200904885 九、發明說明： 【發明所屬之技術領域】 本發明係關於一種含有聚乙烯縮經之樹脂，其於例如 用作為陶瓷生胚片之黏合劑時，可獲得一種具有充分之可 撓性、且即使薄膜化亦難以破損之陶瓷生胚片。又，本發 明係關於一種使用該含有聚乙稀縮醛之樹脂之聚乙烯縮駿 樹脂組成物、陶瓷漿料、陶瓷糊、陶瓷生胚片、導電糊及 汽車用夾層玻璃中間膜。 【先前技術】 如專利文獻1或專利文獻2中所揭示’積層陶瓷電容 器等積層型電子零件通常係經由以下步驟而製造。 首先，添加塑化劑、分散劑等至將聚乙烯丁醛樹脂或 聚（甲基）丙烯酸酯系樹脂等黏合劑樹脂溶解於有機溶劑中 而成之溶液中後，添加陶瓷原料粉末，藉由球磨機等而均 勻混合，脫泡後，獲得具有—絲度之陶究漿料組成物。 使用刮刀、逆輥塗佈機等，將所得之陶莞漿料組成物於缓 脫模處理過之聚對苯二甲酸乙m sus板（補鋼板） 等支持體面上流延成型’再藉由加熱等使有機溶劑等揮發 成分館去後’自支持體上剝離而獲得陶究生胚片。 ^繼而，經由下述步驟而獲得積層陶竞電容器：將於所 侍之陶瓷生胚片上以網版印刷等塗佈作為内部電極之 糊所製成之物交替重疊複數片，實施加熱壓 :而::將;積層體中所包含之黏合劑樹脂成分等進= 解而去除之處理，即所田妝μ 卩所明脫脂處理後，於進行燒成所獲得 200904885 之陶竟燒成物的端面上燒結外部電極。 ，年來，伴隨積層陶瓷電容器之高電容化 片之潯臈化不斷推進，例如，專利文㉟3中揭示有萨 用聚合度4副〜2彻之聚乙稀祕樹脂，來製㈣ 5 以下之陶瓷生胚片的方法。 又為 之薄膜化進一步進展，則對於先 ，存在自支持體上剝離時會導致 然而’若陶瓷生胚片 月'J之t乙稀縮醒·樹脂而言 陶瓷生胚片破損等問題。 因此，為了因應伴隨近年來積層陶瓷電容器之高電容 化的陶瓷生胚片之薄膜化，需要即使在薄膜化時亦可獲得 難以破裂之陶瓷生胚片的黏合劑。 【專利文獻1】曰本專利特公平3_35762號公報 【專利文獻2】曰本專利特公平4_49766號公報 【專利文獻3】曰本專利第3193〇22號公報 【發明内容】 本發明鑒於上述現狀而目的在於提供一種含有聚乙烯 縮醛之樹脂，其於例如用作為陶瓷生胚片之黏合劑時，可 獲得一種具有充分之可撓性、且即使薄膜化亦難以破損之 陶瓷生胚片。又，本發明之目的在於提供一種使用該含有 聚乙烯縮醛之樹脂之聚乙烯縮醛樹脂組成物、陶瓷漿料、 陶瓷糊、陶瓷生胚片、導電糊及汽車用夾層玻璃中間膜。 本發明係一種含有聚乙烯縮醛之樹脂，其含有由聚乙 烯縮搭樹脂所構成之成分A、及由與上述成分a非相容相 溶之樹脂所構成之成分B含有聚乙烯縮搭之樹脂，且由上 200904885 所構成之相、與由上述成分8所構成之相形成海 以下’詳細說明本發明。 本發明者等人專心研究之結果發 谢护娇拔山 竹田聚乙稀縮醛 1月曰所構成之成分A、及由與上述成分A非相容相溶之樹 月曰所構成之成分B形成海島結構的含有 :作為陶宽生胚片等之黏合劑時，所得之陶曼生胚= 有適度之可撓性者，且即传策 「使潯膜化時亦難以產生破裂等破 損，從而完成本發明。 本發明之含有聚乙稀縮酸之樹脂，係包含由聚 酸樹脂所構成之成分A „ 縮 請成之成刀A、及由與上述成分A非相容 樹脂所構成之成分B，且由f·士、八Λ 、.、 且由上述成为Α所構成之相、與由 上述成分B所構成之相係形成海島結構。 藉由具有上述結構，例如可㈣達成機械強度之提高、 及可撓性之賦予等性能。 本發明中，所謂海島4士 ★甚，及& i 月母馬，，、。構，係指由一種成分（島成分 所構成之相分散於由另一種八 種成刀（海成分）所構成之相中的 結構。再者，本發明中 … 字由上述島成分所構成之相的分 散徑為0 _ 0 7 # m以上之愔开；艋全「 义If形％作「具有海島結構」。若由 上述島成分所構成之相的分勒 刀敢k未滿〇 · 〇 7 # m ’則強烈地 表現出海成分之特性，島此 島成分之特性並未充分發揮。 又’本發明中，可為忐八 J馬成刀A為島成分、成分B為海成 分，亦可為成分B為島成分、成分A為海成分。 上述島成刀所構成之相的形狀並無特別限制，例如 200904885 可列舉.球狀、棒狀、板狀、薄膜狀、纖維狀、管狀等。 其中’較佳為球狀。 由上述島成分所構成之相的分散徑例如可藉由使用穿 透弋電子顯祕鏡（TEM，Transmission Electron Microscopy) 觀备樹知之剖面而求得。上述穿透式電子顯微鏡係藉由使 電子束穿透試料，獲得由試料中之原子散射、繞射之電子 乍為電子繞射圖案或穿透電子顯微鏡像，來觀察物質内部 結構的顯微鏡。 於本發明中，例如可利用以下方法來測定分散徑。 首先藉由使用切片機（microtome)進行切斷而製作剖 面試料後，使用穿透式電子顯微鏡（TEM)，以3〇〇〇倍對剖 面進行攝影。測定從所得之圖像可確認到之所有島成分所 構=之±相的直徑，將由島成分所構成之相的全部個數設為 八4 ^將包含80%之島成分所構成之相的直徑範圍作為 政仏再者，上述島成分所構成之相為球狀以外的形狀 日’’將長徑與短徑之平均值作為直徑。 作$構成上述成分A之聚乙烯縮醛樹脂，若為與成分 不相冷、且可與成分B組合形成海島結構之樹脂，則並 …、特別限制，可使用先前公知者。 作為構成上述成分B之樹脂，若為與成分A非相溶之 ^脂、且可與成分A組合形成海島結構之樹脂，則並無特 外限制’可為聚乙烯縮路樹脂’亦可為聚乙稀縮齡樹月旨以 之其他樹脂。本發明中’作為構成上述成分B之樹赌， 又佳為使用聚乙烯縮醛樹脂。 200904885 構成上述成分B之樹脂為聚乙烯縮醛樹脂以外之其他 樹脂時，作為上述其他樹脂，例如可列舉：乙基纖維素、 丙烯酸系樹脂、聚乙烯樹脂、聚丙烯樹脂、乙烯乙酸乙烯 西旨樹脂、聚乙烯醇樹脂、乙稀乙婦醇樹脂、紛樹脂、氣乙 烯樹脂、聚醯胺樹脂、環氧樹脂、矽樹脂、聚酯樹脂、胺 基樹脂、聚胺酯樹脂等。 於本發明之含有聚乙烯縮醛之樹脂中，上述成分A與 f 成分B之混合比較佳為以重量比表示為8: 2〜2: 8。上述 、 混合比在上述範圍外時，強烈地表現出混合比率較大之成 刀的特性，並未充分表現出混合比率較小之成分的特性〇 於不損及本發明之效果的範圍内’本發明之含有聚乙 稀縮醒之樹脂除了含有成分A及成分B以外，亦可包含其 他成分。作為上述其他成分，若為與上述成分A或成分B 非相溶之樹脂，則並無特別限制，例如可列舉：聚乙稀樹 脂、聚丙烯樹脂、乙烯乙酸乙烯酯樹脂、$乙烯醇樹脂、 ( 乙烯乙烯醇樹脂、酚樹脂、t乙烯樹脂、聚醯胺樹脂、環 氧樹脂、矽樹脂、聚酯樹脂、胺基樹脂、聚胺酯樹脂等。 其他態樣之本發明係—種含有聚乙烯縮醛之樹脂其 系將由皂化度不同之兩種以上的聚乙烯醇所構成之混合聚 乙烯醇加以縮醛化所製成者，且上述混合聚乙烯醇係由皂 化度為70莫耳％以上的聚乙烯醇所構成，將主要的兩種聚 乙烯醇中之一種聚乙烯酵的皂化度設為X莫耳％，且將另 一種聚乙烯醇的皂化度設為γ莫耳％時，X及Y具有下述（1) 式的關係，上述混合聚乙烯醇之主要兩種聚乙烯醇的混合 200904885 比以重量比表示為2: 8〜8: 2，且縮醛化度為4〇〜8〇莫耳 %。以下’將其他態樣之本發明的含有聚乙浠㈣之樹脂 亦稱作混合聚乙烯縮醛樹脂。 Ιχ~ ίο 上述混合聚乙烯醇係*皂化度不同之兩種以上的聚乙 C稀醇所構成者。如此使用將專化度不同之聚乙烯醇加以縮 醛化而得之混合聚乙烯縮醛樹脂，與使用皂化度相同之聚 乙稀醇之情形相比，可大幅改善作為薄膜時之可挽性、斷 裂伸長率。將上述皂化度不同之聚乙烤醇作為原料的混合 聚乙烯縮酿樹脂中，息化度高之成分與惠化度低之成分難 =相溶，故以 DSC(differential scanning calorimetry，差示 掃描量熱儀）測定玻璃轉移溫度（Tg)時，存在觀察到兩個Tg =情形。皂化度低之成分因玻璃轉移溫度低，故可撓性較 ( 咼，可藉由將該成分混合而大幅改善片材之可撓性、斷裂 伸長率。 上述混合聚乙烯醇於將主要的兩種聚乙烯醇中之一種 聚乙烯醇的皂化度設為X莫耳％，且將另一種聚乙烯醇的 Kb度設為丫莫耳％時’ XA γ具有上述⑴式的關係。 由於具有上述（1)式之關係，故Tg低之低專化成分與 T、g高之高皂化成分的差變得明顯，從而有效發揮Tg低之 成分賦予可撓性之效果。 再者，於本說明書中，所謂主要的兩種聚乙婦醇，係 10 200904885 指構成上述混合聚乙烯醇之皂化度不同的兩種以上之聚乙 烯醇中含量較多的兩種。 上述混合聚乙烯酵較佳為由皂化度為95莫耳。/〇以上之 聚乙烯醇、與皂化度為85莫耳％之聚乙烯醇構成。 皂化度為95莫耳％以上之聚乙烯醇經縮醛化的部分有 效地形成羥基之氫鍵，故片材之強度易於增強。又，皂化 度為85莫耳％以下之聚乙烯醇經縮醛化的部分由於殘存乙 醯基之影響而難以形成氫鍵，故片材易於成為可撓性。因 此，藉由將不同特性之聚乙烯縮醛樹脂混合，可獲得強度 高、可撓性亦優良之含有聚乙烯縮醛之樹脂。 上述混合聚乙烯醇之皂化度的下限為7〇莫耳％。若上 述混合聚乙烯醇之皂化度未滿70莫耳％，則因聚乙烯醇之 水/容性惡化而難以縮醛化’又，由於羥基量變少，故難以 充分地提高縮醛化度。上述混合聚乙烯醇之皂化度的較佳 下限為72莫耳％。 上述混合聚乙烯醇例如可藉由將乙烯酯與乙烯之共聚 物皂化而獲得。作為上述乙烯酯，例如可列舉：甲酸乙烯 酯、乙酸乙烯酯、丙酸乙烯酯、新戊酸乙烯酯等。其中， 就經濟性之觀點而言，乙酸乙烯酯較適合。 上述混合聚乙烯醇於不損及其他態樣之本發明效果的 範圍内，亦可為將乙烯性不飽和單體共聚合而得者。作為 上述乙烯性不飽和單體，例如可列舉：丙烯酸、甲基丙烯 酸、鄰苯二甲酸（酐）、馬來酸（酐）、衣康酸（酐）、丙烯腈曱 基丙烯腈、丙烯醯胺、曱基丙烯醯胺、三甲基、弘丙烯醯 200904885 胺-3-二甲基丙基）-氣化銨、丙烯醯胺_2_甲基丙磺酸、及其 鈉鹽、乙基乙烯基醚、丁基乙烯基醚、N_乙烯基吡咯烷酮、 氯乙烯、漠 ·乙烯、氟乙烯、偏二氯乙烯、偏二氟乙烯、四 氟乙烯、乙烯基磺酸鈉、烯丙基磺酸鈉等。又，亦可使用 在硫乙酸、巯基丙酸等硫醇化合物之存在下，將乙酸乙烯 醋等乙烯S旨系單體與乙稀共聚合，並將其4化所得之末端 聚乙稀醉。 f 上述混合聚乙烯醇亦可為將上述乙烯酯與〇_烯烴共聚 合而成之共聚物進行皂化所得者。又，進而亦可使上述乙 ，性不飽和單體共聚合，而製成含有來自於乙稀性不飽和 單體成分的聚乙烯醇。X，亦可使用藉由在硫乙酸、酼臭 丙酸等硫醇化合物之存在下，將乙酸乙婦醋等乙稀酿二 體與f烯煙共聚合，並將其皂化所獲得之末端聚乙稀醇。 上述α _烯烴並無特別限制，例如可列舉 烯、異丙烯'丁烯、異丁烯、戊烯、己 基乙烯、環己基丙烯等。 :甲烯、乙烯、丙 稀、環己烯、環己 上述混合聚乙烯醇之聚合度的較佳下限為5〇〇,較佳 上限為述混合聚乙稀醇之聚合度未滿5〇〇,則 無法獲得具有；1夠黏度之混合聚乙烯_樹脂，薄膜化時 的陶竟生胚片之強度並不足。若上述混合聚乙浠醇之聚合 度超過3_ ’則對水之溶解性降低，或水溶液之黏度過於 增…難以縮酸化…溶解於有機溶劑時之黏度過於 増局，故導致陶聽末之分散性及陶究生胚片用陶Μ料 12 200904885 再者’上述混合聚乙稀縮醛樹脂之聚合度可藉由使用 原料即混合聚乙烯醇之聚合度來求得。又，上述混合聚乙 烯醇之聚合度係根據各個聚乙婦醇之聚合度的平均值來求 得。 上述混合聚乙烯醇之主要兩種聚乙烯醇的聚合度之差 (以下，亦僅稱作混合聚乙烯醇之聚合度差）之較佳上限為 3000。若上述混合聚乙烯醇之聚合度的差超過3〇〇〇，則主 要的兩種聚乙烯醇相溶而無法發揮賦予可撓性之效果。再 者’上述混合聚乙烯醇之聚合度差係指聚合度差之絕對 述混合聚乙烯醇之聚合度差為2000 以下時，將主要 將主要的兩200904885 IX. OBJECTS OF THE INVENTION: TECHNICAL FIELD The present invention relates to a resin containing polyethylene shrinkage, which can be obtained with sufficient flexibility when used, for example, as a binder for ceramic green sheets. And the ceramic green sheets which are difficult to break even if they are thinned. Further, the present invention relates to a polyethylene shrink resin composition using the resin containing a polyacetal acetal, a ceramic slurry, a ceramic paste, a ceramic green sheet, a conductive paste, and an interlayer film for a laminated glass for automobiles. [Prior Art] A laminated electronic component such as a laminated ceramic capacitor disclosed in Patent Document 1 or Patent Document 2 is usually manufactured through the following steps. First, a plasticizer, a dispersant, or the like is added to a solution obtained by dissolving a binder resin such as a polyvinyl butyral resin or a poly(meth)acrylate resin in an organic solvent, and then a ceramic raw material powder is added. The ball mill or the like is uniformly mixed, and after defoaming, a ceramic composition having a silkiness is obtained. Using a doctor blade, a reverse roll coater, or the like, the obtained pottery paste composition is cast-molded on a support surface such as a polyethylene terephthalate (supplemented steel plate) which has been subjected to a slow release treatment, and is heated by heating. After the volatile components such as organic solvents are removed, they are peeled off from the support to obtain a ceramic tile. Then, a laminated ceramic capacitor is obtained by the following steps: a plurality of sheets are alternately stacked on a ceramic green sheet to be coated with a paste as an internal electrode by screen printing or the like, and a heating pressure is applied: :: The treatment of the binder resin component contained in the laminate, such as the removal of the resin, and the removal of the surface of the ceramic composition obtained by the decontamination treatment of the product The external electrode is sintered. In the past years, the development of high-capacitance sheets with laminated ceramic capacitors has continued to advance. For example, Patent Document 353 discloses that ceramics with a degree of polymerization of 4 pairs to 2 times of polyethylene are used to make ceramics of (4) 5 or less. The method of birthing the embryo. Further, in order to further advance the film formation, there is a problem that the ceramic green sheet is damaged when the film is peeled off from the support, but the ceramic green sheet is damaged. Therefore, in order to thin the ceramic green sheets which have been highly capacitive with the multilayer ceramic capacitors in recent years, it is necessary to obtain a binder of ceramic green sheets which are difficult to be broken even when thinned. [Patent Document 1] Japanese Patent Application Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. It is an object of the invention to provide a resin containing a polyvinyl acetal which, when used, for example, as a binder for a ceramic green sheet, can obtain a ceramic green