。 x 、 本發月之無機微粒子分散糊中的上述有機溶劑之含量 〇並無特別限定，較佳下限為1〇重量％，較佳上限為6〇重量 %右上述有機溶劑之含量小於1 〇重量°/❶，則有時所得之 :…機微粒子分散糊之黏度、黏著力變得過高而網版印刷性 變差。右上述有機溶劑之含量超過60重量％，則有時所得 之無機微粒子分散糊無法獲得充分之黏度而網版印刷性變 差i又，有時於印刷後之乾燥步驟中乾燥性下降，或因在 、、相内又到送風所導致之表面粗縫增大，纟此燒結層 面平滑性下降。 燒 面 ,再者於對本發明之無機微粒子分散糊進行煅燒之情 形時’較佳為於已將上述有機溶劑或有機化合物乾燥之狀 態下進行般燒。若上述有機溶劑或有機化合物未充分乾燥 :於有機溶劑或有機化合物殘留於内部之狀態下進行炮 則點合樹脂熱分解所生成之煤灰容易吸附於微粒子表 故而與完全乾燥之情形相比較，有時碳殘㈣易增多。 本發明之無機微粒子分散糊含有無機微粒子。 末 金屬氧化物微粒子等。 上述無機微粒子並無特別限定，例如可列舉：玻璃粉 H粉末、螢光體微粒子1氧化物等、金屬㈣子、 上述玻璃粉末並無特別限定，例如可列舉：氧化祕玻 螭、矽酸鹽玻璃、鉛玻螭 ^ ^ ^ 幷圾塥硼玻璃等之破璃粉末， ^ Ca0-Al203-Si02 ^ 'Mg〇.Al2〇3.Si〇 2 ^ Ll〇2-Al2〇3-Si〇2 16 201107389 系等各種矽氧化物之玻璃粉末等。 又’作為上述玻璃粉末，亦可使用：pb〇_B2〇3_Si〇2混 合物、Ba0-Zn0-B203-Si02 混合物、Zn〇_Bi2〇3_B2〇3_si〇2 混合物、Bi2〇3_B2〇3_Ba〇-Cu〇 混合物、S 15 201107389 Ethanol, n-propanol, isopropanol, n-butanol, methyl bromide, xylene, etc. These organic solvents may be used singly or in combination of two or more. x The content of the above organic solvent in the inorganic fine particle dispersion paste of the present month is not particularly limited, and a preferred lower limit is 1% by weight, a preferred upper limit is 6% by weight, and the content of the above organic solvent is less than 1 〇 by weight. °/❶, sometimes obtained: ... the viscosity and adhesion of the machine particle dispersion paste become too high and the screen printing property is deteriorated. When the content of the above organic solvent exceeds 60% by weight, the obtained inorganic fine particle-dispersed paste may not have sufficient viscosity, and the screen printing property may be deteriorated. In some cases, the drying property may be lowered during the drying step after printing, or In the phase, the surface is thickened by the air supply, and the smoothness of the sintered layer is reduced. In the case where the inorganic fine particle-dispersed paste of the present invention is calcined, it is preferred to carry out the above-mentioned organic solvent or organic compound in a dry state. When the organic solvent or the organic compound is not sufficiently dried: when the organic solvent or the organic compound remains in the interior, the coal ash generated by the thermal decomposition of the resin is easily adsorbed to the fine particles, and compared with the case of completely drying. Sometimes carbon residue (four) is easy to increase. The inorganic fine particle-dispersed paste of the present invention contains inorganic fine particles. The metal oxide fine particles and the like. The inorganic fine particles are not particularly limited, and examples thereof include glass powder H powder, phosphor fine particle 1 oxide, and the like, and the metal powder is not particularly limited, and examples thereof include oxidized secret glass and bismuth citrate. Glass, lead glass 螭 ^ ^ ^ 幷 塥 塥 borosilicate glass powder, ^ Ca0-Al203-Si02 ^ 'Mg〇.Al2〇3.Si〇2 ^ Ll〇2-Al2〇3-Si〇2 16 201107389 is a glass powder such as various tantalum oxides. Further, as the above glass powder, a mixture of pb〇_B2〇3_Si〇2, a mixture of Ba0-Zn0-B203-SiO2, a mixture of Zn〇_Bi2〇3_B2〇3_si〇2, and Bi2〇3_B2〇3_Ba〇-Cu may also be used. 〇 mixture,

Bi203-Zn0-B203-Al203-Sr0 混合物、Zn〇_Bi2〇3_B2〇3 混合 物、Bi203-Si02 混合物、p2〇5_Na2〇_Ca〇 Ba〇 Al2〇3 B2〇3 狀·合物、P2〇5-SnO混合物、p2〇5_Sn〇 B2〇3混合物、 P2〇5_SnO-Si02 混合物、Cu〇_p2〇5_R〇 混合物、Bi203-Zn0-B203-Al203-Sr0 mixture, Zn〇_Bi2〇3_B2〇3 mixture, Bi203-SiO2 mixture, p2〇5_Na2〇_Ca〇Ba〇Al2〇3 B2〇3 form, P2〇5- SnO mixture, p2〇5_Sn〇B2〇3 mixture, P2〇5_SnO-SiO2 mixture, Cu〇_p2〇5_R〇 mixture,

Si02-B2〇3-ZnO-Na20-Li2〇-NaF-V2〇5 混 合 物、 P2〇5-ZnO-SnO-R2〇-R〇 混合物、B2〇3_Si〇2-Zn〇 混合物、 B203-Si02-Al203-Zr02 混合物、si〇2-B2〇3-ZnO-R20-RO 混 合物、Si02-B203-A12〇3-R〇-r2〇 混合物、Sr〇Zn〇 p2〇5 混 合物、Sr0-Zn0-P205 混合物、BaO-ZnO-B2〇3-Si02 混合物等 之玻璃粉末。再者’ R為選自由Zn、Ba、Ca、Mg、Sr、Sn、 Ni、Fe及Mn所組成之群中的元素。 特佳為PbO-B2〇3_Si〇2混合物之玻璃粉末、或者不含錯 之 Ba0-Zn0-B203-Si02 混合物或 ZnO-Bi2〇3-B2〇3-Si〇2 混合 物等之無鉛玻璃粉末。 上述陶究粉末並無特別限定，例如可列舉：氧化I呂、 氧化锆、氧化鈦、鈦酸鋇、氮氧化鋁、氮化矽、氮化硼等。 又’亦可適合地使用透明電極材料中所使用之奈米IT0 (Indium Tin Oxide，氧化銦錫）或色素增感太陽電池中所 使用之奈米氧化鈦等。 上述螢光體微粒子並無特別限定，例如可列舉· 17 201107389Si02-B2〇3-ZnO-Na20-Li2〇-NaF-V2〇5 mixture, P2〇5-ZnO-SnO-R2〇-R〇 mixture, B2〇3_Si〇2-Zn〇 mixture, B203-Si02-Al203 -Zr02 mixture, si〇2-B2〇3-ZnO-R20-RO mixture, SiO2-B203-A12〇3-R〇-r2〇 mixture, Sr〇Zn〇p2〇5 mixture, Sr0-Zn0-P205 mixture, A glass powder of a BaO-ZnO-B2〇3-Si02 mixture or the like. Further, 'R is an element selected from the group consisting of Zn, Ba, Ca, Mg, Sr, Sn, Ni, Fe, and Mn. Particularly preferred is a glass powder of a PbO-B2〇3_Si〇2 mixture, or a lead-free glass powder containing no erroneous Ba0-Zn0-B203-SiO2 mixture or ZnO-Bi2〇3-B2〇3-Si〇2 mixture. The ceramic powder is not particularly limited, and examples thereof include oxidized Ilu, zirconia, titanium oxide, barium titanate, aluminum oxynitride, tantalum nitride, and boron nitride. Further, nano-IT0 (Indium Tin Oxide) used in a transparent electrode material or nano titanium oxide used in a dye-sensitized solar cell can be suitably used. The above-mentioned phosphor fine particles are not particularly limited, and for example, 17 201107389

