200925192 九、發明說明： 【發明所屬之技術領域】 本發明係關於一種片材，其含有於各種化學反應領域 中，用以將液體狀或氣體狀之被處理流體改性或分解之觸 媒粒子。 【先前技術】 近年來’汽車之排氣限制’於強化限制值之方向實施的 地域正在世界範圍性地擴大。特別是於米國，已預定對 〇 HC或NOx進行階段性限制強化。於日本，自2〇〇〇年起強化 對汽油車之排氣限制。 車用觸媒係於汽車之排氣管的引擎與消音器之中間位 置以轉換器之形式安裝。於轉換器中，裝填有於蜂窩狀之 堇青石載體上塗層有氧化鋁以及貴金屬（pt、pd、Rh)等之 觸媒。塗佈層包含作為觸媒成分之貴金屬、氧化鋁、用以 抑制其等燒結之穩定化之副成份、以及具有被稱為〇sc (Oxygen Storage Component)功能的二氧化鈽（Ce〇2)等。 β 然而’於如上述之先前技術中，存在於平面之片材狀觸 媒中’觸媒被黏合劑覆蓋，從而被埋沒之缺點，進而觸媒 片材並未具有通水性甚至通氣性，因此於觸媒與被處理流 體之接觸效率中，於觸媒表面之有效利用方面並不充分。 即，存在觸媒未能更有效地發揮功能，從而限制處理能力 之問題。 自實際之觸制制技術方面考慮，對於作為被處理流 體之液體或氣體’為獲得目標物之更有效的分解處理能 135221.doc 200925192 力’提高被處理流體中之處理對象物與觸媒的接觸效率係 最有效的方法。 【發明内容】 本發明係為了解決如上述之先前技術所存在之問題而成 者，其目的在於提供-種耐熱片#，該耐熱片材藉由提高 觸媒表面與被處理流體之接觸效率，而進—步提高將被處 理流體中所含之有機物、無機物等分解之處理能力。200925192 IX. Description of the Invention: [Technical Field] The present invention relates to a sheet material which is contained in various chemical reaction fields for modifying or decomposing catalytic particles in a liquid or gaseous treated fluid. . [Prior Art] In recent years, the area where the "exhaust gas restriction of automobiles" has been implemented in the direction of strengthening the limit value is expanding worldwide. Especially in the country, it has been scheduled to phase-enhance the 〇 HC or NOx. In Japan, the exhaust restrictions on gasoline vehicles have been strengthened since the following year. The vehicle catalyst is mounted in the form of a converter in the middle of the engine and muffler of the exhaust pipe of the car. In the converter, a honeycomb-like cordierite support is coated with a catalyst such as alumina and a noble metal (pt, pd, Rh). The coating layer contains a noble metal as a catalyst component, alumina, an auxiliary component for suppressing stabilization such as sintering, and ceria (Ce〇2) having a function called 〇sc (Oxygen Storage Component). .然而 However, in the prior art as described above, the catalyst is present in a planar sheet-like catalyst, and the catalyst is covered by the binder, thereby being buried, and the catalyst sheet is not water-permeable or even ventilating. In the contact efficiency between the catalyst and the fluid to be treated, the effective use of the catalyst surface is not sufficient. That is, there is a problem that the catalyst fails to function more effectively, thereby limiting the processing capability. From the point of view of actual tactile technology, it is more effective to decompose the liquid or gas as the fluid to be treated. 135221.doc 200925192 Force' to improve the treatment target and catalyst in the fluid to be treated Contact efficiency is the most effective method. SUMMARY OF THE INVENTION The present invention has been made in order to solve the problems of the prior art as described above, and an object thereof is to provide a heat-resistant sheet # which improves the contact efficiency between a catalyst surface and a fluid to be treated, Further, the processing ability for decomposing organic substances, inorganic substances, and the like contained in the fluid to be treated is increased.