sheet which has sufficient flexibility and is hard to be broken even if it is thinned. Further, an object of the present invention is to provide a polyvinyl acetal resin composition, a ceramic slurry, a ceramic paste, a ceramic green sheet, a conductive paste, and a laminated glass interlayer film for automobiles using the polyethylene acetal-containing resin. The present invention relates to a resin containing a polyvinyl acetal, which comprises a component A composed of a polyethylene shrink resin and a component B composed of a resin which is incompatible with the component a, and contains a polyethylene shrinkage. The present invention will be described in detail with respect to the resin, and the phase composed of the above-mentioned 200,904,885 and the phase composed of the above-mentioned component 8 are formed below the sea. As a result of intensive research by the inventors of the present invention, it is believed that the component A composed of the polyacetal acetal acetal in January, and the component B composed of the tree scorpion which is incompatible with the above component A In the case of forming a sea-island structure, the obtained Tauman green embryos have a moderate flexibility, and it is said that it is difficult to cause breakage such as cracking when the film is formed, thereby completing the present invention. The polyacetic acid-containing resin of the present invention comprises a component A formed by a polyacid resin, a component A formed by shrinkage, and a component B composed of a non-compatible resin with the component A, and The sea-island structure is formed by the phase formed by the above-mentioned component B and the phase formed by the above-mentioned component B. By having the above configuration, for example, (4) improvement in mechanical strength and impartability of flexibility can be achieved. In the present invention, the so-called island 4, ★, and & i month mare,,,. The structure is a structure in which one phase (the phase composed of the island component is dispersed in a phase composed of another eight kinds of knives (sea components). Further, in the present invention, the word is composed of the above-mentioned island components. The dispersion of the phase is 0 _ 0 7 # m or more; 艋 「 「 If 形 形 % 作 具有 。 。 。 。 。 。 。 。 。 。 。 。 。 若 。 若 若 若 若 若 若 若 若 若 若 若 若 若 若 若 若 若 若 若 若 若7 # m 'strongly expresses the characteristics of the sea component, and the characteristics of the island's ingredients are not fully utilized. In the present invention, it can be that the eight horses are the island component and the component B is the sea component. The component B may be an island component, and the component A may be a sea component. The shape of the phase formed by the island forming blade is not particularly limited. For example, 200904885 may be exemplified by a spherical shape, a rod shape, a plate shape, a film shape, a fiber shape, or a tubular shape. In the above, 'the shape is preferably spherical. The dispersion diameter of the phase composed of the above-mentioned island component can be obtained, for example, by observing the cross section of the tree using a transmission electron microscopy (TEM). Transmissive electron microscope The sample is permeable to obtain a microscope which observes the internal structure of the substance by scattering the atoms in the sample, diffracting the electron 乍 into an electron diffraction pattern, or penetrating an electron microscope image. In the present invention, for example, the following method can be used to determine the dispersion diameter. First, a cross-section sample was prepared by cutting with a microtome, and then a cross-section electron microscope (TEM) was used to photograph the cross-section at 3 times. The measurement was confirmed from the obtained image. The diameter of the ± phase of all the island components = the total number of phases formed by the island components is 八 4 ^ The diameter range of the phase composed of 80% of the island components is taken as the political The phase formed by the component is a spherical shape other than the average diameter of the major axis and the minor axis. The polyvinyl acetal resin constituting the component A is not phase-cooled with the component. When the component B is combined to form a resin having a sea-island structure, it is particularly limited, and a conventionally known one can be used. The resin constituting the component B is a compound which is incompatible with the component A and can be combined with the component A. The resin of the island-in-the-sea structure is not particularly limited to 'can be a polyethylene shrinkage resin' or other resin which is used for the purpose of the polystyrene tree. In the present invention, 'as a tree gambling constituting the above component B, In addition, when the resin constituting the component B is a resin other than the polyvinyl acetal resin, examples of the other resin include ethyl cellulose, acrylic resin, and polyethylene resin. , polypropylene resin, ethylene vinyl acetate resin, polyvinyl alcohol resin, ethylene glycol alcohol resin, resin, gas vinyl resin, polyamide resin, epoxy resin, enamel resin, polyester resin, amine resin A polyurethane resin, etc. In the polyvinyl acetal-containing resin of the present invention, the mixing of the above component A and the f component B is preferably 8: 2 to 2: 8 by weight. When the mixing ratio is outside the above range, the characteristics of the forming tool having a large mixing ratio are strongly exhibited, and the characteristics of the component having a small mixing ratio are not sufficiently exhibited in the range which does not impair the effects of the present invention. The resin containing the polyethylene acetal of the present invention may contain other components in addition to the component A and the component B. The other component is not particularly limited as long as it is a resin which is incompatible with the component A or the component B, and examples thereof include a polyethylene resin, a polypropylene resin, an ethylene vinyl acetate resin, and a vinyl alcohol resin. (ethylene vinyl alcohol resin, phenol resin, t vinyl resin, polyamide resin, epoxy resin, enamel resin, polyester resin, amine resin, polyurethane resin, etc. The other aspect of the invention is a type containing polyethylene shrinkage The aldehyde resin is obtained by acetalizing a mixed polyvinyl alcohol composed of two or more kinds of polyvinyl alcohols having different degrees of saponification, and the mixed polyvinyl alcohol has a degree of saponification of 70 mol% or more. It is composed of polyvinyl alcohol, and the degree of saponification of one of the two main polyvinyl alcohols is set to X mole %, and when the degree of saponification of the other polyvinyl alcohol is γ mole %, X and Y has the relationship of the following formula (1), and the mixture of the two main polyvinyl alcohols of the above-mentioned mixed polyvinyl alcohol is 200904885, which is represented by a weight ratio of 2:8 to 8:2, and the degree of acetalization is 4〇8. 