BaMgAl10〇l7:Eu、Zn2Si04:Mn、（Y，Gd)B〇3:Eu 等。 上述金屬微粒子並無特別限定，例如可列舉由鎳 '鈀' 鉑、金、銀、鋁、鎢或該等之合金等所構成之粉末等。 又，亦可適合地使用與緩基、胺基、酿胺基等之吸附 特性良好而容易被氧化之銅或鐵等金屬。該等金屬粉末可 單獨使用’亦可併用兩種以上。 曰本發明之無機微粒子分散糊中的上述無機微粒子之含 ^並無特別限^ ’較佳下限為2G重量％，較佳上限為％重 罝/。。右上述無機微粒子之含量小於2〇重量％，則有時所 得之無機微粒子分散糊無法獲得充分之黏度，網版印刷性 變差’又’有時於印刷後之乾 步射因在烘箱内受到送 几所導致之表面粗糙增大，由此燒結層之表面平滑性下 降。右上述無機微粒子之含量超過9〇重量％，則有 之無機微粒子分散糊之黏度變得過高’網版印刷性變差。 為了使上述有機化合物與其他材料之相容性轉定 發明之無機微粒子分散糊較佳為含有界面活 面=劑並無特別限定，較佳為非離子系界面活性劑 本發明之無機微粒子分散糊中的上述非離 性劑之含量並盔特 糸界面活 升“么 …、特別限疋，較佳上限為5重量％。雖铁上试 旦界面活性劑之熱分解性良好，但若其含量超、“ 重以’則有時無機微粒子分散糊之熱分解性下降。k 製作本發明之無機微粒 定，可列舉先前公知之撥抹太、土 去並無特別限 利用三輥研磨機等 ’，具體而5 ’例如可列舉： 專對上逑選自由乙基纖維素、（甲基）丙烯 18 201107389 酸樹脂及聚乙埽_樹脂所組成之群中的至少—種，上述 有機化σ上述有機溶劑，上述無機微粒子及視需要添 加之其他成分進行攪拌之方法等。 本發明之無機微粒子分散糊於印刷後之乾燥步驟中可 =好地乾燥，並且因在烘箱内受到送風所導致之表面粗輪 =丨抑制而且可防止乾燥時之結皮現象之不良影響，故 可形成表面平滑性優異之燒結層。因&，例如適合用作使 用破璃粉末作為無機微粒子時之玻璃糊、使㈣竞粉末作 為’、、、機微粒子時之m使用等金屬或導電性粉末作 為無機微粒子時之導電糊。 其中，使用玻璃粉末作為無機微粒子時之玻璃糊適合 :於形成電漿顯示面板之介電質層等。使用此種玻璃糊而 製造之玻璃介電體亦為本發明之一。 任進而，本發明之無機微粒子分散糊具有可防止乾燥時 :皮見象且可迅速乾燥之特徵。因此，亦可適合地用 於右使用先剐之樹脂糊則乾燥時會流動而難以維持形狀之 構件。再者，如此般無法維持形狀之狀態亦稱為「塌陷」。 例如，於使用先前之樹脂糊來製造電漿顯示器之背面 :中的早元内之螢光體、或太陽電池單元之表面電極等 日守乾、燥時產生塌m而導致於印刷後無法維持高度，但藉 使用本發明之無機微粒子分散糊，在乾燥過程中可於產 f塌陷而流動得高度較低之前將有機溶劑去除，因而本發 “、、機微粒子刀散糊亦可適合地用作平板顯示器之材 19 201107389 使用本發明之無機微粒子分散糊而製造之平板顯示器 亦為本發明之一。 根據本發明’可提供一種能夠形成表面平滑性優異之 燒結層之無機微粒子分散糊。 【實施方式】 以下揭示實施例來對本發明加以更詳細之說明，但本 發明並非僅限定於該等實施例。 (聚合例1 ) 於具備授拌機、冷凝器、溫度計、油浴及氮氣導入口 之2 L可分離式燒瓶中，將曱基丙烯酸異丁酯（ιβμα) ι〇〇 重畺份、及作為有機溶劑之Texanol 1 00重量份混合，而庐 得單體混合液。 使用氮氣使所得之單體混合液起泡20分鐘，藉此將溶 氧去除’然後以氮氣對可分離式燒瓶體系内進行置換，一 邊授拌一邊升溫直至油槽達到i 3〇〇c為止。添加將作為聚合 起始劑之2,2，-偶氮雙[2_甲基_Ν_(2·羥基乙基）丙醯胺]分散 於Texan〇l中而成之溶液。又，於聚合過程中數次添加含有 聚合起始劑之Texanol溶液，合計添加相對於單體1〇〇重量 份而為1.5重量份之聚合起始劑。 自聚合開始起經過7小時後，將反應液冷卻至室溫而 使聚合結束。藉此獲得於分子末端具有醯胺基之（甲基）丙烯 酸樹脂（Poly(IBMA))之 Texanol 溶液。 對於所得之聚合物’使用Column LF-804 (昭和電工公 司製造）作為管柱進行凝膠滲透層析法分析，結果由聚苯 201107389 乙烯換算所得之重量平均分子量為4萬。 (聚合例2) 於具備攪拌機、冷凝器、溫度計、油浴及氮氣導入口 之2L可分離式燒瓶中，將曱基丙烯酸丁酯與甲基丙烯酸甲 酯之1 : 1混合液（BMA/MMA) 100重量份、及作為有機溶 劑之Texanol 1〇〇重量份混合，而獲得單體混合液。 使用氮氣使所得之單體混合液起泡2〇分鐘，藉此將溶 氧去除，然後以氮氣對可分離式燒瓶體系内進行置換，一 邊攪拌一邊升溫直至油槽達到13(rc為止。添加將作為聚合 起始劑之2,2，-偶氮雙[2·甲基_N_(2_羥基乙基）丙醯胺]分散 於Texanol中而成之溶液。又，於聚合過程中數次添加含有 聚合起始劑之Texan〇l溶液，合計添加相對於單體1〇〇重量 份而為1.5重量份之聚合起始劑。 自聚合開始起經過7小時後，將反應液冷卻至室溫而 使聚合結束。藉此獲得於分子末端具有醯胺基之（甲基）丙烯 酸樹脂（Poly(BMA/MMA))之 Texanol 溶液 〇 對於所得之聚合物，使用c〇lumn LF_8〇4 (昭和電工公 司製造為管柱進行凝膠滲透層析法分析，結果由聚苯 乙烯換算所得之重量平均分子量為4萬。 (聚合例3) 於具備攪拌機、冷凝器、溫度計、油浴及氮氣導入口 之2L可分離式燒瓶中，將甲基丙烯酸丁酯與甲基丙烯酸羥 基乙酯之混合液（BMA/HEMA=9/1) 1〇〇重量份、及作為 有機溶劑之松脂醇100重量份混合，而獲得單體混合液。BaMgAl10〇l7: Eu, Zn2Si04: Mn, (Y, Gd) B〇3: Eu, and the like. The metal fine particles are not particularly limited, and examples thereof include a powder composed of nickel 'palladium' platinum, gold, silver, aluminum, tungsten, or the like. Further, a metal such as copper or iron which is easily oxidized by a slow-acting group, an amine group or an amine group can be suitably used. These metal powders may be used singly or in combination of two or more. The content of the above inorganic fine particles in the inorganic fine particle-dispersed paste of the present invention is not particularly limited. The lower limit is preferably 2% by weight, and the upper limit is preferably % by weight. . When the content of the above inorganic fine particles is less than 2% by weight, the obtained inorganic fine particle-dispersed paste may not obtain sufficient viscosity, and the screen printing property may be deteriorated, and sometimes the dry step after printing may be received in the oven. The surface roughness caused by the feeding is increased, whereby the surface smoothness of the sintered layer is lowered. When the content of the above inorganic fine particles exceeds 9% by weight, the viscosity of the inorganic fine particle-dispersed paste becomes too high, and the screen printing property is deteriorated. In order to adjust the compatibility of the above-mentioned organic compound with other materials, the inorganic fine particle-dispersed paste of the invention is preferably contained in an interface-containing active surface = agent, and is preferably a nonionic surfactant. The inorganic fine particle-dispersed paste of the present invention The content of the above-mentioned non-seizure agent and the turret-specific interface increase "what..., especially limited, the upper limit is 5% by weight. Although the thermal decomposition property of the test agent on the iron is good, if the content is good, When the "heavier" is used, the thermal decomposition property of the inorganic fine particle dispersion paste may be lowered. k The inorganic fine particles of the present invention are prepared by a conventionally known method of using a three-roll mill or the like, and specifically, 5 ', for example, the specific upper layer is selected from ethyl cellulose. And (meth) propylene 18 201107389 At least one of the group consisting of an acid resin and a polyethylene hydrazine resin, the organic σ organic solvent, a method of stirring the inorganic fine particles and other components added as needed, and the like. The inorganic fine particle-dispersed paste of the present invention can be dried well in the drying step after printing, and the surface rough wheel is suppressed by the air blown in the oven, and the adverse effect of the skinning phenomenon during drying can be prevented. A sintered layer excellent in surface smoothness can be formed. For example, it is suitable for use as a glass paste in the case of using a glass frit as an inorganic fine particle, a conductive paste in which a metal or a conductive powder is used as an inorganic fine particle when (4) is used as a powder, or when a fine particle is used. Among them, the glass paste when glass powder is used as the inorganic fine particles is suitable for forming a dielectric layer of a plasma display panel or the like. A glass dielectric manufactured using such a glass paste is also one of the inventions. Further, the inorganic fine particle-dispersed paste of the present invention has a feature of preventing drying when the skin is visible and can be quickly dried. Therefore, it is