本發明係提供-種耐熱片材，其特徵在於其係含有觸媒 粒子、芳香族聚醯胺纖條體以及耐熱纖維而成之片材，於 片材中觸媒之體積分率至少為2%，芳香族聚醯胺纖條體 之體積分率至少為4%。 本發明之耐熱片材，由於芳香族聚醯胺纖條體之較高之 觸媒粒子捕獲效果，可較多地填充觸媒粒子，且片材為多 孔性，因此具有被處理流體效率良好地與觸媒粒子接觸且 自片材中通過之效果。又，本發明之耐熱片材包含本質上 耐熱〖生較向之芳香族聚醯胺纖條體與耐熱纖維，因此可提 高環境溫度而提高反應速度。 以下，對本發明之耐熱片材加以更詳細之說明。 <觸媒粒子> 作為本發明之耐熱片材中可含有之觸媒粒子，包含於汽 車之排氣處理中使用之金屬、金屬硫化物、金屬氧化物等 之粒子，具體而言，作為包含單一金屬之金屬粒子，例如 可列舉鎳、@、銅、鋅、金、銀、鉑、鈀、鍺、銥等之粒 子；又，作為包含金屬硫化物之金屬硫化物粒子，例如可 135221.doc 200925192 列舉硫化鑛、硫化敍、硫化鎳、硫化鐵、硫化銘、硫化 釘、硫化銀、硫化鋅、硫化銦等之粒子。又，作為包含金 屬氧化物之金屬氧化物粒子，例如可列舉氧化鑛、氧化 鉛、氧化鎳、氧化鐵、氧化鈷、氧化釕、氧化銀、氧化 鋅、氧化銦等之粒子。 <芳香族聚醢胺纖條體> . 力本說明書中，芳香族聚醯胺係表示分子中之醯胺鍵 (•NHCO-)之60%以上直接鍵結於芳香環（例如苯環、萘環 • $ )上之線狀結構之高分子化合物’具體而言，例如可列 舉聚間笨二甲醯間苯二胺以及其共聚物、聚對苯二子酿對 苯二胺以及其共聚物、聚（對苯）_共聚（34二苯醚）對苯二 胺等。其等中，於具有良好之成型加工性、熱融著性之方 面，較好的是聚間苯二甲酿間苯二胺。聚間苯二甲醯間苯 一胺例如可藉由使用間苯二甲醯氯以及間苯二胺之其自身 已知之界面聚合法、溶液聚合法等而進行工業性製造。 • 芳香族聚醯胺纖條體表示具有抄紙性之膜狀芳香族聚醯 胺粒子，亦稱為芳香族聚醯胺紙漿（例如參照日本專利特 公昭35-1 1851號公報等）芳香族聚酿胺纖條體與通常之木 漿相同，可用作可實施纖維分離、打漿處理之抄紙原料。 於此情形時，可良好地維持所形成之芳香族聚醯胺紙之特 性，因此較好的是芳香族聚醯胺纖條體通常具有以加拿大 寺示準游離度為10 ml以上且未滿500 mi之渡水度（游離度）， 特別是具有20〜150 ml之範圍内的濾水度（游離度）。芳香族 聚醢fe·纖條體之渡水度（游離度）的調整例如可藉由纖維分 135221.doc 200925192 離機、打漿機等以與通常之木滎相同之方式進行。 <耐熱纖維> 本發明中可使用之耐熱纖維，包含於約2耽以下之溫 度下並不軟化或者溶融以及分解之有機或無機系纖維具 體而言，例如可列舉以芳香族聚酿胺、全芳香族㈣、全 芳香族多偶氮化合物、全芳香族聚醋醯胺、全芳香族聚 謎、聚賴網、聚苯硫驗、聚對伸苯基苯并二㈣、聚苯 ❹ ❹ 并米嗤$對伸苯基苯并二吟。坐、聚酿胺-酿亞胺、聚酿 亞胺、雙馬來醯亞胺•三噪、聚胺基雙馬來酿亞胺、聚四 氣乙烯、陶究、氧化紹、二氧化石夕、氧化紹二氧化珍、玻 璃、岩棉、氮化石夕、碳化石夕、碳、氧化錯、欽酸卸、氧硫 化鎖、合成石夕酸約、娜、金屬等耐熱性素材為主成分之纖 維其等中，以芳香族聚醯胺纖維，特別是間位芳香族聚 醯胺纖維較好。 較好的是其等料纖維—般具有qgi I以上且未滿^ dtex，特別是具有〇.!〜22 dtex之範圍内的纖度。其中，纖 度定義為每则蚊纖維重量（g)。纖度未滿㈣—之纖 維於使用濕式法之製造（後述）中易導致凝集；又，25 — 以上之纖維’因纖維直徑變得過大’例如若為圓形且密度 為i_hw，則直徑為45 μιη以上，容易產生縱橫比降 低、力學增強效果降低、耐熱片材之均一性不良等問題。 其中’所謂耐熱片材之均-性不良係表示空隙尺寸之分布 變寬，觸媒粒子之配置產生不均一性。The present invention provides a heat-resistant sheet characterized by comprising a catalyst particle, an aromatic polyamine fibrid, and a heat-resistant fiber, wherein the catalyst has a volume fraction of at least 2 in the sheet. %, the aromatic polyamine fibrids have a volume fraction of at least 4%. The heat-resistant sheet of the present invention has a high catalytic particle-trapping effect of the aromatic polyamine fibrid, and can be filled with a large amount of catalyst particles, and the sheet is porous, so that the fluid to be treated is efficiently used. The effect of contact with the catalyst particles and passing through the sheet. Further, the heat-resistant sheet of the present invention contains an aromatic heat-resistant aromatic polyamide fiber and a heat-resistant fiber in an inherently heat-resistant manner, thereby increasing the ambient temperature and increasing the reaction rate. Hereinafter, the heat-resistant sheet of the present invention will be described in more detail. <catalyst particles> The catalyst particles which may be contained in the heat-resistant sheet of the present