〇莫耳%. The following 'will be the other aspects of this The resin containing polyethylene (IV) according to the invention is also referred to as a mixed polyvinyl acetal resin. Ιχ~ ίο The above-mentioned mixed polyvinyl alcohol system* is composed of two or more kinds of polyethylene glycols having different degrees of saponification. The mixed polyvinyl acetal resin obtained by acetalization of polyvinyl alcohol having different degrees of chemistry can greatly improve the pullability and elongation at break when used as a film, compared with the case of using a polyethylene glycol having the same degree of saponification. Among the mixed polyethylene condensed resins in which the above-mentioned polyethylenyl alcohol having a different degree of saponification is used as a raw material, a component having a high degree of recombination is difficult to be compatible with a component having a low degree of favorability, so DSC (differential scanning calorimetry, differential) Scanning calorimeter) When measuring the glass transition temperature (Tg), two Tg = cases were observed. The component with a low degree of saponification has a lower flexibility due to the lower glass transition temperature ( 咼, by mixing the components The flexibility and elongation at break of the sheet are greatly improved. The above-mentioned mixed polyvinyl alcohol has a degree of saponification of one of the two main polyvinyl alcohols as X mole %, and another polyvinyl alcohol. Kb degree is set to In the case of Mohr%, XA γ has the relationship of the above formula (1). Since the relationship of the above formula (1) is obtained, the difference between the low specific component of Tg and the high saponification component of T and g is high, and the difference is effectively exhibited. The component having a low Tg imparts flexibility. Further, in the present specification, the main two types of polyglycolic alcohol are 10 200904885, which means two or more kinds of polyethylenes having different degrees of saponification of the mixed polyvinyl alcohol. The mixed polyvinyl alcohol is preferably composed of a polyvinyl alcohol having a degree of saponification of 95 mol/min or more and a polyvinyl alcohol having a degree of saponification of 85 mol%. The degree of saponification is The acetalized portion of 95 mol% or more of the polyvinyl alcohol is effective to form a hydrogen bond of a hydroxyl group, so that the strength of the sheet is easily enhanced. Further, in the acetalized portion of the polyvinyl alcohol having a degree of saponification of 85 mol% or less, it is difficult to form a hydrogen bond due to the influence of the residual ethyl ketone group, so that the sheet tends to be flexible. Therefore, a polyethylene acetal-containing resin having high strength and excellent flexibility can be obtained by mixing polyvinyl acetal resins having different characteristics. The lower limit of the degree of saponification of the above mixed polyvinyl alcohol is 7 〇 mol%. When the degree of saponification of the above-mentioned mixed polyvinyl alcohol is less than 70 mol%, it is difficult to acetalize due to deterioration of water/capacity of polyvinyl alcohol. Further, since the amount of hydroxyl groups is small, it is difficult to sufficiently increase the degree of acetalization. A preferred lower limit of the degree of saponification of the above mixed polyvinyl alcohol is 72 mol%. The above mixed polyvinyl alcohol can be obtained, for example, by saponifying a copolymer of vinyl ester and ethylene. Examples of the vinyl esters include vinyl formate, vinyl acetate, vinyl propionate, and vinyl pivalate. Among them, vinyl acetate is suitable from the viewpoint of economy. The above-mentioned mixed polyvinyl alcohol may be obtained by copolymerizing an ethylenically unsaturated monomer insofar as it does not impair the effects of the present invention in other aspects. Examples of the ethylenically unsaturated monomer include acrylic acid, methacrylic acid, phthalic acid (anhydride), maleic acid (anhydride), itaconic acid (anhydride), acrylonitrile acrylonitrile, and acrylonitrile. Amine, mercapto acrylamide, trimethyl, hydrazine 200904885 amine-3-dimethylpropyl)-aluminum hydride, acrylamide 2_methylpropane sulfonic acid, and its sodium salt, ethyl Vinyl ether, butyl vinyl ether, N_vinyl pyrrolidone, vinyl chloride, desert ethylene, vinyl fluoride, vinylidene chloride, vinylidene fluoride, tetrafluoroethylene, sodium vinyl sulfonate, allyl sulfonate Sodium and so on. Further, in the presence of a thiol compound such as thioacetic acid or mercaptopropionic acid, an ethylene S-type monomer such as vinyl acetate or the like may be copolymerized with ethylene, and the terminal obtained by the crystallization may be intoxicated. f The above-mentioned mixed polyvinyl alcohol may be obtained by saponifying a copolymer obtained by copolymerizing the above vinyl ester with a ruthenium-olefin. Further, the ethylenically unsaturated monomer may be copolymerized to form a polyvinyl alcohol containing a monomer component derived from an ethylenically unsaturated. X. It is also possible to use a terminal polymerization obtained by copolymerizing an ethylene diacetate such as ethyl vinegar and f-ene in the presence of a thiol compound such as sulfuric acid or odorous propionic acid, and saponifying it. Ethylene glycol. The α-olefin is not particularly limited, and examples thereof include an olefin, isopropylene 'butene, isobutylene, pentene, hexylethylene, and cyclohexylpropene. The preferred lower limit of the degree of polymerization of the mixed polyvinyl alcohol of the above-mentioned vinylene, ethylene, propylene, cyclohexene and cyclohexene is 5 Å, and the upper limit is that the polymerization degree of the mixed polyethylene glycol is less than 5 〇〇. , it is impossible to obtain a mixed polyethylene_resin having a viscosity of 1; the strength of the ceramic green sheet at the time of film formation is insufficient. If the degree of polymerization of the above mixed polyethylene glycol exceeds 3 _ ', the solubility in water is lowered, or the viscosity of the aqueous solution is too large... It is difficult to reduce the acidity... The viscosity in the organic solvent is too low, which leads to the dispersion of the terracotta Sex and ceramics for ceramic sheets 12 200904885 Furthermore, the degree of polymerization of the above-mentioned mixed polyacetal acetal resin can be determined by using the polymerization degree of the raw material, that is, the mixed polyvinyl alcohol. Further, the degree of polymerization of the above mixed polyvinyl alcohol is determined from the average value of the degree of polymerization of each of the polyethylols. The upper limit of the degree of polymerization of the main two kinds of polyvinyl alcohols of the above-mentioned mixed polyvinyl alcohol (hereinafter, simply referred to as the difference in polymerization degree of the mixed polyvinyl alcohol) is preferably 3,000. When the difference in polymerization degree of the above-mentioned mixed polyvinyl alcohol exceeds 3 Å, the two main polyvinyl alcohols are compatible and the effect of imparting flexibility cannot be exhibited. Further, the difference in polymerization degree of the above-mentioned mixed polyvinyl alcohol means that the difference in polymerization degree is absolute. When the difference in polymerization degree of the mixed polyvinyl alcohol is 2,000 or less, the main two will be mainly
佳為具有下述（2)式之關係。 為了更有效地發揮其他態樣之本發明的優良效果，上 30= IX- Y|^ 12 若 ΙΥ — VI 丄·^ “Jia has the relationship of the following formula (2). In order to more effectively exert the excellent effects of the present invention in other aspects, upper 30= IX- Y|^ 12 if ΙΥ — VI 丄·^ “
1700、皂化度為95莫耳°/。之聚 南’ 溶解‘ 稀縮i 1 13 200904885 乙烯醇時，若將其與人 之聚乙烯醇之混合聚：：1000、皂化度為80莫耳％ 他態樣之本發明的效果，/;；^化，雖可充分獲得其 画、皂化度S 85莫耳％之—$在即使將其與聚合度為 縮搭化亦無法獲得充分效果之^Γ。醇u聚乙烯醇加以 …::情:合醇之聚合度差大於测、且為 f Π::::…C = = : = X 、）時又及¥較佳為具有下述(3)式之關係。 3〇g jx— Y|g 20 (3) _丨Y丨小於2〇，則所混合之聚乙烯醇的相溶性掸 南，，難以發揮出賦予可撓性之效果。 曰 A 丨大於3 〇，則皂化度低之聚乙稀醇對水的溶解 t降低’故難以進行縮醛化反應，或所得之混合聚乙烯縮 醛樹脂對溶劑之溶解性降低。 、’ 例如’使用聚合度為3300、皂化度為99莫耳〇/。之聚 乙婦醇時，右將其與聚合度為1咖 ' 息化度為75莫耳％ 之聚乙烯醇的混合聚乙烯醇加以縮醛化，雖可充分獲得其1700, the degree of saponification is 95 moles /. Poly South 'Soluble' thinning i 1 13 200904885 When vinyl alcohol is mixed with human polyvinyl alcohol: 1000, the degree of saponification is 80 mol%. The effect of the present invention is /; ^^, although it can be fully obtained, the degree of saponification, S 85 mol% - $ even if it is combined with the degree of polymerization can not achieve sufficient results. Alcohol u polyvinyl alcohol is added to:::: The difference in polymerization degree of the alcohol is greater than the measured value, and f Π::::...C = = : = X , ) and ¥ is preferably as follows (3) Relationship. 3〇g jx— Y|g 20 (3) When _丨Y丨 is less than 2〇, the compatibility of the mixed polyvinyl alcohol is too large, and it is difficult to exert the effect of imparting flexibility. When 曰 A 丨 is more than 3 〇, the dissolution of water by the polyethylene having a low degree of saponification is lowered, so that it is difficult to carry out the acetalization reaction, or the solubility of the obtained mixed polyvinyl acetal resin in the solvent is lowered. For example, the degree of polymerization is 3,300 and the degree of saponification is 99 moles/. In the case of polyglycol, the mixture is acetalized with a polyvinyl alcohol having a degree of polymerization of 75 mol% of polyvinyl alcohol, although it can be sufficiently obtained.