also suitable for a member in which the resin paste of the right-hand use is used to flow while drying, and it is difficult to maintain the shape. Moreover, the state in which the shape cannot be maintained in this way is also called "collapse". For example, in the case where the resin paste is used to manufacture the back surface of the plasma display: the phosphor in the early element or the surface electrode of the solar cell unit is dry and dry, causing collapse and m cannot be maintained after printing. Highly, but by using the inorganic fine particle dispersion paste of the present invention, the organic solvent can be removed before the production f collapses and the flow rate is low during the drying process, so that the present invention can be suitably used. A flat panel display manufactured by using the inorganic fine particle-dispersed paste of the present invention is also one of the inventions. According to the present invention, an inorganic fine particle-dispersed paste capable of forming a sintered layer excellent in surface smoothness can be provided. BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in more detail, but the present invention is not limited to the examples. (Polymer Example 1) A mixer, a condenser, a thermometer, an oil bath, and a nitrogen gas introduction port are provided. In a 2 L separable flask, isobutyl methacrylate (ιβμα) ι〇〇, and Texanol 1 00 as an organic solvent The parts were mixed and the monomer mixture was extracted. The obtained monomer mixture was bubbled with nitrogen for 20 minutes to remove dissolved oxygen, and then the inside of the separable flask system was replaced with nitrogen while stirring. The temperature is raised until the oil tank reaches i 3 〇〇c. 2,2,-azobis[2-methyl-indole-(2.hydroxyethyl)propanamide is added as a polymerization initiator to Texan〇l Further, a solution of a Texanol containing a polymerization initiator was added several times during the polymerization, and a total of 1.5 parts by weight of a polymerization initiator based on 1 part by weight of the monomer was added. After 7 hours, the reaction liquid was cooled to room temperature to complete the polymerization, thereby obtaining a Texanol solution of a (meth)acrylic resin (Poly (IBMA)) having a mercaptoamine group at the molecular end. The gel osmosis chromatography analysis was carried out using Column LF-804 (manufactured by Showa Denko Co., Ltd.) as a column, and the weight average molecular weight obtained from the conversion of polystyrene 201107389 to ethylene was 40,000. (Polymerization Example 2) Agitator and condenser were provided. ,thermometer, In a 2 L separable flask of a bath and a nitrogen inlet, 100 parts by weight of a 1:1 mixture of butyl methacrylate and methyl methacrylate (BMA/MMA), and a Texanol 1 weight as an organic solvent. The mixture was mixed to obtain a monomer mixture. The obtained monomer mixture was bubbled with nitrogen for 2 minutes to remove dissolved oxygen, and then the inside of the separable flask system was replaced with nitrogen, and the temperature was raised while stirring. The oil bath reached 13 (rc), and a solution obtained by dispersing 2,2,-azobis[2·methyl_N_(2-hydroxyethyl)propanamide] as a polymerization initiator in Texanol was added. Further, a Texan® solution containing a polymerization initiator was added several times during the polymerization, and a total of 1.5 parts by weight of a polymerization initiator based on 1 part by weight of the monomer was added. After 7 hours from the start of the polymerization, the reaction liquid was cooled to room temperature to complete the polymerization. Thus, a Texanol solution of a (meth)acrylic resin (Poly(BMA/MMA)) having a mercapto group at the end of the molecule was obtained. For the obtained polymer, c〇lumn LF_8〇4 (manufactured by Showa Denko Co., Ltd.) was used. The gel permeation chromatography analysis showed that the weight average molecular weight obtained by polystyrene conversion was 40,000. (Polymerization Example 3) 2L separable flask equipped with a stirrer, a condenser, a thermometer, an oil bath, and a nitrogen gas introduction port. A mixture of butyl methacrylate and hydroxyethyl methacrylate (BMA/HEMA=9/1) in an amount of 1 part by weight and 100 parts by weight of rosin as an organic solvent are mixed to obtain a monomer mixture. liquid.

S 21 201107389 使用氮氣使所得之單體 4 ^ ^ 合液m0分鐘，藉此將溶 乳去除，然後以氮氣對可分 刀離式燒瓶體糸内進行詈拖，一 邊攪拌一邊升溫直至油描。 俠 知 m 1 130 c為止。添加將作為聚合 起始劑之偶氮雙異丁腈分散於松脂醇十而成之溶液。又， 於聚合過財數次添加含有聚合起始狀松脂醇溶液，合 計添加相對於單體100重量 伤而為0.8重置份之聚合起始 劑0 自聚合開始起經過7小時後’將反應液冷卻至室溫而 使聚合結束。獲得具有異丁腈基的（甲基)丙烯酸樹脂 (P〇ly(BMA/HEMA))之松脂醇溶液。S 21 201107389 The obtained monomer was mixed with nitrogen for 10 minutes, thereby removing the solution, and then the inside of the separable flask was purged with nitrogen, and the mixture was heated while stirring until oil was drawn. Chi knows m 1 130 c so far. A solution in which azobisisobutyronitrile as a polymerization initiator was dispersed in rosinol was added. Further, a polymerization start-up rosin alcohol solution was added several times in the polymerization, and a total of 0.8 parts by weight of the polymerization initiator 0 was added to the monomer weight loss, and the reaction was carried out 7 hours after the start of the polymerization. The solution was cooled to room temperature to complete the polymerization. A rosinol solution of a (meth)acrylic resin (P〇ly (BMA/HEMA)) having an isobutyronitrile group was obtained.