invention are contained in particles such as metals, metal sulfides, metal oxides and the like used in exhaust treatment of automobiles, specifically Examples of the metal particles containing a single metal include particles of nickel, @, copper, zinc, gold, silver, platinum, palladium, rhodium, iridium, and the like; and, as the metal sulfide particles containing the metal sulfide, for example, 135221. Doc 200925192 Lists particles such as sulfide ore, sulfide, nickel sulfide, iron sulfide, sulfide, vulcanized nail, silver sulfide, zinc sulfide, indium sulfide, etc. Further, examples of the metal oxide particles containing a metal oxide include particles of oxidized ore, lead oxide, nickel oxide, iron oxide, cobalt oxide, cerium oxide, silver oxide, zinc oxide, and indium oxide. <Aromatic Polyamide Fibrids> In the present specification, an aromatic polyamine means that 60% or more of a guanamine bond (•NHCO-) in a molecule is directly bonded to an aromatic ring (for example, a benzene ring). And a polymer compound of a linear structure of a naphthalene ring; and the polyphenylene diphenyl phenylenediamine and a copolymer thereof, polyparaphenylene diphenylene p-phenylenediamine, and copolymerization thereof are exemplified. , poly(p-phenylene)-copolymerization (34 diphenyl ether) p-phenylenediamine and the like. Among them, in terms of good moldability and hot meltability, poly(m-phenylene terephthalate) is preferred. The poly(m-xylylenediphenyl) meta-phenyleneamine can be industrially produced, for example, by an interfacial polymerization method, a solution polymerization method, or the like which is known per se using m-xylylene chloride and m-phenylenediamine. • Aromatic polyamide fibrids are membranous aromatic polyamide particles having papermaking properties, and are also known as aromatic polyamine pulps (for example, see Japanese Patent Publication No. Sho 35-1 1851, etc.). The aramid fiber strip is the same as the usual wood pulp, and can be used as a papermaking raw material capable of performing fiber separation and beating treatment. In this case, the characteristics of the formed aromatic polyamide paper can be favorably maintained. Therefore, it is preferred that the aromatic polyamine fibrids generally have a quasi-freeness of 10 ml or more and less than 500 in Canada. The fertility (freeness) of mi, especially the degree of filtration (freeness) in the range of 20 to 150 ml. The adjustment of the degree of freeness (freeness) of the aromatic polyfemoroids can be carried out, for example, in the same manner as the usual raft by means of a fiber 135221.doc 200925192, a machine, a beater or the like. <Heat-resistant fiber> The heat-resistant fiber which can be used in the present invention, the organic or inorganic fiber which is not softened or melted and decomposed at a temperature of about 2 Torr or less, specifically, for