他態樣之本發明& < $ y ^ ^ L 知月的效果，但亦存在即使將其與聚合度為 1000皂化度為80莫耳❶/〇之聚乙烯醇的混合聚乙烯醇加以 縮醛化亦無法獲得充分效果之情形。 進而’於所混合之聚乙烯醇之聚合度差大於2500的情 200904885 $夺將主要的兩種聚乙烯醇中之一種聚乙烯醇之皂化度 。:士（莫耳/〇)，且將另一種聚乙烯醇之皂化度設為γ(莫 耳/〇)蚪，X及Y較佳為具有下述（4)式之關係。 (4) 30> IX- Υ|^ 25 古^ 丨！於2 5，則所混合之聚乙烯醇的相溶性增 咼，故難以發揮出賦予可撓性之效果。 1 Υ|大於3G ’則皂化度低之聚乙烯醇對水的溶解 =對！Γ進行縮'化反應，或所得之混合聚乙稀縮 酪树知對溶劑之溶解性降低。 =，使用聚合度為3·、4化度為99莫耳％之聚 :=，若將其與聚合度為…化度為73莫耳%之 離樣之本:混合聚乙稀醇加以縮盤化，雖可充分獲得其他 :化声tl:效果，但亦存在即使將其與聚合度為5。〇、 亦心二:充：之聚乙烯醇的混合聚乙婦醇加_化 …、沄獲传充分效果之情形。 之混ίΓΤ稀醇中專化度不同的主要兩種聚乙稀醇 之混合比’以重量比表示為料 述範圍之外時（例如，重量1Q〜、8.2。上述混合比在上 相溶性增高，故難以發揮賦予了二，上述混合聚乙婦醇之 重量比為一:2，：=挽性之效果。再者，所謂 專化度低之聚乙稀醇的重量歹舉4化度高之聚乙烯醇與 上述混合聚乙稀醇亦可為=〜8:2之情形等。 為將聚合度及皂化度不同之3 15 200904885 種以上的聚乙稀醇混合而葡出本 1卿扣《向袈成者。其中，該情形時較佳為 滿足上述聚合度及專化度之範圍。 例如，可列舉將聚合度為1700、卷化度為99莫耳％ 之聚乙烯醇，聚合度為1700、4化度為95莫耳％之聚乙 稀醇，及聚合度為1700、專化度為75莫耳％之聚乙稀醇， 以1 . 1 . 1之重量比混合所得之混合聚乙婦醇等。 上述縮盤化t方法並無特別P艮制，τ使用先前公知之 方法，例如可列舉於鹽酸等酸觸媒之存在Τ，添力σ 丁搭及/ 或乙酸於上述此合聚乙稀醇之水溶液中之方法等。 上述縮醛化中，較佳為使用丁醛及/或乙醛。藉此，可 獲得溶劑溶解性、可撓性、片材強度之平衡優良的混合聚 乙烯縮醛樹脂。 藉由將上述混合聚乙烯醇加以縮醛化，可獲得混合聚 乙烯縮醛樹脂。 上述混合聚乙烯縮醛樹脂之縮醛化度的下限為40莫耳 /〇，上限為80莫耳％。若上述混合聚乙烯縮醛樹脂之縮醛 化度未滿40莫耳％，則所得之混合聚乙烯縮醛樹脂不溶於 有機溶劑中，從而對陶瓷生胚片用陶瓷漿料之製作造成阻 礙。若上述混合聚乙烯縮醛樹脂之縮醛化度超過莫耳 /〇，則殘存羥基減少，所得之混合聚乙烯縮醛樹脂之強韌 文損。上述混合聚乙歸縮駿樹脂之縮酸化度的較佳下限 為55莫耳％，較佳上限為7〇莫耳％。 再者，本說明書中，所謂縮醛化度，係指混合聚乙浠 醇之羥基數中經縮醛化之羥基數的比例，作為縮醛化度之 200904885 S十算方法，由於混合聚乙烯縮醛樹脂之縮醛基係由2個羥 基進行縮醛化而形成，故採用數算經縮醛化之2個羥基的 方法來算出縮醛化度之莫耳％。 上述混合聚乙烯縮醛樹脂可藉由將由皂化度不同之兩 種以上的聚乙烯醇所構成之混合聚乙_溶解後，進行縮 搭化而獲得’亦可藉由利用通常之方法製造皂化度不同之 兩種以上的聚乙烯祕樹脂後，加以混合而製成混合聚乙 烯縮醛樹脂。其中，該等中前者方法較合適。 本發明之含有聚乙烯縮醛之樹脂可藉由例如混合有機 =來使用作為聚乙稀祕樹脂M成物。上述聚乙稀縮搭 秘脂組成物亦為本發明之一。 ^^有機溶劑並無特別限制，例如可列舉：銅類、醇 類、方香族烴類、酯類等有機溶劑。 作2述酮類之有機溶劑’例如可歹W、甲乙 —丙酮、二異丁酮等。 ^為上述醇類之有機溶劑’例如 異丙醇、丁醇等。 T衧Q吁 二甲述芳香族_之有機溶劑，例如可列舉··甲苯、 · ·、、述酯類之有機溶劑，例如可列棗. 丙酸乙酿、丙酸丁 gt J如了列舉·丙酸甲s曰、 戊酸甲醋、戊酸I:、丁酸甲醋、丁酸乙醋、丁酸丁醋、 己酸丁顆、… 戊酸丁醋、己酸甲醋、己酸乙醋、 乙駚2_乙基己酯、丁酸2_乙其p 又，作為上述 土己S0等〇 有機溶劑’例如亦可使用甲基溶纖劑、 17 200904885 乙基溶纖劑、丁基溶纖劑、α_松脂醇、丁基溶纖劑乙酸醋、 丁基卡必醇乙酸酯等。 該等有機溶劑可單獨使用，亦可併用兩種以上。 本發明之聚乙烯縮醛樹脂組成物中之含有聚乙烯縮醛 之樹脂的含量較佳下限為1重量％，較佳上限為50重量％。 右上述含有聚乙烯縮醛之樹脂的含量未滿1重量％，則成 膜，能差，若上述含有聚乙烯縮醛之樹脂之含量超過50 f重量％，則黏度高，故操作性不良。上述含有聚乙稀縮路 。之樹脂之含量的更佳下限為3重量％，更佳上限為33重量 %。上述含有聚乙烯縮醛之樹脂的含量的進一步較佳下限 為5重量％，進一步較佳上限為2〇重量％。 本發明之聚乙烯縮醛樹脂組成物藉由例如使陶瓷粉 末、導電粉末等無機粉末分散，而可使用作為良好地分散 有無機粉末之漿料組成物、塗佈糊。 ^用作為上述漿料組成物之際，使用陶瓷粉末作為無機 泰末a寺，上述漿料組成物可用作為陶:光漿料。所得之陶瓷 装料可適宜用作為積層陶竟電容器之陶竟生胚片的材料。 上述陶瓷漿料亦為本發明之一。 又，藉由使用本發明之陶瓷漿料，可製作即使厚度為 从m以下呀，自支持體上剝離時亦難以破損之陶瓷生胚 片。 上述陶瓷生胚片亦為本發明之一。 用作為上述塗佈糊之際，使用陶瓷粉末作為無機粉末 寺上述塗佈糊可用作為陶瓷糊。所得之陶瓷糊亦可適宜 18 200904885 用作為下述陶究糊，該陶咨她产告丨 際，為了埴輔道贵 糊在製這積層陶瓷電容器之 *為了填補導電糊進行網版印刷後 佈於未形成導電層之部分。上述陶究糊亦為本發明之—係塗 :述陶竞粉末並無特別限制，例如可列舉：氧化銘、 _ ,、 *化鈦、戰化鋅、鈦酸铜、氧化鎂、賽 隆（Sialon)、尖晶石、莫來石 資 &切、氮切、氮化鋁等。 使用導電粉末作為上述無機粉 作為導電糊。由所得之導電糊心Ή述塗佈糊可用 于之導電糊形成之導電層難以破損，可 k宜用於積層陶瓷電容器之製造中。 〇 上述導電糊亦為本發明之 則 ,作為上述導電粉末，若為表現出充分之導電性者， 並無特別限制’例如可列舉由鎳、鈀、鉑、金、銀、銅 等之σ金等所構成之粉末。該等導電粉末可單獨使用 亦可併用兩種以上。 ▲本發月之陶竟製料、陶竟糊及導電糊於不損及本發明 之效果的範圍内’亦可適宜添加塑化劑、潤滑劑、分 抗靜電劑等。 將本發明之聚乙烯縮醛樹脂組成物用於汽車中所使用 2夾層破璃用的中間膜時，可獲得玻璃破損時亦難以斷 d並且拉伸步驟中破損較少，生產效率優良之夾層玻璃 用中間膜。上述汽車用夾層玻璃中間膜亦為本發明之一。 藉由本發明，可提供一種含有聚乙烯縮醛之樹脂，其 於用作為例如陶瓷生胚片之黏合劑時，可獲得一種具有充 刀可撓性、且即使薄膜化時亦難以破損之陶瓷生胚片。 200904885 尤其於使用本發明之含有聚乙稀縮搭之樹脂時，可大 幅減少添加於陶甍生胚片中之塑化劑的添加量。其結果 為，不僅可防止陶竟生胚片之破損等，亦可有效防止由塑 化劑所引起之變形或塑化劑之滲出。 進而’藉由使用該聚乙烯縮醛樹脂組成物，可提供具 有優良性能之聚乙稀縮㈣脂組成物、陶U料、陶竟糊: 陶瓷生胚片、_電糊及汽車用夾層玻璃中間膜。 【實施方式】 以下，列舉實施例來進一步詳細說明本發明，然而本 發明並非僅限於該等實施例。 (實施例1) 將130 g之聚合度為17〇〇、皂化度為8〇莫耳％之聚乙 稀醇及130 g之聚合度為17〇〇、息化度為99莫耳％之聚 乙烯醇添加至3000 g之純水中，於90°C之溫度下攪拌約2 小時，使其溶解。將該溶液冷卻至4〇〇c ,向其中添加8 之濃度為35重量％之鹽酸與125 g之正丁醛，將液體溫度 降低為1 0 C，保持該溫度進行縮醛化反應，並使反應生成 物析出。其後’ α 3小時將液體溫度保持為40。。，使反應 結束，利用通常之方法經由中和、水洗及乾燥，而獲得聚 乙烯縮醛樹脂之白色粉末。將所得之聚乙烯縮醛樹脂溶解 於DMS〇-d6(二甲基亞颯）中，使用13C-NMR(核磁共振光譜） 測定丁路化度，丁醛化度為56莫耳％。 將10重量份之所得之聚乙烯縮醛樹脂添加於45重量 伤之甲笨與4 5重量份之乙醇的混合溶劑中，進行授摔容 20 200904885 解以乾燥後之膜厚成為20 //m之方式塗佈於經脫模處 理之聚對苯二甲酸乙二酯（PET，p〇lyethylene terephthalate) 膜上，進行乾燥而製成聚乙烯縮醛樹脂之樹脂片材。 (實施例2) 除了使用195 g之聚合度為17〇〇、皂化度為99莫耳％ 之聚乙烯醇，65 g之聚合度為1700、皂化度為80莫耳0/〇 之聚乙烯醇，135 g之正丁醛以外，以與實施例】相同之 方法’獲得聚乙烯丁醛樹脂。 所得之聚乙烯丁醛樹脂的丁醛化度為62莫耳〇/0。 使用所得之聚乙烯丁醛樹脂，以與實施例1相同之方 式製作聚乙烯縮醛樹脂之樹脂片材。 (實施例3) 1700、皂化度為99莫耳％之聚 17〇〇 '皂化度為80莫耳％之聚 以與實施例1相同之方法， 使用65 g之聚合度為 乙烯醇，195 g之聚合度為 乙稀醇’ 115 g之正丁搭， 得聚乙烯丁醛樹脂。 所得之聚乙烯丁醛樹脂的丁醛化度為5 1莫耳％。 使用所得之聚乙稀丁路樹脂’以與實施例1相同之 式製作聚乙烯縮醛樹脂之樹脂片材。 (實施例4 ) 使用130 g之聚合度為1700、皂化度為96.5莫耳％之 聚乙烯醇’ 130 g之聚合度為1700、皂化度為80莫耳％之 聚乙烯醇，120 g之正丁醛’以與實施例1相同之方法 獲得聚乙烯丁醛樹脂。 21 200904885 所得之聚乙烯丁醛樹脂的丁醛化度為55莫耳％。 使用所得之聚乙烯丁醛樹脂，以與實施例1相同之方 式製作聚乙稀縮醛樹脂之樹脂片材。 (實施例5) 使用130 g之聚合度為2500、皂化度為99莫耳°/。之聚 乙烯醇，130 g之聚合度為25 00、皂化度為8〇莫耳％之聚 乙烯醇，120g之正丁醛，以與實施例i相同之方法，獲 得聚乙烯丁醛樹脂。 所得之聚乙烯丁醛樹脂的丁醛化度為58莫耳％。 使用所得之聚乙烯丁醛樹脂，以與實施例1相同之方 式製作聚乙烯縮醛樹脂之樹脂片材。 (實施例6) 使用130 g之聚合度為33〇〇、皂化度為99莫耳。/〇之聚 乙稀醇’ 130 g之聚合度為1100、皂化度為78莫耳％之聚 乙烯醇，120 g之正丁醛，以與實施例i相同之方法， 得聚乙烯丁醛樹脂。 所知之聚乙烯丁路樹脂的丁酿化度為56莫耳〇/〇。 使用所得之聚乙烯丁醛樹脂，以與實施例1相同之方 式製作聚乙烯縮醛樹脂之樹脂片材。 (實施例7) 使用130 g之聚合度為n〇〇、皂化度為99莫耳％之聚 乙烯醇，130 g之聚合度為17〇〇、皂化度為87 5莫耳％ 聚乙烯醇，13〇 g之正丁醛，以與實施例1相同之方之 獲得聚乙烯丁醛樹脂。 、’ 22 200904885 所得之聚乙烯丁醛樹脂的丁醛化度為6〇莫耳％。 使用所得之聚乙烯丁醛樹脂，以與實施例1相同之方 式製作聚乙烯縮醛樹脂之樹脂片材。 (實施例8) 使用86 g之聚合度為1700、皂化度為99莫耳％之聚 乙烯醇，86 g之聚合度為1700、皂化度為9〇莫耳％之聚 乙烯醇，88.5 g之聚合度為1700、皂化度為8〇莫耳％之聚 乙烯醇，及125 g之正丁醛，以與實施例丨相同之方法， 獲得聚乙烯丁醛樹脂。 所得之聚乙烯丁醛樹脂的丁醛化度為56莫耳％。 使用所得之聚乙稀丁醛樹脂，以與實施例1相同之方 式製作聚乙烯縮醛樹脂之樹脂片材。 (實施例9) 使用130 g之聚合度為600、皂化度為98.5莫耳0/〇之 聚乙稀醇’ 130 g之聚合度為25 00、皂化度為80莫耳D/〇之 聚乙烯醇，125 g之正丁醛，以與實施例丨相同之方法， 獲得聚乙烯丁醛樹脂。 所得之聚乙烯丁醛樹脂的丁醛化度為57莫耳0/〇β 使用所得之聚乙烯丁醛樹脂，以與實施例丨相同之方 式製作聚乙烯縮醛樹脂之樹脂片材。 (實施例10) 使用130 g之聚合度為33〇〇、皂化度為99莫耳％之聚 乙烯醇，130 g之聚合度為5〇〇、皂化度為73莫耳％之聚 乙烯醇，116 g之正丁醛，以與實施例i相同之方法，獲 23 200904885 得聚乙烯丁醛樹脂。 所得之聚乙烯丁醛樹脂的丁醛化度為52莫耳％。 使用所得之聚乙烯丁醛樹脂，以與實施例1相同之方 式製作聚乙稀縮醛樹脂之樹脂片材。 (實施例11) 使用130 g之聚合度為1100、皂化度為99莫耳％之聚 乙浠醇，130 g之聚合度為U00、皂化度為78莫耳％之聚 乙烯醇，120 g之正丁醛，以與實施例i相同之方法， 得聚乙烯丁醛樹脂。 所得之聚乙烯丁醛樹脂的丁醛化度為5 6莫耳％。 使用所得之聚乙烯丁醛樹脂，以與實施例丨相同之方 式製作聚乙烯縮醛樹脂之樹脂片材。 (實施例12) ' 首先，使用260 g之聚合度為17〇〇、皂化度為99 耳％之聚乙烯醇，150 g之正丁醛，以與實施例1相同之方 法，獲得聚乙婦丁駿樹脂Αβ所得之聚乙烯丁㈣脂 丁醛化度為66莫耳％。 的 繼而，使用260 g之聚合度為17〇〇、息化度為8 耳％之聚乙烯醇，異 1〇 g之正丁醛，以與實施例丨相同 法，獲得聚乙稀丁齡椒R α 驗樹知Β。所得之聚乙烯丁醛樹脂 丁醛化度為46莫耳％。 之 將5重量份所得之聚乙缚丁搭樹脂Α及5重量份聚 稀丁駿樹脂B添加於45番曰八 ^ &乙 刀於45重置份之甲苯及45重量 的混合溶劑中，進行 重伤之乙醇 仃攬件，令解。以乾燥後之膜厚成為 ί'ί 24 200904885 m之方式，塗佈於經脫模處理之聚對苯二甲酸乙二酯（ρΗτ) 膜上，進行乾燥而製成聚乙烯縮醛樹脂之樹脂片材。 (比較例1) 使用260 g之聚合度為17〇〇、皂化度為99莫耳％之聚 乙烯醇，150 g之正丁醛，以與實施例】相同之方法，獾 得聚乙烯丁醛樹脂。 所得之聚乙烯丁醛樹脂的丁醛化度為66莫耳〇/〇。 使用所得之聚乙烯丁醛樹脂，以與實施例丨相同之方 式製作聚乙烯縮醛樹脂之樹脂片材。 (比較例2) 使用234 g之聚合度為17〇〇、息化度為99莫耳％之聚 乙烯醇，26g之聚合度為17〇〇、皂化度為8〇莫耳％之聚 乙烯醇’ 146 g之正丁醛’以與實施你"相同之方 得聚乙烯丁醛樹脂。 所得之聚乙烯丁醛樹脂的丁醛化度為65莫耳0/〇。 ,使用所得之聚乙稀丁_脂，以與實施例1相同之方 式製作聚乙烯縮醛樹脂之樹脂片材。 (比較例3) 使用26 g之聚合度為1700、矣化度為99莫耳％之聚 乙烯醇，234 g之聚合度為17〇〇、息化度為8〇莫耳％之聚 :烯醇’ H)6 g之正丁搭’以與實施#"相同之方法，獲 得聚乙烯丁醛樹脂。 化度為45莫耳％。 以與實施例1相同之方 所得之聚乙烯丁醛樹脂的丁駿 使用所得之聚乙烯丁醛樹脂， 25 200904885 式製作聚乙烯縮醛樹脂之樹脂片材。 (比較例4) 使用130 g之聚合度為1700、皂化度為98莫耳％之聚 乙烯醇，130 g之聚合度為1700、皂化度為90莫耳％之聚 乙烯醇’ 130 g之正丁醛，以與實施例1相同之方法，择 得聚乙烯丁醛樹脂。 所得之聚乙烯丁醛樹脂的丁醛化度為61莫耳％。 使用所得之聚乙烯丁醛樹脂，以與實施例1相同之方 式製作聚乙稀縮醛樹脂之樹脂片材。 (比較例5) 使用130 g之聚合度為1700、皂化度為88.5莫耳％之 聚乙烯醇，130 g之聚合度為1700、皂化度為80莫耳。/〇之 聚乙烯醇’ 1 10 g之正丁醛，以與實施例1相同之方法， 獲得聚乙烯丁醛樹脂。 所得之聚乙烯丁醛樹脂的丁醛化度為5丨莫耳％。 使用所得之聚乙烯丁链樹脂’以與實施例1相同之方 式製作聚乙烯縮醛樹脂之樹脂片材。 (比較例6) 使用260 g之聚合度為1450、皂化度為99莫耳％之聚 乙烯醇，157 g之正丁醛，以與實施例丨相同之方法，獲 得聚乙烯丁醛樹脂。 所得之聚乙烯丁醛樹脂的丁醛化度為69莫尊。/〇。 使用所得之聚乙烯丁醛樹脂，以與實施例丨相同之方 式製作聚乙烯縮醛樹脂之樹脂片材。 26 200904885 (評估） 對實施例1〜12及比較例1~6中所得之樹脂片材進行 以下之評估。 、、’口不不"、’、1 τ -行苓，1她例ι~δ及比較例丨〜5之 結果示於表1中，實施例94 !及比較例6之結果示於表2 中，實施例12之結果示於表3中。 又，表1及表2中記載有··根據混合重量比之比例將 兩種聚乙烯醇之皂化度進行傾斜分配所算出之計算皂 度、以及根據各自之混合莫耳比的比例將兩種聚乙 聚合度進行傾斜分配所算出之計算聚合度。 、 (剖面狀態之確認） 於自所得之樹脂片材中採集之試料，使用切片機進 :丁切斷’藉此製作剖面試料後，使用 錄 (ΤΕΜ)，以3000倍對剖 I子顯倣鏡 及比較例2、4、；中::再者:心 料的圖像分別示於圖卜8中。*之樹月曰片材中採集之試 繼而，測定從所得之圖像 之相的直檀，將由島成分所構成之；^斤有島成分所構成 時，將包含80%之島成分所 U個數设為1〇〇% 徑。再者，上述島成分AC的直徑範圍作為分散 將長徑與短徑之平均值作為直徑。目為球狀以外之形狀時， 根據所得之圖像及分散徑來 將海成分與島成分之邊界明_、W是否形成海島結構。 0.07 以上之分散徑進行二：由島成分所構成之相以 π之情形認定為「海島結 27 200904885 構」’將海成分與島成分之邊界不明確之情形、或分散徑 未滿0·07以m之情形認定為「相溶」。 再者’對於海成分與島成分之邊界並不明確之比較例 4、5，不進行分散徑之測定。又，對於使用一種聚乙烯醇 之比較例1、2 ’不進行剖面狀態之確認。 (拉伸彈性模數） 依照 JIS K 7113 ’ 使用 TENSILON(ORIENTEC 公司製 造），於拉伸速度為20 mm/分鐘之條件下進行拉伸彈性模 數（MPa)之測定。 (降伏點應力、斷裂伸長率） 依照JIS K 6301「硫化橡膠物理試驗方法」，使用自 板狀成形體切出之啞鈴狀3號形試驗片，於20。(：、50〇/〇RH 之氣體環境下’以5 0 mm/分鐘之拉伸速度進行拉伸試驗， 測定降伏點應力（MPa)及斷裂伸長率（％)。 28 200904885 鬥I<】 彈性模數 (MPa) 1600 1650 1580 1600 1590 1600 1630 1600 1700 1500 1550 1600 1550 降伏點應力 (MPa) IT) m CN m in m in CN CN m 斷裂伸長率 _(%)^ 〇 〇\ V〇 ♦-H JO s \〇 in 00 «η cn 〇 w^> CN cn 縮醛化度 (莫耳％) (N »7» ITi 00 IT) m in in Ό jr> s vn 分散徑 _(㈣)_ 0.1-0.4 0.08-0.2 0.08-0.3 0.1-0.3 0.2-0.6 0.1-0.3 0.1-0.3 0.1-0.2 1 0.01-0.05 0.01 〜0.05 1 1 剖面狀態 海島結構 海島結構 海島結構 海島結構 海島結構 海島結構 海島結構 海島結構 1 相溶 相溶 相溶 相溶 計算聚合度 1700 1700 1700 1700 r 2500 1900 1700 1700 1700 1700 1700 1700 1 1700 計算皂化度 89.5 94.2 84.3 00 00 89.5 89.5 92.5 89.5 On ON ON 00 混合比 (%) JO 3 CO fO 1 Ο o 聚合度 1 17001 I 1700 1700 Ί 1 1700 1 I 1700 1 I 1700 ! 1700 1700 | I 2500 I I 2500 | I 3300 1 1100 | 1 1700J | 1700」 丨1700」 1700 1700 | Li700. | 1700」 1700 1 1700 1700 1 1700 1 1700」 1700 1700 皂化度 (莫耳％) g； § § 96.5 i 00 87.5 § §： 88.5 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 比較例1 比較例2 比較例3 比較例4 比較例5 6m 200904885 彈性模數 (MPa) 1610 J- 1600 1610 1500 降伏點應力 (MPa) ΓΛ m 斷裂伸長率 (%) (N 00 00 (N r-H 縮醛化度 (莫耳％) CN in ON 分散徑 (/zm) 0.08-0.2 0.08-0.15 0.1-0.3 1 剖面狀態 海島結構 海島結構 >每島結構 1 計算聚合度 1230 1290 1100 1450 計算皂化度 00 88.5 〇\ 〇\ 混合比 (%) 1 聚合度 600 2500 3300 〇 in 1100 1100 1450 皂化度 (莫耳％) 98.5 § % 〇〇 實施例9 實施例10 實施例11 比較例6 200904885 彈性模數 (MPa) 1600 斷裂點應力 (MPa) 斷裂伸長率 (%) ψ·^ 分散徑 ("m) 0.1-2.2 剖面狀態 海島結構 計算聚合度 1700 混合比 (%) 縮醛化度 (莫耳％) VO Ό 聚合度 1700 1700 皂化度 (莫耳％) § 實施例12 200904885 使用TEM進行剖面狀態確認之結果，可確認到··實施 例1 12中所得之聚乙稀縮搭樹脂形成了海島結構（參照 1 〜5)。 另一方面可確認到：比較例中所得之聚乙稀縮越樹脂 之樹脂彼此之間相溶’並未形成海島結構（參照圖㈣。 藉此如表1中所不，可知實施例中所得之聚乙稀縮 酿樹脂與比較例中所得之聚乙稀祕樹脂相比，斷裂伸長 率增大。另-方面’拉伸彈性模數、降伏點應力方面，實 施例中所得之聚乙烯祕樹脂與轉例巾所得之聚乙稀縮 醛樹脂係相同程度。 根據該等可知，實施例中 七、 只1”所侍之聚乙烯縮醛樹脂具有 充刀之強度與可撓性。 (產業利用性） 依據本發明，可提供—種含 ^ . ν , 有聚乙烯縮醛之樹脂，其 於用作為例如陶窨生胚片之办人成丨+ 分之可Μ 劑時，可獲得-種具有充 刀之了撓性、且即使薄膜化亦難以破損之陶 可提供使用該含有聚乙烯縮醛之 1, fL, ^ 的眾乙烯縮醛樹脂組The invention of the invention &< $ y ^ ^ L knows the effect of the moon, but there is also a mixed polyvinyl alcohol which is even mixed with a polyvinyl alcohol having a degree of polymerization of 1000 saponification degree of 80 moles / 〇 The acetalization also fails to achieve sufficient effects. Further, the difference in polymerization degree of the mixed polyvinyl alcohol is more than 2,500. The amount of saponification of the polyvinyl alcohol which is one of the two main polyvinyl alcohols. : (mole / 〇), and the degree of saponification of another polyvinyl alcohol is γ (mol/〇) 蚪, and X and Y preferably have the relationship of the following formula (4). (4) 30> IX- Υ|^ 25 Ancient ^ 丨! At 25, the compatibility of the polyvinyl alcohol to be mixed is increased, so that it is difficult to exhibit the effect of imparting flexibility. 1 Υ|greater than 3G ’, the solubility of polyvinyl alcohol with low saponification degree in water = right! The hydrazine is subjected to a reduction reaction, or the obtained mixed polyethylene condensate is known to have a reduced solubility in a solvent. =, using a polymerization degree of 3 ·, a degree of polymerization of 99 mole % of poly: =, if it is combined with a degree of polymerization of 73 degrees of separation of the sample: mixed polyethylene glycol to shrink Although the disk can be fully obtained: the sound of tl: effect, but there is even a degree of polymerization of 5. 〇 亦 亦 : : : : : : : : : : : : : : : : : : : : : : : : : : : :: When the mixing ratio of the main two kinds of polyethylenes with different degree of specialization of the mixed alcohol is less than the range of the weight ratio (for example, the weight is 1Q~, 8.2. The above mixing ratio is increased in compatibility) Therefore, it is difficult to exert the effect that the weight ratio of the above-mentioned mixed polyglycolic alcohol is one: 2::=tractivity. Moreover, the weight of the polyethylene having a low degree of specialization is high. The polyvinyl alcohol and the above-mentioned mixed polyethylene glycol may be in the case of =~8:2, etc. In order to mix the polyethyl alcohol of 3 15 200904885 or more different in degree of polymerization and saponification degree, the present invention may be In this case, it is preferable to satisfy the range of the degree of polymerization and the degree of specialization. For example, polyvinyl alcohol having a degree of polymerization of 1,700 and a degree of entrainment of 99 mol% can be cited. a mixture of 1700, a degree of polymerization of 95% by mole of polyethylene glycol, and a degree of polymerization of 1700, a degree of specialization of 75 mole % of polyethylene glycol, mixed by a weight ratio of 1.1. Polyethylene glycol alcohol, etc. The above-mentioned shrinkage t method is not particularly P-made, and τ is a previously known method, and for example, it can be exemplified by a salt. In the presence of an acid catalyst such as an acid, a method of adding σ 搭 and/or acetic acid to the above aqueous solution of the polyethylene glycol, etc. In the acetalization, it is preferred to use butyraldehyde and/or acetaldehyde. Thereby, a mixed polyvinyl acetal resin excellent in solvent solubility, flexibility, and sheet strength balance can be obtained. By mixing the above-mentioned mixed polyvinyl alcohol to acetalize, a mixed polyvinyl acetal resin can be obtained. The lower limit of the degree of acetalization of the mixed polyvinyl acetal resin is 40 mol/〇, and the upper limit is 80 mol%. If the degree of acetalization of the mixed polyvinyl acetal resin is less than 40 mol%, the obtained The mixed polyvinyl acetal resin is insoluble in the organic solvent, thereby hindering the production of the ceramic slurry for the ceramic green sheet. If the degree of acetalization of the mixed polyvinyl acetal resin exceeds the molar/〇, the residual hydroxyl group remains. The reduction of the toughness of the obtained mixed polyvinyl acetal resin is preferably 55 mol%, and the upper limit is 7 〇 mol%. In this specification, the degree of acetalization refers to mixing The ratio of the number of acetalized hydroxyl groups in the number of hydroxyl groups of polyethene alcohol, as a method of calculating the degree of acetalization of 200,904,885 S, since the acetal group of the mixed polyvinyl acetal resin is acetalized by two hydroxyl groups. Since it is formed, the molar percentage of acetalization is calculated by a method of counting two acetalized hydroxyl groups. The mixed polyvinyl acetal resin can be obtained by using two or more kinds of polyvinyl alcohols having different degrees of saponification. The mixed polyethylene _ which is formed is melted and then condensed to obtain 'a polyethylene resin which is different in saponification degree by a usual method, and then mixed to prepare a mixed polyethylene acetal Resin. Among them, the former method is suitable. The polyvinyl acetal-containing resin of the present invention can be used as a polyethylene compound M by, for example, mixing organic =. The above polycondensation composition is also one of the inventions. The organic solvent is not particularly limited, and examples thereof include organic solvents such as coppers, alcohols, aromatic hydrocarbons, and esters. The organic solvent of the above ketones can be, for example, W, methyl ethyl acetate, acetone or diisobutyl ketone. ^ is an organic solvent of the above alcohols such as isopropyl alcohol, butanol or the like. The organic solvent of the 二甲 吁 _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ · formazan propionate, methyl valerate, valeric acid I: methyl vinegar butyrate, ethyl butyrate, butyric acid butyrate, butyl hexanoate, ... butyl valerate, methyl hexanoate, caproic acid Ethyl vinegar, acetophenone 2-ethylhexyl ester, butyric acid 2 _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ A fiber, α-rosin, butyl cellosolve acetate, butyl carbitol acetate, and the like. These organic solvents may be used singly or in combination of two or more. The lower limit of the content of the polyvinyl acetal-containing resin in the polyvinyl acetal resin composition of the present