對於所付之聚合物，使用c〇1_ LF_8〇4 (昭和電工公 司製造）作為管柱進行凝膠滲透層析法分析，_果由聚苯 乙烯換算所得之重量平均分子量為14萬。 A (聚合例4) 於具備授摔機、冷凝器、溫度計、油浴及氮氣導入口 之2L可分離式燒槪中，將甲基丙烯酸丁 g旨與甲基丙稀酸甲 醒及甲基丙稀酸經基乙自旨之混合液（bma/Mma/hema = 4/4/2) H)()重量份、及作為有機溶劑的松料丨⑽重量份混 合，而獲得單體混合液。 使用氮氣使所得之單體混合液起泡2〇分鐘，藉此將溶 氧去除，然後以氮氣對可分離式燒瓶體系内進行置換，一 邊攪拌一邊升溫直至油槽達到13(rc為止。添加將作為聚合 起始劑之偶氮雙異丁腈分散於松脂醇中而成之溶液。又， 於聚合過程中數次添加含有聚合起始劑之松脂醇溶液，合 201107389 計添加相對於單體1〇〇重量份而為1 5重量份之聚合起始 劑。 自聚合開始起經過7小時後，將反應液冷卻至室溫而 使聚合結束。藉此獲得於分子末端具有醯胺基之（甲基）丙稀 酸樹脂（P〇ly(BMA/MMA/HEMA))之松脂醇溶液。對於所 得之聚合物’使用Column LF-804 (昭和電工公司製造）作 為管柱進行凝膠滲透層析法分析，結果由聚苯乙烯換算所 得之重量平均分子量為5萬。 (聚合例5) 於具備攪拌機、冷凝器、溫度計、熱水浴及氮氣導入 口之2 L可分離式燒瓶中，將甲基丙烯酸環己酯與曱基丙烯 酉久甲酿及甲基丙烯酸羥基乙酯之混合液 (CHMA/MMA/HEMA=4/5/l) 100重量份、作為鏈轉移劑 之疏基丙二醇〇·2重量份、及作為有機溶劑之松脂醇1〇〇重 量份混合’而獲得單體混合液。 —使用II氣使所得之單體混合液起 '泡2〇 /分鐘，藉此將溶 氧去除，然後以氮氣對可分離式燒瓶體系内進行置換，一 邊攪拌-邊升溫直至熱水槽沸騰為止。添加〇1重量份之作 為聚合起始劑之有機氧化物聚合觸媒 司製造），並於聚合過程中數次添加 (Peroyl 355，曰油公 聚合起始劑，合計添 15重量份之聚合起始 加相對於單體100重量份而合計為 劑。 自聚合開始起經過7 ,丨、祕，收r* 幻/小時後，將反應液冷卻至室溫而 使聚合結束。藉此獲得於八士 *山曰丄 于於刀子末知具有羥基之（甲基）丙烯酸 23 201107389 樹脂（Poly(CHMA/MMA/HEMA))之松脂醇溶液。對於所 得之聚合物，使用Column LF-804(昭和電工公司製造）作 為管柱進行凝膠滲透層析法分析，結果由聚苯乙烯換算戶斤 得之重量平均分子量為5萬。 (聚合例6) 代替聚合例5中之松脂醇而使用Texanol，與聚合例5 同樣地獲得於分子末端具有羥基之（甲基）丙烯酸樹脂 (Poly(CHMA/MMA/HEMA))之 Texanol 溶液。對於所得之 聚合物，使用Column LF-804 (昭和電工公司製造）作為管 柱進行凝膠滲透層析法分析，結果由聚苯乙烯換算所得之 重量平均分子量為8萬。 (實施例1 ) 使乙基纖維素STD4溶解於松脂醇中。對該松脂醇溶 液，以達到表1所示之組成比的方式添加作為有機化合物 之1，6 -己一醇，而獲得媒劑組成物。 對所得之媒劑組成物’以達到表1所示之組成比的方 式添加作為非離子系界面活性劑之BL_4 2(; Nikko Chemical 公司製造）、及作為無機微粒子之平均粒徑為2_〇 #爪之 玻璃微粒子（含有32.5%之Si〇2、2〇 5%之b2〇3、18。/〇之For the polymer to be used, gel permeation chromatography analysis was carried out using c〇1_ LF_8〇4 (manufactured by Showa Denko Co., Ltd.) as a column, and the weight average molecular weight converted from polystyrene was 140,000. A (Polymerization Example 4) In a 2L separable roasting machine equipped with a dentifier, a condenser, a thermometer, an oil bath, and a nitrogen gas inlet, butyl methacrylate and methyl methacrylate are awake and methyl Acrylic acid is mixed with a mixture of a base (bma/Mma/hema = 4/4/2) H) () by weight and a bulking agent (10) by weight as an organic solvent to obtain a monomer mixture . The obtained monomer mixture was bubbled with nitrogen for 2 minutes to remove dissolved oxygen, and then the inside of the separable flask system was replaced with nitrogen, and the temperature was raised until stirring until the oil bath reached 13 (rc). A solution of a polymerization initiator which is obtained by dispersing azobisisobutyronitrile in rosin alcohol. Further, a rosin alcohol solution containing a polymerization initiator is added several times during the polymerization, and is added to the monomer 1 2011. 15 parts by weight by weight of the polymerization initiator. After 7 hours from the start of the polymerization, the reaction solution was cooled to room temperature to complete the polymerization, thereby obtaining a mercapto group at the molecular end. A rosin alcohol solution of a acrylate resin (P〇ly (BMA/MMA/HEMA)). For the obtained polymer 'Column LF-804 (manufactured by Showa Denko KK) as a column for gel permeation chromatography analysis As a result, the weight average molecular weight obtained by polystyrene conversion was 50,000. (Polymerization Example 5) In a 2 L separable flask equipped with a stirrer, a condenser, a thermometer, a hot water bath, and a nitrogen inlet, methacrylic acid was used. ring a mixture of hexyl ester and mercaptopropene hydrazine and hydroxyethyl methacrylate (CHMA/MMA/HEMA=4/5/l) 100 parts by weight, thioglycol hydrazide as a chain transfer agent, 2 parts by weight And mixing the mixture of rosin as an organic solvent in 1 part by weight to obtain a monomer mixture. - using II gas, the resulting monomer mixture is 'bubbled 2 〇 / min, thereby removing dissolved oxygen, and then The inside of the separable flask system was replaced with nitrogen, and the mixture was heated while stirring until the hot water tank was boiled. 1 part by weight of the organic oxide polymerization catalyst used as a polymerization initiator was added, and the number was increased during the polymerization. Addition (Peroyl 355, eucalyptus male polymerization initiator, a total of 15 parts by weight of the polymerization start plus a total of 100 parts by weight of the monomer to add a total of 7. From the beginning of the polymerization, after 7 , 丨, secret, receive r * After illusion/hour, the reaction solution was cooled to room temperature to complete the polymerization, thereby obtaining (meth)acrylic acid 23 201107389 resin (Poly(CHMA/MMA/) which is known as a hydroxyl group at the end of the knife. HEMA)) rosinol solution. For the resulting polymer, The gel osmosis chromatography analysis was carried out using Column LF-804 (manufactured by Showa Denko Co., Ltd.) as a column, and the weight average molecular weight of the polystyrene-converted household was 50,000. (Polymerization Example 6) Instead of Polymerization Example 5 Texanol was used to obtain a Texanol