example, an aromatic polyamine , wholly aromatic (four), wholly aromatic polyazo compounds, wholly aromatic polyacetamide, fully aromatic polymymy, polylaid network, polyphenylene sulfide, polyparaphenylene benzobis(tetra), polyphenylene ❹ and rice bran $ phenyl benzoquinone. Sit, melamine-enamine, styrene, bismaleimide, tri-noise, polyamine-based bismaleimide, polytetraethylene, ceramics, oxidized, and sulphur dioxide , oxidation of sulphur dioxide, glass, rock wool, nitrite, carbon carbide, carbon, oxidation, acid decompression, oxygen vulcanization lock, synthetic stone acid, na, metal and other heat-resistant materials as the main component Among the fibers and the like, aromatic polyamine fibers, particularly meta-aramid fibers, are preferred. It is preferred that the fibers of the material generally have a qgi I or more and are less than dtex, especially having a fineness in the range of 〇.!~22 dtex. Among them, the fineness is defined as the weight (g) of each mosquito fiber. The fiber having a fineness (4) is liable to cause agglomeration in the production using the wet method (described later); in addition, the fiber of 25 to above is too large due to the fiber diameter, for example, if it is circular and the density is i_hw, the diameter is Above 45 μmη, problems such as a decrease in the aspect ratio, a decrease in the mechanical reinforcement effect, and a poor uniformity of the heat-resistant sheet are likely to occur. Among them, the term "uniformity of the heat-resistant sheet" means that the distribution of the void size is broadened, and the arrangement of the catalyst particles causes unevenness.
耐熱纖維以長度為！ _以上且未滿5〇_，特別是MO 135221.doc 200925192 mm之範圍内的短纖維狀耐熱纖維為宜。若耐熱纖維之長 度小於1 mm，則耐熱片材之力學特性降低，另一方面， mm以上者，於後述之使用濕式法製造耐熱片材時，容易 產生「接結」或「系結」等，容易成為產生缺陷之原因， 因此欠佳。 <对熱片材>Heat resistant fiber in length! _ above and less than 5〇_, especially short-fiber heat-resistant fibers in the range of MO 135221.doc 200925192 mm. When the length of the heat-resistant fiber is less than 1 mm, the mechanical properties of the heat-resistant sheet are lowered. On the other hand, when the heat-resistant sheet is produced by the wet method as described later, it is easy to cause "bonding" or "tie". Etc., it is easy to be the cause of defects, so it is not good. <pair hot sheet>
❹ 本發明之耐熱片材係以如上所述之觸媒粒子、芳香族聚 醯胺纖條體以及耐熱纖維為主而構成之片材狀物該耐執 片材，於片材中觸媒之體積分率至少為2%，較好的是 2〜4。/。之範_ ’且芳香族聚醯胺纖條體之體積分率至= 為4%’較好的是5〜15%之範圍内。又，本發明之耐熱片材 中之觸媒含量、纖條趙含量、耐熱纖維含量、基重以及密 度（基重/厚度）並無嚴格限制，可於片材中觸媒之體積分率 以及芳香族聚醯胺纖條體之體積分率為上述範圍内，相應 使用目的等自較廣泛之範圍内選擇。 然而’本發明之耐熱片材—般多以觸媒粒子、芳香族 醯胺纖條體為主成分，料熱纖維成為少量成分，耐 維之體積分率一般為9.5%以下，通常以成為 範圍 内之情形較多。 固 又，敉好的是本發 <瓜、々何一般具有〕〜Αυυυ μιη、 特別是Η)〜500叫之範圍内的厚度。片材之厚度小於 之情：時，機械特性降低，且容易於作為片材之形態保持 或於製造步驟中之搬送等操作上 座生問題，相反於超過 1000 μη!之情形時，容易產生 ‘、、、片材之均一性不良等問 135221.doc 200925192 題。 進而’本發明之耐熱片材可具有一般為5〜1000 g/m2、 較好的是10〜500 g/m2之範圍内的基重。