invention is preferably 1% by weight, and the upper limit is preferably 50% by weight. When the content of the resin containing the polyvinyl acetal to the right is less than 1% by weight, the film formation is poor, and when the content of the resin containing the polyvinyl acetal exceeds 50 f% by weight, the viscosity is high, and the handleability is poor. The above contains a polyethylene shrinkage path. A more preferred lower limit of the content of the resin is 3% by weight, and a more preferred upper limit is 33% by weight. A further preferred lower limit of the content of the above-mentioned polyvinyl acetal-containing resin is 5% by weight, and a still more preferable upper limit is 2% by weight. The polyvinyl acetal resin composition of the present invention can be used as a slurry composition in which an inorganic powder is well dispersed, and a coating paste can be used, for example, by dispersing an inorganic powder such as a ceramic powder or a conductive powder. When used as the above slurry composition, ceramic powder is used as the inorganic sapphire a temple, and the above slurry composition can be used as a ceramic:light paste. The obtained ceramic charge can be suitably used as a material for the ceramic green sheet of the laminated ceramic capacitor. The above ceramic slurry is also one of the inventions. Further, by using the ceramic slurry of the present invention, it is possible to produce a ceramic green sheet which is hard to be broken even when peeled off from the support even when the thickness is from m or less. The above ceramic green sheets are also one of the inventions. When the coating paste is used, ceramic powder is used as the inorganic powder. The above-mentioned coating paste can be used as a ceramic paste. The obtained ceramic paste can also be used as the following ceramics for the use of the following ceramics, which is used in the production of the laminated ceramic capacitors in order to fill the conductive paste. In the portion where the conductive layer is not formed. The above-mentioned ceramic paste is also the invention of the invention - the coating: the Tao Jing powder is not particularly limited, for example, oxidized Ming, _, * titanium, zinc, copper titanate, magnesium oxide, sialon ( Sialon), spinel, mullite & cut, nitrogen cut, aluminum nitride, etc. A conductive powder was used as the above inorganic powder as a conductive paste. From the obtained conductive paste, the conductive paste formed by the conductive paste can be easily broken, and it is suitable for use in the manufacture of a laminated ceramic capacitor. In the above-mentioned conductive paste, the conductive powder is not particularly limited as long as it exhibits sufficient conductivity. For example, σ gold such as nickel, palladium, platinum, gold, silver or copper may be mentioned. The powder formed by the composition. These conductive powders may be used singly or in combination of two or more. ▲ The ceramics of the present month, the ceramic paste and the conductive paste are within the range that does not impair the effects of the present invention. Plasticizers, lubricants, antistatic agents, and the like may be suitably added. When the polyvinyl acetal resin composition of the present invention is used for an interlayer film for a two-layered glass used in an automobile, it is possible to obtain an interlayer which is difficult to break when the glass is broken and which has less damage during the stretching step and has excellent production efficiency. An intermediate film for glass. The above laminated glass interlayer film for automobiles is also one of the inventions. According to the present invention, a resin containing a polyvinyl acetal can be provided, which can be used as a binder for, for example, a ceramic green sheet, to obtain a ceramic having a knife-filling flexibility and being difficult to break even when thinned. Embryo. 200904885 In particular, when the resin containing the polyethylene shrinkage of the present invention is used, the amount of the plasticizer added to the ceramic green sheet can be greatly reduced. As a result, it is possible to prevent not only the damage of the ceramic sheet, but also the deformation caused by the plasticizer or the bleeding of the plasticizer. Furthermore, by using the polyvinyl acetal resin composition, it is possible to provide a polyethylene (tetra) lipid composition having excellent properties, a ceramic material, a ceramic paste, a ceramic green sheet, an electric paste, and a laminated glass for automobiles. Intermediate film. [Embodiment] Hereinafter, the present invention will be described in further detail by way of examples, but the invention is not limited to the embodiments. (Example 1) 130 g of a polyethylene having a degree of polymerization of 17 Å, a degree of saponification of 8 〇 mol%, and a polymerization degree of 130 g of a polymerization degree of 17 Å and a degree of recombination of 99 mol% Vinyl alcohol was added to 3000 g of pure water, and stirred at a temperature of 90 ° C for about 2 hours to dissolve. The solution was cooled to 4 〇〇c, 8 of which was added with a concentration of 35% by weight of hydrochloric acid and 125 g of n-butyraldehyde, and the temperature of the liquid was lowered to 10 C, and the temperature was maintained to carry out an acetalization reaction. The reaction product precipitated. Thereafter, the liquid temperature was maintained at 40 for 3 hours. . The reaction was completed, and a white powder of a polyethylene acetal resin was obtained by neutralization, water washing and drying by a usual method. The obtained polyvinyl acetal resin was dissolved in DMS 〇-d6 (dimethyl fluorene), and the degree of degree of butylation was measured by 13 C-NMR (nuclear magnetic resonance spectroscopy), and the degree of butyralization was 56 mol%. 10 parts by weight of the obtained polyvinyl acetal resin was added to a mixed solvent of 45 weights of the wounded and 45 parts by weight of ethanol, and the film thickness was 20,04,04, and the film thickness after drying was 20 //m. The method is applied to a release-treated polyethylene terephthalate (PET) film and dried to obtain a resin sheet of a polyvinyl acetal resin. (Example 2) In addition to using 195 g of polyvinyl alcohol having a polymerization degree of 17 Å and a degree of saponification of 99 mol%, 65 g of a polyvinyl alcohol having a degree of polymerization of 1700 and a degree of saponification of 80 mol / 〇 A polyvinyl butyral resin was obtained in the same manner as in the Example except that 135 g of n-butyraldehyde was used. The obtained polyvinyl butyral resin had a degree of butyralization of 62 moles/0. A resin sheet of a polyvinyl acetal resin was produced in the same manner as in Example 1 using the obtained polyvinyl butyral resin. (Example 3) 1700, a polysaponification degree of saponification degree of 99 mol%, a degree of saponification of 80 mol%, in the same manner as in Example 1, using a polymerization degree of 65 g of vinyl alcohol, 195 g The polymerization degree is a positive butadiene of ethylene glycol '115 g, and a polyvinyl butyral resin is obtained. The obtained polyvinyl butyral resin had a butyraldehyde degree of 51% by mole. A resin sheet of a polyvinyl acetal resin was produced in the same manner as in Example 1 using the obtained polyethylene butyl resin. (Example 4) 130 g of polyvinyl alcohol having a degree of polymerization of 1700, a degree of saponification of 96.5 mol%, a degree of polymerization of 130 g, a degree of polymerization of 1700, a degree of saponification of 80 mol%, and 120 g of positive Butyraldehyde' was obtained in the same manner as in Example 1 to obtain a polyvinyl butyral resin. 