solution of a (meth)acrylic resin (Poly(CHMA/MMA/HEMA) having a hydroxyl group at the molecular terminal in the same manner as in Polymerization Example 5. For the obtained polymer, Column LF- was used. 804 (manufactured by Showa Denko Co., Ltd.) was subjected to gel permeation chromatography as a column, and as a result, the weight average molecular weight obtained by polystyrene conversion was 80,000. (Example 1) Ethylcellulose STD4 was dissolved in rosinol. To the rosin alcohol solution, 1,6-hexanol as an organic compound was added in such a manner as to achieve the composition ratio shown in Table 1, to obtain a vehicle composition. BL_4 2 (manufactured by Nikko Chemical Co., Ltd.) as a nonionic surfactant, and an average particle diameter as inorganic fine particles of 2_〇 were added to the obtained vehicle composition 'to achieve the composition ratio shown in Table 1 as a nonionic surfactant. #爪的玻璃颗粒子 (containing 32.5% of Si〇2, 2〇5% of b2〇3,18./〇之之

ZnO、10%之 Al2〇3、3.5%之 BaO、9%之 Li2〇、6%之 Na20 及0.5%之Sn〇2 )後，使用高速攪拌裝置進行充分混練，利 用二輥研磨機進行處理直至變均勻為止，而製作無機微粒 子分散糊。 (實施例2) 24 201107389 代替乙基纖維素STD4而使用乙基纖維素STD45，使用 肉丑蔻醇代替1，6·己二醇作為有機化合物，且變更為表丄 所不之組成比，除此以外，與實施例丨同樣地製作無機微 粒子分散糊。 (實施例3) 代替乙基纖維素STD4之松脂醇溶液而使用聚合例i中 獲得之（甲基）丙烯酸樹脂（Poly(IBMA))之Texan〇l溶液， 且變更為表1所示之組成比，除此以外，與實施例丨同樣 地製作無機微粒子分散糊。 (實施例4 ) 代替乙基纖維素STD4之松脂醇溶液而使用聚合例2中 獲得之（甲基）丙烯酸樹脂（p〇ly(BMA/MMA))之 溶液，且變更為表丨所示之組成比，除此以外，與實施例丄 同樣地製作無機微粒子分散糊。 (實施例5) (聚乙烯縮醛樹脂之合成） 將聚合度為1700、皂化度為98莫耳％之聚乙烯醇193g 添加至純水2900 g中，於90°C之溫度下攪拌約2小時而使 其溶解。 將該溶液冷卻至4CTC，於其中添加濃度為35重量％之 鹽酸20 g及正丁醛145 g，將液溫下降至15&lt;t，並保持該 溫度而進行縮醛化反應，使反應產物析出。 其後’使液溫為4(TC並保持3小時而使反應結束，藉 由常規方法經過中和、水洗及乾燥，而獲得聚乙烯縮醛樹 25 201107389 脂之白色粉末。 使所付之聚乙烯縮醛樹脂溶解於DMS〇_d6(二曱基亞 爾）中使肖C NMR (核磁共振光譜）測定縮路化度， 結果縮醛化度為78莫耳％。 將所得之聚乙烯縮丁醛樹脂5重量份添加至甲苯22重 量份與乙醇11重量份之混合溶劑中，攪拌溶解，進而以達 到表1所記載之組成比的方式添加作為塑化劑之鄰苯二甲 酸二丁酯2重量份、作為有機化合物之2,2_二曱基_13_丙二 醇，擾拌料。於所得H容液中添加料㈣粉末之 鈦酸鋇（堺化學工業公司製造之「BT_〇1(平均粒徑為〇 3 # m)」）50重量份，利用球磨機混合48小時而製作無機微 粒子分散糊組成物。 (實施例6 ) 對聚合例3中所得之（甲基）丙烯酸樹脂 (Poly(BMA/HEMA))之松脂醇溶液，以達到表i所記載之 組成比的方式添加松脂醇，使其溶解。於其中以達到表1 所6己載之組成比的方式進一步添加作為有機化合物之2 2_ 二甲基-1，3-丙二醇，利用高速分散機使其分散。 進而，以達到表1所記載之組成比的方式添加作為導 電性微粒子之鋁微粒子（平均粒徑為5 &quot;m)、及可實現 煅燒穿通（fire through)之低熔點玻璃微粒子（平均粒徑 為1 #m)，使用高速攪拌裝置充分混練後，一邊注意不 將鋁微粒子壓成扁平狀一邊利用三輥研磨機進行處理，製 備導電性微粒子分散糊。 26 201107389 (實施例7) 使用使乙基纖維素STD4溶解於松脂醇中而成之溶 液、及聚合例4中所得之（甲基）丙烯酸樹Z (P〇ly(BMA/MMA/HEMA))之松脂醇溶液，且變更為表ι 所記載之組成比，除此以外，與實施例丨同樣地製作無機 微粒子分散糊。 (實施例8) 使用聚合例5中所得之（甲基）丙烯酸樹脂 (Poly(CHMA/MMA/HEMA))之松脂醇溶液、松香化合物 (KR85，荒川化學公司製造）、作為無機微粒子之PDp (Plasma display panel，電漿顯示面板）用綠色營光體 (Zn2Si〇4:Mn，日亞化學公司製造），且變更為表1所兮己 載之組成比，除此以外’與實施例1同樣地製作無機微粒 子分散糊。 (實施例9) 使用聚合例 6中所得之（甲基）丙烯酸樹脂 (Poly(CHMA/MMA/HEMA))之 Texanol 溶液、乙基纖維素 (STD7 )、及作為無機微粒子之銀粉（粒徑為2 // m，昭 榮化學公司製造），且變更為表1所記載之組成比，除此 以外，與實施例1同樣地製作無機微粒子分散糊。 (比較例1 ) 不使用作為有機化合物之1，6_己二醇’且變更為表1 所示之組成比，除此以外，與實施例1同樣地製作無機微 粒子分散糊。 27 201107389 (比較例2) 不使用作為有機化合物之1，6-己二醇，且變更為表1 所不之組成比，除此以外’與實施例3同樣地製作無機微 粒子分散糊。 (比較例3) 不使用作為有機化合物之2,2-二甲基-1，3-丙二醇，且變 更為表1所示之組成比，除此以外’與實施例6同樣地製 作無機微粒子分散糊。 (比較例4) 代替作為有機化合物之2,2-二甲基丙二醇，而使用 具有經基’於常溫下為固體但沸點為3〇(rc以上之季戊四 醇，除此以外，與實施例6同樣地製作無機微粒子分散糊。 (比較例5) 代替作為有機化合物之2,2-二甲基-1，3_丙二醇，而使用 具有^基’於常溫下為液體之2_甲基丙二醇，除此以 外’與實施例6同樣地製作無機微粒子分散糊。 (比較例6) 代替作為有機化合物 旦古^ 一甲基]，3-丙二醇，而使用 ^ ^ 土，於节溫下為液體之2_甲基-】，3·丙二醇，除此以 ，、貫施例8同樣地製作無機微粒子分散糊。 (比較例7) 代替作為有機化合物 旦右^ 2’2-—甲基-1，3_丙二醇，而使用 具有羥基，於常溫下為液 _而使用 外，與實施例9同_^ m，3-丙二醇，除此以 ’ 裏作無機微粒子分散糊。 (s) 28 201107389 〈評價〉 獲知' 之無機微粒子分散糊進行以 對實施例及比較例中 下s平價。結果示於表2中 (1 )燒結性 使用設定為5密耳之敷料器，將無機微粒子分散糊塗 佈於玻璃基板上，於⑽之送風供箱中乾燥3〇分鐘後， 於5〇(TC之電爐中锻燒3G分鐘。對所得之燒結層藉由碳硫 分析裝置（堀場製作所公司製造）測定殘留碳（ppm)，又， 目視確認炮燒顏色。當殘留碳為15G ppm以下時將燒結性 評價為「〇」’殘留碳超過150ppm時將燒結性評價為「X」。 (2 )表面平滑性 使用設定為5密耳之敷料器’將無機微粒子分散糊塗 佈=玻璃基板上，於15〇。(：之送風烘箱中乾燥％分鐘。對 所仔之無機微粒子分散糊塗佈層’利用依據JIS B 之 方法測定表面之中心線平均粗糙度（Ra)，當Ra為以 m以下時將表面平滑性評價為「〇」，超過丨〇 _時將 表面平滑性評價為「X」。測定中使用觸針式粗糙度計（東 尽精密公司製造，Surfcom 1400D)。 再者，比較例2中所得之無機微粒子分散糊之黏度較 高’塗佈該無機微粒子分散糊而獲得之塗佈層可見膜厚起 伏變動。 (3 )不塌陷乾燥性 使用乳劑厚度為20 // m、不鏽鋼絲網# 3〇〇、乳劑之 開口部之線寬為100 #m、間隔為300以爪之條紋狀網版ZnO, 10% Al2〇3, 3.5% BaO, 9% Li2〇, 6% Na20, and 0.5% Sn〇2) were thoroughly kneaded using a high-speed stirring device and processed by a two-roll mill. The inorganic fine particle-dispersed paste was prepared until it became uniform. (Example 2) 24 201107389 Ethyl cellulose STD45 was used instead of ethyl cellulose STD4, and meat ugly alcohol was used instead of 1,6·hexanediol as an organic compound, and was changed to the composition ratio of the surface, except Otherwise, an inorganic fine particle-dispersed paste was produced in the same manner as in Example 。. (Example 3) A Texan® solution of (meth)acrylic resin (Poly (IBMA)) obtained in Polymerization Example i was used instead of the rosin alcohol solution of ethylcellulose STD4, and was changed to the composition shown in Table 1. In the same manner as in Example 丨, an inorganic fine particle-dispersed paste was prepared. (Example 4) A solution of (meth)acrylic resin (p?ly (BMA/MMA)) obtained in Polymerization Example 2 was used instead of the rosin alcohol solution of ethylcellulose STD4, and was changed to the one shown in Table 丨. An inorganic fine particle-dispersed