於基重小於5 g/m2 之If形時，機械強度不足，因此於捲取等製造步驟中之各 種操作中容易產生破斷；另一方面於大於1000 g/m2之基 ί的耐熱片材中’發現厚度增A或者被處理流體之含浸· 浸透降低之傾向。 本發明之耐熱片材之密度係藉由基重/厚度算出之值。 β 再者，並不滿足上述片材中觸媒之體積分率以及芳香族 聚醯胺纖條體之體積分率之條件的财熱片#，未能在一定 的工間中保持足夠量的觸冑，因此產生被處理流體之接觸 效率降低之問題。 —又’較好的是本發明之耐熱片材以哥雷式冑氣測定法測 定之單位厚度的透氣度，即透氣度（秒/100 厚度（㈣至 夕為1.2 ’特別是1.5〜4.5之範圍内。#中，哥雷式透氣度 _ 係、以具有外徑為28.6 mm之圓孔的緊固板挾持樣品，將通 過該樣品流出100 cm3之空氣所需之時間以秒單位表示 者。透氣度（秒/100 cc)/厚度㈣小於12之耐熱片材具有 無法使被處理流體與觸媒粒子充分接觸之可能性。 進而，較好的是本發明之耐熱片材之抗拉強度（gf/15 mm)/厚度（_至少為6、特別是至少為ι〇。抗拉強度㈣$ —/厚度㈣小於6之耐熱片材，存在機械特性降低，且 作為片材之形態保持或者於製造步驟中之搬送等操作上產 生問題之可能性。 13522 丨.doc -10- 200925192 <耐熱片材之製造法>耐热 The heat-resistant sheet of the present invention is a sheet material mainly composed of the catalyst particles, the aromatic polyamine fibrids, and the heat-resistant fibers as described above, and the sheet is formed in the sheet. The volume fraction is at least 2%, preferably 2 to 4. /. The volume fraction of the aromatic polyamine fibrids to = 4%' is preferably in the range of 5 to 15%. Further, the catalyst content, the fiber content, the heat-resistant fiber content, the basis weight, and the density (basis weight/thickness) in the heat-resistant sheet of the present invention are not strictly limited, and the volume fraction of the catalyst in the sheet can be The volume fraction of the aromatic polyamine fibrids is within the above range, and the purpose of use is selected from a wide range. However, the heat-resistant sheet of the present invention generally contains catalyst particles and aromatic guanamine fibrids as the main component, and the heat fiber is a small component, and the volume fraction of the dimensional resistance is generally 9.5% or less, and is usually in the range. There are many situations inside. Solid, what is good is the hair &me; melon, why generally have a thickness of ~ Αυυυ μιη, especially Η) ~ 500 called the range. When the thickness of the sheet is smaller than that of the case: when the mechanical properties are lowered, it is easy to maintain the problem as a form of the sheet or a conveyance in the manufacturing step, and when it is more than 1000 μη, it is easy to generate ', , the uniformity of the sheet, etc. 135221.doc 200925192 questions. Further, the heat-resistant sheet of the present invention may have a basis weight in the range of usually 5 to 1000 g/m2, preferably 10 to 500 g/m2. When the basis weight is less than 5 g/m2, the mechanical strength is insufficient, so that breakage is likely to occur in various operations in the manufacturing steps such as winding; on the other hand, heat-resistant sheets of more than 1000 g/m2 are used. In the middle, it was found that the thickness increased by A or the impregnation and impregnation of the fluid to be treated decreased. The density of the heat-resistant sheet of the present invention is a value calculated from the basis weight/thickness. β Further, the fins #, which do not satisfy the conditions of the volume