21 200904885 The obtained polyvinyl butyral resin has a degree of butyralization of 55 mol%. A resin sheet of a polyacetal acetal resin was produced in the same manner as in Example 1 using the obtained polyvinyl butyral resin. (Example 5) The degree of polymerization using 130 g was 2,500, and the degree of saponification was 99 mol/. Polyvinyl alcohol, 130 g of a polymerization degree of 25 00, a saponification degree of 8 〇 mol% of polyvinyl alcohol, and 120 g of n-butyraldehyde were obtained in the same manner as in Example i to obtain a polyvinyl butyral resin. The obtained polyvinyl butyral resin had a butyraldehyde degree of 58 mol%. A resin sheet of a polyvinyl acetal resin was produced in the same manner as in Example 1 using the obtained polyvinyl butyral resin. (Example 6) A polymerization degree of 130 g was used, and the degree of saponification was 99 mol. / Polyethylene glycol of hydrazine - 130 g of polyvinyl alcohol having a degree of polymerization of 1100, a degree of saponification of 78 mol%, and 120 g of n-butyraldehyde, in the same manner as in Example i, a polyvinyl butyral resin was obtained. . The degree of brewing of the known polyethylene butadiene resin is 56 moles per gram. A resin sheet of a polyvinyl acetal resin was produced in the same manner as in Example 1 using the obtained polyvinyl butyral resin. (Example 7) 130 g of polyvinyl alcohol having a degree of polymerization of n〇〇 and a degree of saponification of 99 mol%, a degree of polymerization of 130 g of 17 Å, and a degree of saponification of 87 5 mol% of polyvinyl alcohol were used. A 13 〇g n-butyraldehyde was obtained in the same manner as in Example 1 to obtain a polyvinyl butyral resin. The degree of butyralization of the polyvinyl butyral resin obtained by '22 200904885 is 6 〇 mol%. A resin sheet of a polyvinyl acetal resin was produced in the same manner as in Example 1 using the obtained polyvinyl butyral resin. (Example 8) 86 g of polyvinyl alcohol having a degree of polymerization of 1700 and a degree of saponification of 99 mol%, a degree of polymerization of 86 g of 1,700, a polyvinyl alcohol having a degree of saponification of 9 〇 mol%, and 88.5 g of a polyvinyl alcohol having a degree of polymerization of 1,700 g were used. A polyvinyl butyral resin was obtained in the same manner as in Example , a polyvinyl alcohol having a degree of polymerization of 1,700, a degree of saponification of 8 〇 mol%, and 125 g of n-butyraldehyde. The obtained polyvinyl butyral resin had a degree of butyralization of 56 mol%. A resin sheet of a polyvinyl acetal resin was produced in the same manner as in Example 1 using the obtained polyacetal butyral resin. (Example 9) 130 g of polyethylene having a polymerization degree of 600, a degree of saponification of 98.5 mol/0/〇, a polymerization degree of 130 g, a degree of polymerization of 25 00, and a degree of saponification of 80 mol D/〇 was used. An alcohol, 125 g of n-butyraldehyde, was obtained in the same manner as in Example , to obtain a polyvinyl butyral resin. The obtained polyvinyl butyral resin had a degree of butyralization of 57 mol/0. Using the obtained polyvinyl butyral resin, a resin sheet of a polyvinyl acetal resin was produced in the same manner as in Example 。. (Example 10) 130 g of polyvinyl alcohol having a polymerization degree of 33 Å and a degree of saponification of 99 mol%, 130 g of polyvinyl alcohol having a polymerization degree of 5 Å and a degree of saponification of 73 mol% was used. 116 g of n-butyraldehyde was obtained in the same manner as in Example i to obtain a polyethylene butyral resin of 23 200904885. The obtained polyvinyl butyral resin had a degree of butyraldehyde degree of 52 mol%. A resin sheet of a polyacetal acetal resin was produced in the same manner as in Example 1 using the obtained polyvinyl butyral resin. (Example 11) 130 g of polyvinyl alcohol having a degree of polymerization of 1100 and a degree of saponification of 99 mol%, 130 g of polyvinyl alcohol having a degree of polymerization of U00 and a degree of saponification of 78 mol%, 120 g was used. Into butyraldehyde, a polyvinyl butyral resin was obtained in the same manner as in Example i. The obtained polyvinyl butyral resin had a degree of butyraldehyde degree of 5 6 mol%. Using the obtained polyvinyl butyral resin, a resin sheet of a polyvinyl acetal resin was produced in the same manner as in Example 。. (Example 12) ' First, a polyethylene chelate was obtained in the same manner as in Example 1 using 260 g of polyvinyl alcohol having a polymerization degree of 17 Å, a degree of saponification of 99 Å, and 150 g of n-butyraldehyde. The polyethylene butadiene (IV) obtained by Ding Jun resin Αβ had a butyral degree of 66 mol%. Then, using 260 g of polyvinyl alcohol having a degree of polymerization of 17 Å, a degree of recombination of 8 Å, and n-butyraldehyde of 1 〇g, in the same manner as in Example 获得, a polyethylene butyl sylvestre was obtained. R α is a tree of knowledge. The obtained polyvinyl butyral resin had a degree of butanalization of 46 mol%. 5 parts by weight of the obtained polybutadiene resin and 5 parts by weight of polybutylene resin B are added to 45 parts of the toluene and 45 parts of the mixed solvent, Carry out a serious injury to the ethanol, and solve the problem. Applying to a release-treated polyethylene terephthalate (ρΗτ) film and drying it to form a resin of a polyvinyl acetal resin in a manner that the film thickness after drying is ί'ί 24 200904885 m Sheet. (Comparative Example 1) Using 260 g of polyvinyl alcohol having a polymerization degree of 17 Å, a degree of saponification of 99 mol%, and 150 g of n-butyraldehyde, a polyvinyl butyral was obtained in the same manner as in the Example Resin. The obtained polyvinyl butyral resin had a degree of butyraldehyde degree of 66 moles per oxime. Using the obtained polyvinyl butyral resin, a resin sheet of a polyvinyl acetal resin was produced in the same manner as in Example 。. (Comparative Example 2) 234 g of polyvinyl alcohol having a polymerization degree of 17 Å and a degree of recombination of 99 mol%, 26 g of a polyvinyl alcohol having a degree of polymerization of 17 Å and a degree of saponification of 8 〇 mol% was used. '146 g of n-butyraldehyde' is the same as the one that implements you. The obtained polyvinyl butyral resin had a butyraldehyde degree of 65 mol/min. A resin sheet of a polyvinyl acetal resin was produced in the same manner as in Example 1 using the obtained polyethylene condensate. (Comparative Example 3) 26 g of polyvinyl alcohol having a degree of polymerization of 1700 and a degree of deuteration of 99 mol%, a polymerization degree of 234 g of 17 Å, and a degree of polycomposition of 8 〇 mol% were used. Alcohol 'H) 6 g of n-butylene 'in the same manner as in the implementation #", a polyvinyl butyral resin was obtained. The degree of conversion is 45 mol%. Using a polyethylene butyral resin obtained in the same manner as in Example 1, a resin sheet of a polyvinyl acetal resin was produced by using the obtained polyvinyl butyral resin, 25 200904885. (Comparative Example 4) 130 g of polyvinyl alcohol having a degree of polymerization of 1700 and a degree of saponification of 98 mol%, a degree of polymerization of 130 g of 1700, and a degree of saponification of 90 mol% of polyvinyl alcohol '130 g were used. In the same manner as in Example 1, butylene aldehyde, a polyvinyl butyral resin was selected. The obtained polyvinyl butyral resin had a degree of butyralization of 61 mol%. A resin sheet of a polyacetal acetal resin was produced in the same manner as in Example 1 using the obtained polyvinyl butyral resin. (Comparative Example 5) 130 g of polyvinyl alcohol having a degree of polymerization of 1700 and a degree of saponification of 88.5 mol% was used, and the degree of polymerization of 130 g was 1,700 and the degree of saponification was 80 mol. A polyvinyl butyral resin was obtained in the same manner as in Example 1 except that polyvinyl alcohol was used as 1 10 g of n-butyraldehyde. The obtained polyvinyl butyral resin had a butyraldehyde degree of 5 丨 mol%. A resin sheet of a polyvinyl acetal resin was produced in the same manner as in Example 1 using the obtained polyethylene butadiene resin. (Comparative Example 6) A polyvinyl butyral resin was obtained in the same manner as in Example 260, using 260 g of a polyvinyl alcohol having a degree of polymerization of 1450, a degree of saponification of 99 mol%, and 157 g of n-butyraldehyde. The obtained polyvinyl butyral resin had a degree of butyralization of 69 moles. /〇. Using the obtained polyvinyl butyral resin, a resin sheet of a polyvinyl acetal resin was produced in the same manner as in Example 。. 