paste was produced in the same manner as in Example 除 except for the composition ratio. (Example 5) (Synthesis of polyvinyl acetal resin) 193 g of polyvinyl alcohol having a degree of polymerization of 1700 and a degree of saponification of 98 mol% was added to 2900 g of pure water, and stirred at a temperature of 90 ° C for about 2 Allow it to dissolve in an hour. The solution was cooled to 4 CTC, and 20 g of hydrochloric acid having a concentration of 35% by weight and 145 g of n-butyraldehyde were added thereto, and the temperature of the liquid was lowered to 15 lt. t, and the temperature was maintained to carry out an acetalization reaction to precipitate a reaction product. . Thereafter, the liquid temperature was 4 (TC and held for 3 hours to complete the reaction, and the mixture was neutralized, washed with water and dried by a conventional method to obtain a white powder of a polyvinyl acetal tree 25 201107389 fat. The ethylene acetal resin was dissolved in DMS〇_d6 (didecyl yar) to determine the degree of decarburization by Xiao C NMR (nuclear magnetic resonance spectroscopy), and the degree of acetalization was 78 mol%. 5 parts by weight of butyral resin was added to a mixed solvent of 22 parts by weight of toluene and 11 parts by weight of ethanol, and the mixture was stirred and dissolved, and further, dibutyl phthalate as a plasticizer was added so as to achieve the composition ratio shown in Table 1. 2 parts by weight of 2,2-didecyl-13-propanediol as an organic compound, and a mixture of the material (4) powder of barium titanate ("BT_〇1" manufactured by 堺Chemical Industries Co., Ltd.) 50 parts by weight (average particle diameter: 〇3 #m)"), and the inorganic fine particle-dispersed paste composition was prepared by mixing in a ball mill for 48 hours. (Example 6) (meth)acrylic resin (Poly) obtained in Polymerization Example 3 (BMA/HEMA)) rosinol solution to achieve the group listed in Table i In a specific manner, rosinol was added and dissolved, and 2 2 -dimethyl-1,3-propanediol as an organic compound was further added so as to achieve the composition ratio of 6 in Table 1, and it was made by a high-speed disperser. Further, aluminum fine particles (average particle diameter: 5 &quot;m) as conductive fine particles and low-melting glass fine particles capable of achieving fire through are added so as to achieve the composition ratio shown in Table 1 (average After the particle size was 1 #m), the aluminum microparticles were pressed into a flat shape while being sufficiently kneaded by a high-speed stirring device to prepare a conductive fine particle-dispersed paste. 26 201107389 (Example 7) a solution obtained by dissolving ethyl cellulose STD4 in rosin and a rosinol solution of (meth)acrylic acid tree Z (P?ly (BMA/MMA/HEMA)) obtained in Polymerization Example 4, and changing to In the same manner as in Example 丨, an inorganic fine particle-dispersed paste was prepared in the same manner as in Example 。. (Example 8) The (meth)acrylic resin (Poly(CHMA/MMA/HEMA) obtained in Polymerization Example 5 was used. ))) a lipo alcohol solution, a rosin compound (KR85, manufactured by Arakawa Chemical Co., Ltd.), a green campsite (Zn2Si〇4: Mn, manufactured by Nichia Chemical Co., Ltd.), which is a PDp (Plasma display panel) of inorganic fine particles, and The inorganic fine particle-dispersed paste was produced in the same manner as in Example 1 except that the composition ratio of the composition shown in Table 1 was changed. (Example 9) The (meth)acrylic resin (Poly (CHMA) obtained in Polymerization Example 6 was used. /MMA/HEMA)) Texanol solution, ethyl cellulose (STD7), and silver powder as inorganic fine particles (particle size: 2 // m, manufactured by Zhaorong Chemical Co., Ltd.), and changed to the composition ratio shown in Table 1. An inorganic fine particle-dispersed paste was produced in the same manner as in Example 1 except the above. (Comparative Example 1) An inorganic fine particle-dispersed paste was produced in the same manner as in Example 1 except that the composition ratio of the 1,6-hexanediol as the organic compound was changed. 27 201107389 (Comparative Example 2) An inorganic fine particle-dispersed paste was produced in the same manner as in Example 3 except that 1,6-hexanediol was used as the organic compound, and the composition ratio of Table 1 was changed. (Comparative Example 3) In the same manner as in Example 6, except that 2,2-dimethyl-1,3-propanediol was used as the organic compound, and the composition ratio shown in Table 1 was changed, the inorganic fine particle dispersion was produced in the same manner as in Example 6. paste. (Comparative Example 4) The same procedure as in Example 6 was carried out, except that 2,2-dimethylpropanediol was used as the organic compound, and pentaerythritol having a boiling point of 3 〇 (rc or more) was used as the solid at room temperature. The inorganic fine particle-dispersed paste was prepared. (Comparative Example 5) Instead of 2,2-dimethyl-1,3-propanediol as an organic compound, 2-methylpropanediol having a liquid at room temperature was used. In the same manner as in Example 6, an inorganic fine particle-dispersed paste was produced. (Comparative Example 6) Instead of being an organic compound, danco-methyl, 3-propanediol, it was used as a liquid at a temperature of 2 In the same manner as in Example 8, the inorganic fine particle-dispersed paste was prepared in the same manner as in Example 8. (Comparative Example 7) Instead of being an organic compound, 2'2-methyl-1,3 _ propylene glycol, and the use of a hydroxyl group, at room temperature for liquid use, and the same as in Example 9, _^ m, 3-propanediol, except for the use of inorganic fine particles dispersed paste. (s) 28 201107389 <Evaluation> Know 'Inorganic microparticle dispersion paste is carried out in the examples and comparative examples The results are shown in Table 2. (1) The sinterability was set to 5 mil applicator, and the inorganic fine particle dispersion paste was applied onto a glass substrate, and dried in an air supply box of (10) for 3 minutes, at 5 〇. (3G minutes of calcination in an electric furnace of TC. The residual sintered carbon (ppm) was measured by a carbon-sulfur analyzer (manufactured by Horiba, Ltd.), and the color of the burnt was visually confirmed. When the residual carbon was 15 Gppm or less When the sinterability was evaluated as "〇", the sinterability was evaluated as "X" when the residual carbon exceeded 150 ppm. (2) Surface smoothness The inorganic fine particle dispersion paste was applied onto a glass substrate using an applicator set to 5 mils. (15: dry in a blown air oven for % minutes. For the inorganic fine particle dispersion paste coating layer of 'taken ones, use the method according to JIS B to measure the center line average roughness (Ra) of the surface, when Ra is less than m) The surface smoothness was evaluated as "〇", and the surface smoothness was evaluated as "X" when it exceeded 丨〇_. A stylus type roughness meter (Surfcom 1400D, manufactured by Tosoh Corporation) was used for the measurement. Nothing in 2 The viscosity of the microparticle-dispersed paste is higher. The coating layer obtained by coating the inorganic fine particle-dispersed paste shows a fluctuation in the thickness of the coating layer. (3) The drying property is not collapsible. The thickness of the emulsion is 20 // m, stainless steel mesh # 3〇〇 The line width of the opening of the emulsion is 100 #m, and the interval is 300.

S 29 201107389 印刷版’將實施例8 ' 9及比較例6、7中獲得之無機微粒 子分散糊印刷於玻璃基板上，於設定為120°C之送風式块箱 中乾燥20分鐘。然後，使用雷射顯微鏡評價印刷形狀之高 為「〇」，脾认 〜间反芍//m以上之情形評 於1 〇 β m之一 塌陷而印刷形狀之咼度變虑丨 之向度的情形評價為「χ 。 成小 ⑧ 30 201107389 1 無機微粒子分散糊 1 低熔點玻璃微粒子 含量 (重量°/。） 1 • — - • • 1 - • - m 無機微粒子 含量 (重量％) 〇 〇 〇 〇 r^· 〇 〇 〇 〇 種類 玻璃微粒子 玻璃微粒子 玻璃微粒子 玻璃微粒子 鈦酸鋇 鋁微粒子 玻璃微粒子 Zn2Si〇4：Mn 銀粒子 1玻璃微杜子1 1玻璃微粒子1 1鋁微粒子1 鈦酸鋇 鋁微粒子 Zn2Si〇4：Mn 銀粒子 界面活性劑 含量 (重量％) - - - - - • - - ' • • 塑化劑 含量 (重量％) • • ίΝ • • • ' (N • • 種類 • • 鄰笨二甲酸二丁酯 • • ' • 鄰笨二甲酸二丁酯 • 1 媒剤組成物 1 1 有機溶劑 1 含量 (重量％) r^t 〇\ rn ίΝ — &lt;Ν — 12.5 35.6 ΓΝ ΡΛ ? 3 二 ΙΛ (N 35.6 &lt;Ν 種類 松脂醇 松脂酵 Texanol Texanol 甲苯 乙醇 松脂醇 松脂醇 松脂醇 Texanol 1松脂酵1 | Texanol | 1松脂醇1 曱笨 乙醇 忪脂醇 松脂酵 Texanol I 有機化合物 I 沸點（°C) 250 S rs &lt;N 264 〇 ίΝ 210 210 210 210 1 • &lt; 300 ΓΊ rn &lt;N &lt;N 含量 (重量％) 〇 〇 〇 ο 〇 xrt ΙΛ • • • 〇 寸 種類 /—S η 駐回 »1 ^ Γϋ ^ -¥ 肉豆蔻酵 (於常溫下為固體） 培囫 ι| ^ rO卜 —φ6· 肉豆蔻酵 (於常溫下為固體） 钼 ίϋ r«i ，t钼 «Ν 结* Θ m «Λ «5* 3, ^ (N '1 ^ ίϋ (Ν ，1餒 ^ a Λ ^ I ^ (N 1 • • 季戊四醇 (於常溫下為固體） 2-甲基-1,3-丙二酵 (於常溫下為液體） »1 «ί 21 Λ -^ Ί Λ ^ -^ 1 黏合樹脂 1 含f (重量％) 〇 卜 ir&gt; Ξ〜 -S fS &lt;N (N -2 &lt;N &lt;N 種類 乙基纖維素STD4 乙基纖維素STD45 Poly(IBMA) Poly(BMA/MMA) 聚乙烯缩醛 Poly(BMAZHEMA) P〇]y(BMA/MMA/HEMA) 乙基織維素STD4 Poly(CHMA/MMA/HEMA) 松香化合物 P〇]y(CHMA/MMA/HEMA) 乙基埴維素（STD7) 1 乙基織維素STD4 1 I 田 S Poly(BMA/HEMA) | 聚乙烯缩醛 1 Poly(BMAZHEMA) Poly(CHMA/MMA/HEMA) 松香化合物 P〇]y(CHMA/MMA/HEMA) 乙基埴維素（STD7) 實施例1 實施例2 實施例3 實施例4 實施例5 實施例6 實施例7 實施例8 實施例9 1比較例ι| 1比較例2| 1比較例3| 比較例4 比較例5 比較例6 比較例7 201107389 [表2]S 29 201107389 Printing plate The inorganic fine particle-dispersed paste obtained in Example 8 '9 and Comparative Examples 6 and 7 was printed on a glass substrate, and dried in a blower box set at 120 ° C for 20 minutes. Then, using a laser microscope to evaluate the height of the printed shape as "〇", the situation of the spleen recognizing ~ 芍 芍 / / m or more is evaluated as the collapse of one of the 〇β m and the degree of the shape of the printed shape is changed. The situation is evaluated as "χ. Cheng Xiao 8 30 201107389 1 Inorganic fine particle dispersion paste 1 Low melting point glass fine particle content (weight ° /.) 