26 200904885 (Evaluation) The resin sheets obtained in Examples 1 to 12 and Comparative Examples 1 to 6 were evaluated as follows. The results of 'Examples ι δ and Comparative Examples 5 5 are shown in Table 1, and the results of Example 94 and Comparative Example 6 are shown in the table. In 2, the results of Example 12 are shown in Table 3. Further, in Tables 1 and 2, the calculated soapiness calculated by obliquely distributing the saponification degrees of the two polyvinyl alcohols according to the ratio of the mixing weight ratio, and the ratio of the molar ratios of the respective molar ratios are described. The degree of polymerization of the polyethylation degree was calculated by oblique distribution. (Confirmation of the cross-sectional state) The sample collected from the obtained resin sheet is cut into the mold using a microtome. After the cross-section sample is prepared, the recording is performed using a recording (ΤΕΜ), and the sub-division is performed by 3000 times. Mirror and Comparative Example 2, 4, ; Medium:: Again: The images of the heart material are shown in Figure 8 respectively. * The test collected in the tree of the moon is measured, and the straight sandalwood of the phase obtained from the obtained image will be composed of the island components; when it is composed of the island component, it will contain 80% of the island components. The number is set to 1〇〇%. Further, the diameter range of the above-mentioned island component AC is defined as the diameter of the average of the major axis and the minor axis. When the shape is a spherical shape, the boundary between the sea component and the island component is determined based on the obtained image and the dispersion diameter, and whether or not the island structure is formed. The dispersion path of 0.07 or more is performed as follows: the phase consisting of island components is identified as "island knot 27 200904885 structure" in the case of π. The boundary between the sea component and the island component is unclear, or the dispersion path is less than 0·07. It is considered to be "compatible" in the case of m. Further, in Comparative Examples 4 and 5, where the boundary between the sea component and the island component is not clear, the measurement of the dispersion diameter is not performed. Further, in Comparative Examples 1 and 2' using a polyvinyl alcohol, the cross-sectional state was not confirmed. (Tensile elastic modulus) The tensile modulus (MPa) was measured in accordance with JIS K 7113 ' using TENSILON (manufactured by ORIENTEC Co., Ltd.) at a tensile speed of 20 mm/min. (Falling point stress, elongation at break) A dumbbell-shaped No. 3 test piece cut out from a plate-shaped formed body was used in accordance with JIS K 6301 "Vulcanized rubber physical test method". (:, 50 〇 / 〇 RH in a gas atmosphere 'stretching test at a tensile speed of 50 mm / min, measuring the point stress (MPa) and elongation at break (%). 28 200904885 Buck I <] elasticity Modulus (MPa) 1600 1650 1580 1600 1590 1600 1630 1600 1700 1500 1550 1600 1550 Falling point stress (MPa) IT) m CN m in m in CN CN m Elongation at break _(%)^ 〇〇\ V〇♦- H JO s \〇in 00 «η cn 〇w^> CN cn acetalization degree (% by mole) (N »7» ITi 00 IT) m in in Ό jr> s vn dispersion path _((4))_ 0.1-0.4 0.08-0.2 0.08-0.3 0.1-0.3 0.2-0.6 0.1-0.3 0.1-0.3 0.1-0.2 1 0.01-0.05 0.01 ~0.05 1 1 Island State Island Island structure Island island structure Island island structure Island island structure Structure 1 Competing, dissolving, dissolving, phase-solving, calculating degree of polymerization, 1700 1700 1700 1700 r 2500 1900 1700 1700 1700 1700 1700 1700 1 1700 Calculating the degree of saponification 89.5 94.2 84.3 00 00 89.5 89.5 92.5 89.5 On ON ON 00 Mixing ratio (%) JO 3 CO fO 1 Ο o Degree of polymerization 1 17001 I 1700 1700 Ί 1 1700 1 I 1700 1 I 1700 1700 1700 | I 2500 II 2500 | I 3300 1 1100 | 1 1700J | 1700" 丨1700" 1700 1700 | Li700. | 1700" 1700 1 1700 1700 1 1700 1 1700" 1700 1700 Saponification degree (% by mole) g § § 96.5 i 00 87.5 § §: 88.5 Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 6m 200904885 Elastic modulus (MPa) 1610 J- 1600 1610 1500 Falling point stress (MPa) ΓΛ m Elongation at break (%) (N 00 00 (N rH acetalization degree (mole %) CN in ON Dispersion diameter ( /zm) 0.08-0.2 0.08-0.15 0.1-0.3 1 Profile state island structure island structure> Per island structure 1 Calculate the degree of polymerization 1230 1290 1100 1450 Calculate the degree of saponification 00 88.5 〇\ 〇\ Mix ratio (%) 1 Degree of polymerization 600 2500 3300 〇in 1100 1100 1450 Saponification degree (% by mole) 98.5 § % 〇〇 Example 9 Example 10 Example 11 Comparative Example 6 200904885 Elastic modulus (MPa) 1600 Break point stress (MPa) Elongation at break (%) ) ψ·^ Dispersion path ("m) 0.1-2.2 State island structure calculation degree of polymerization 1700 Mixing ratio (%) Degree of acetalization (% by mole) VO Ό Degree of polymerization 1700 1700 Degree of saponification (% by mole) § Example 12 200904885 The result of confirming the profile state by TEM can be confirmed The polyethylene-seal resin obtained in Example 1 12 forms an island structure (see 1 to 5). On the other hand, it was confirmed that the resins of the polyethylene-shrinkable resin obtained in the comparative example were incompatible with each other 'the sea-island structure was not formed (see FIG. 4). Thus, as shown in Table 1, the results obtained in the examples are known. Compared with the polyethylene resin obtained in the comparative example, the polyethylene elongation shrinkage resin has an increased elongation at break. In another aspect, the tensile modulus of elasticity and the point of stress at the point of depression, the polyethylene secret obtained in the examples. The resin is the same degree as the polyacetal acetal resin obtained by the transfer of the towel. According to the above, in the examples, the polyvinyl acetal resin which is only 1" is required to have the strength and flexibility of filling. According to the present invention, there can be provided a resin containing a polyethylene acetal which can be obtained by using, for example, a sputum sputum sputum + saponin. A ceramic acetal resin group having a flexibility of filling a knife and being hard to be broken even if it is thinned can be provided using the polyvinyl acetal resin group containing 1, acetal, acetal.
成物、陶瓷漿料、陶瓷糊、陶瓷生胚H 夾層玻璃中間膜。 刑汉八早用 【圖式簡單說明】 圖1係拍攝實施例1中所得之槲γ κ从 片 侍之樹月曰片材的剖面ΤΕΜ照 片 圖2係拍攝實施例2中所得之樹脂片材的 剖面ΤΕΜ照 32 200904885 圖3係拍攝實施例3中所得之樹脂片材的剖面 圖4係拍攝實施例9中所得之樹脂片材的剖面 圖5係拍攝實施例12中所得之樹脂片材的与 圖6係拍攝比較例2中所得之樹脂片材的剖面 圖 7係aw '、拍攝比較例4中所得之樹脂片材的剖面 圖8係拍攝比較例5中所得之樹脂片材的剖面 【主要元件符號說明】 無 TEM照 TEM照 面TEM TEM照 TEM照 TEM照 33Forming, ceramic slurry, ceramic paste, ceramic green embryo H laminated glass interlayer film. The early morning of the sentence is as follows: Figure 1 is a photograph of the 槲γ κ obtained from Example 1 from the section of the sashimi tree 曰 ΤΕΜ ΤΕΜ 图 图 图 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 Cross-sectional view 32 200904885 FIG. 3 is a cross-sectional view of the resin sheet obtained in Example 3, FIG. 4 is a cross-sectional view of the resin sheet obtained in the photographing example 9, and FIG. 5 is a photograph of the resin sheet obtained in Example 12. 6 is a cross-sectional view of the resin sheet obtained in Comparative Example 2, and a cross-sectional view of the resin sheet obtained in Comparative Example 4 is a section of the resin sheet obtained in Comparative Example 5. Explanation of main component symbols] TEM-free TEM TEM TEM TEM TEM photographic 33