1 • — • • 1 - • - m Inorganic fine particle content (% by weight) 〇〇〇〇 r^· 〇〇〇〇 type glass microparticles glass microparticles glass microparticles glass microparticles barium titanate aluminum microparticles glass microparticles Zn2Si〇4: Mn silver particles 1 glass micro-dip 1 1 glass microparticles 1 1 aluminum microparticles 1 barium titanate aluminum microparticles Zn2Si 〇4: Mn silver particle surfactant content (% by weight) - - - - - - - - - ' • • Plasticizer content (% by weight) • • ίΝ • • • ' (N • • Type • • Dibutyl formate • • ' • Dibutyl phthalate • 1 Media composition 1 1 Organic solvent 1 Content (% by weight) r^t 〇\ rn ίΝ — &lt;Ν — 12.5 35.6 Γ ΙΛ ΡΛ ? 3 ΙΛ (N 35.6 &lt; 种类 species rosinol rosin yeast Texanol Texanol toluene ethanol rosin rosin rosin alcohol Texanol 1 rosin yeast 1 | Texanol | 1 rosinol 1 曱 忪 ethanol 忪 醇 松 T T Texanol I organic Compound I Boiling Point (°C) 250 S rs &lt;N 264 〇ίΝ 210 210 210 210 1 • &lt; 300 ΓΊ rn &lt;N &lt;N Content (% by weight) 〇〇〇ο 〇xrt ΙΛ • • • 〇 Type /—S η Resident»1 ^ Γϋ ^ -¥ Nutmeg fermented (solid at room temperature) Pei ι| ^ rO卜—φ6· Nutmeg (solid at room temperature) Molybdenum « r«i tMo*«Ν结* Θ m «Λ «5* 3, ^ (N '1 ^ ίϋ (Ν ,1馁^ a Λ ^ I ^ (N 1 • • Pentaerythritol (solid at room temperature) 2-methyl -1,3-propanedialdehyde (liquid at room temperature) »1 «ί 21 Λ -^ Ί Λ ^ -^ 1 Adhesive resin 1 Contains f (% by weight) 〇 ir> Ξ~ -S fS &lt;N (N -2 &lt;N &lt;N type ethyl cellulose STD4 ethyl cellulose STD45 Poly(IBMA) Poly(BMA/MMA) polyethylene acetal Poly(BMAZHEMA) P〇]y (BMA/MMA/HEMA) Ethyl acetate ST D4 Poly(CHMA/MMA/HEMA) Rosin Compound P〇]y(CHMA/MMA/HEMA) Ethyl sulphate (STD7) 1 Ethyl stellate STD4 1 I Field S Poly(BMA/HEMA) | Polyethylene Acetal 1 Poly (BMAZHEMA) Poly (CHMA/MMA/HEMA) Rosin Compound P〇]y (CHMA/MMA/HEMA) Ethyl ursin (STD7) Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Example 9 1 Comparative Example ι| 1 Comparative Example 2| 1 Comparative Example 3| Comparative Example 4 Comparative Example 5 Comparative Example 6 Comparative Example 7 201107389 [Table 2]

燒結性 表面平滑性 不塌陷乾燥性 殘留碳（ppm) 判定 中心線平均粗縫度（Ra) (^m) 判定 實施例1 150 〇 0.7 〇 - 實施例2 150 〇 0.8 〇 - 實施例3 100 〇 0.5 〇 - 實施例4 100 〇 0.6 〇 - 實施例5 150 〇 0.7 〇 - 實施例6 110 〇 0.6 〇 - 實施例7 90 〇 0.7 〇 - 實施例8 110 〇 0.7 〇 〇 實施例9 80 〇 0.8 〇 〇 比較例1 250 X 1.4 X - 比較例2 250 X 1.7 X - 比較例3 150 〇 1.5 X - 比較例4 300 X 1.8 X - 比較例5 200 X 1.7 X - 比較例6 110 〇 1.4 X X 比較例7 60 〇 1.7 X XSintering surface smoothness does not collapse dry residual carbon (ppm) Determination center line average roughness (Ra) (^m) Judgment Example 1 150 〇 0.7 〇 - Example 2 150 〇 0.8 〇 - Example 3 100 〇 0.5 〇 - Example 4 100 〇 0.6 〇 - Example 5 150 〇 0.7 〇 - Example 6 110 〇 0.6 〇 - Example 7 90 〇 0.7 〇 - Example 8 110 〇 0.7 〇〇 Example 9 80 〇 0.8 〇 〇Comparative Example 1 250 X 1.4 X - Comparative Example 2 250 X 1.7 X - Comparative Example 3 150 〇 1.5 X - Comparative Example 4 300 X 1.8 X - Comparative Example 5 200 X 1.7 X - Comparative Example 6 110 〇 1.4 XX Comparative Example 7 60 〇1.7 XX

[產業上之可利用性] 根據本發明，可提供一種能夠形成表面平滑性優異之 燒結層之無機微粒子分散糊。 【圖式簡單說明】 無 【主要元件符號說明】 無 32[Industrial Applicability] According to the present invention, it is possible to provide an inorganic fine particle-dispersed paste capable of forming a sintered layer excellent in surface smoothness. [Simple description of the diagram] None [Key component symbol description] None 32

Claims (1)

201107389 七、申請專利範圍： 1.一種無機微粒子分散糊，其含有選自由乙基纖維素、 (甲基）丙烯酸樹脂及聚乙稀縮輕樹脂所組成之群中的至少 一種、有機化合物、無機微粒子以及有機溶劑，其特徵在 於： 個以上之羥基’且於常溫下為固 該有機化合物具有 體’沸點低於30(TC。 Μ 粒 2.如申請專利範圍第 機微粒子為選自由無錯 子所組成之群中的至少 1項之無機微粒子分散糊，其中， 玻璃微粒子、陶瓷微粒子及鋁微 一種0 3·一種玻璃介電體，其特徵在於·· 其係使用申請專利範圍第 糊所製造。 或2項之無機微粒子分散 4· 一種陶瓷生片，其特徵在於·· 項之無機微粒子分散 其係使用申請專利範圍第1或2 糊所製造。 ’其特徵在於： 圍第1或2項之無機 其特徵在於： 5. —種太陽電池單元 其係使用申請專利範 糊所製造。 6. —種平板顯示器， 其係使用申請專利範圍第 糊所製造❶ 微粒子分散 1或2項之無機微粒子分散 八、圖式： (無） S 33201107389 VII. Patent application scope: 1. An inorganic fine particle dispersion paste containing at least one selected from the group consisting of ethyl cellulose, (meth)acrylic resin and polyethylene thin resin, organic compound, inorganic The microparticles and the organic solvent are characterized in that: more than one hydroxyl group' and solid at normal temperature, the organic compound has a body 'boiling point lower than 30 (TC. Μ granule 2. As claimed in the patent scope, the granule is selected from the erroneous An inorganic fine particle-dispersed paste of at least one of the group consisting of glass fine particles, ceramic fine particles, and aluminum micro--a glass dielectric body, which is characterized in that it is manufactured using the patent application No. Or two inorganic fine particle dispersions 4. A ceramic green sheet characterized in that the inorganic fine particle dispersion of the item is produced by using the first or second paste of the patent application scope. 'It is characterized by: Section 1 or 2 Inorganic is characterized by: 5. A solar cell unit is manufactured using a patent application. 6. A flat panel display, Patent application range of the system using the fine particle paste produced ❶ 1 or dispersing inorganic fine particles 2 disperse eight, FIG formula: (None) S 33
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