fraction of the catalyst in the above sheet and the volume fraction of the aromatic polyamine fibrid, fail to maintain a sufficient amount in a certain work space. Touching, thus causing a problem of reduced contact efficiency of the fluid to be treated. - Again, it is preferred that the heat-resistant sheet of the present invention has a gas permeability per unit thickness measured by the GRAY-type helium gas measurement, that is, a gas permeability (second/100 thickness ((4) to 1.2: especially 1.5 to 4.5 Within the range, #哥,哥雷式气气_, the sample is held by a fastening plate having a circular hole with an outer diameter of 28.6 mm, and the time required to flow 100 cm3 of air through the sample is expressed in seconds. The heat-resistant sheet having a gas permeability (second/100 cc)/thickness (four) of less than 12 has a possibility that the treated fluid and the catalyst particles are not sufficiently contacted. Further, the tensile strength of the heat-resistant sheet of the present invention is preferably ( Gf / 15 mm) / thickness (_ at least 6, especially at least ι 〇. Tensile strength (four) $ - / thickness (four) less than 6 heat-resistant sheet, there are mechanical properties are reduced, and as a form of sheet remains or The possibility of causing problems in handling such as transportation in the manufacturing step. 13522 丨.doc -10- 200925192 <Manufacturing method of heat-resistant sheet>
具有如上所述之特性的本發明之耐熱片材，一般可藉由 將上述之觸媒粒子與芳香族聚醯胺纖條體以及耐熱纖維混 合後加以片材化之方法進行製造。具體而言，例如可應用 將上述觸媒粒子、芳香族聚醯胺纖條體以及耐熱纖維乾式 摻合之後，利用氣流形成片材之方法；將觸媒粒子、芳香 族聚醯胺纖條體以及耐熱纖維於液體介質中分散混合之 後，噴出至液體透過性之支撐體，例如網或帶上而片材 化’除去液體而加以乾燥之方法等’其等中較好的是使用 水作為介質的所謂濕式抄造法。 作為濕式抄造法 …q 〜干领言有觸媒粒子、芳 香族聚醯胺纖條體以及耐熱纖維之水性聚料或者含有觸媒 粒子、芳香族聚酿胺纖條體以及耐熱纖維之2種或3種成分 之混合物的水性漿料送液至抄紙機加以分散之後進行脫 水、榨水以及乾燥操作，藉此捲取為片材之方法。作為抄 紙機’可利用長網式抄紙機、圓網式抄紙機、傾斜型抄紙 :、將其等組合而成之組合抄紙機等。以組合抄紙機進行 j造之情形時’將調配比率不同之漿料成形為片材後合為 一體’藉此可獲得包含複數個紙層之複合體片#。於抄造 :’可視需要使用分散性促進劑、凝集劑、消泡劑、紙力 八s 冑&除此之外亦可添加其他纖維狀成 二原纖化纖維成分(例如纖維質纖維、Μ系纖維、聚 添乙::、纖維，纖維、聚萘二甲酸乙二㈣ '、等以外之纖維狀成分及/或原纖化纖維成 135221.doc 200925192 ^之情形時，較理想的是其調配量以片材中總纖維成分之 合計重量為基準通常為50%以下、特別是娜以下。芳香 族聚酿胺纖條體具有作為黏合劑優異之特性，因此效率良 好地補足觸媒粒子、对熱纖維以及其他添加成分，故於本 發明之耐熱片材之製造中，原料成品率良好。 如此而獲得之耐熱片材，例如可藉由於一對平板之或金 屬製滾筒間，於高溫高壓下進行熱壓而提高密度、機械強 度。熱壓之條件，例如於使用金屬製滾筒之情形時’可例 象不溫度為100〜350°C、線壓為50〜3000 kg/cm之範圍内，但 並非限疋於該等。亦可並不進行加熱操作而僅於常溫下單 純地進行壓製。於熱壓時，亦可積層複數個对熱片材。亦 可以任意之順序進行複數次上述之熱壓加工。 本發明之耐熱片材具有如下之優異特性：（1)具備耐熱 性、阻燃性等優異之特性；（2)包含難以熱熔融之芳香族聚 酿胺纖條體，適度維持片材之空隙性，因此並不損及被處 > 理流體之移動性；（3)由於芳香族聚醯胺纖條體之保持性的 觸媒粒子之保持量較多；（4)芳香族聚醯胺之比重為1.4左 右’較小且輕量等；故可較好地用作含有於各種化學反應 之領域中’用以使液體狀或氣體狀之被處理流體改性或分 解之觸媒粒子的耐熱片材。 【實施方式】 以下’藉由實施例對本發明加以更具體之說明，但其等 實施例僅為單純之例示，並不對本發明之内容作任何限 定。 135221.doc •12· 200925192 (測定方法） (1) 片材之基重、厚度之測定 依據JIS C2111實施。 (2) 抗拉強度之測定 使用TENSILON拉伸試驗機，於寬度為15 mm、失盤間 隔為50 mm、拉伸速度為50 mm/min下實施。 (3)透氣度 將使用王研式透氣度計所測定出之透氣度換算為哥雷式 ❿ 透氣度。關於一系列之片材，該時間越短越可以說是多孔 質。 (4) 耐熱性 觀察於250°C下加熱1〇分鐘後的外觀。 (5) 觸媒性能 自片材之單面，以L0 NL/分鐘之流速導入包含Ν〇χ: 120 ppm、ΝΗ3 : 120 ppm以及 〇2 : 12 ν〇1%之 2〇〇β(：混合氣 ⑩ 冑，藉由NQX自動計測器測定自片材單面導人之混合氣體 的NOx濃度、通過片#自相反侧之面出來之混合氣體的 NOx濃度’藉由下式算出隐減少率，評價片材之觸媒性 • 能。 NOx減少率（％M(導人之混合氣體的Ν〇χ濃度）_(通過之 氣體的Ν〇Χ濃度）/(導入之混合氣體的NOx濃度）]χ 100 參考例1 (原料製備） 使用日本專利特公昭35_11851號公報中揭示的使用濕式 沈殿機之方法，製造聚間苯二甲酿間苯n纖條體，將 135221.doc -13- 200925192 其以纖維分離機、打漿機進行處理，將加拿大標準游離度 調整為100 ml’獲得芳香族聚醯胺纖條體。 另一方面，作為耐熱纖維，將杜邦公司製造之間位芳香 族聚醯胺纖維（NOMEX(註冊商標））切斷為長6 mm，作為原 料。 另一方面，為了比較，使用混合機將聚乙烯紙漿（三井 • 化學股份公司製造、SWP(註冊商標）E620、熔點為135。〇 於水中分散之後’以纖維分離機、打漿機進行處理，將加 〇 拿大標準濾水度調整為300 ml。 實施例1〜3 (片材之製造） 將芳香族聚酿胺纖條體、間位芳香族聚醯胺纖維以及作 為觸媒之翻粒子分別於水中分散而製作漿料。將其等漿料 進行混合以使芳香族聚醯胺纖條體、間位芳香族聚醯胺纖 維以及鉑成為如表1中所得之調配比率，藉由TAPPI式手抄 機制作片材狀物。繼而，以金屬製呀光輥於表丨中所示之 瘳 條件對其進行熱壓加工’獲得耐熱片材。 將如此而獲得之对熱片材的主要特性值示於表1。 135221.doc 14- 200925192The heat-resistant sheet of the present invention having the above characteristics can be generally produced by mixing the above-mentioned catalyst particles with an aromatic polyamine fibrid and heat-resistant fibers and then sheet-forming them. Specifically, for example, a method of forming a sheet by a gas flow after dry blending the above-mentioned catalyst particles, aromatic polyamine fibrids, and heat-resistant fibers can be applied; the catalyst particles and the aromatic polyamine fibrids are used. And the heat-resistant fibers are dispersed and mixed in a liquid medium, and then ejected to a liquid-permeable support, such as a mesh or a belt, and sheeted to remove a liquid and dried, etc., and water is preferably used as a medium. The so-called wet papermaking method. As a wet-type papermaking method...q~ dry-lead, there are catalyst particles, aromatic polyamine fibrids, and water-based aggregates of heat-resistant fibers or catalyst particles, aromatic polystyrene fibrids, and heat-resistant fibers. The aqueous slurry of the mixture of the three components or the three components is sent to a paper machine to be dispersed, and then subjected to dehydration, water extraction, and drying operations, thereby winding the film into a sheet. As the paper machine, a combination paper machine such as a long net type paper machine, a rotary net type paper machine, a tilt type papermaking machine, or the like can be used. In the case of a combination papermaking machine, the slurry having different blending ratios is formed into a sheet and joined together, whereby a composite sheet # comprising a plurality of paper layers can be obtained. For papermaking: 'Dispersibility promoters, aggregating agents, defoamers, paper force s 胄 amp & can also be used to add other fibrous fibrillated fiber components (such as cellulosic fibers, enamel) It is preferable that the fiber, the fiber, the fiber, the polyethylene naphthalate (tetra), and other fibrous components and/or fibrillated fibers are 135221.doc 200925192 ^ The blending amount is usually 50% or less, particularly preferably not more than the total weight of the total fiber component in the sheet. The aromatic polystyrene fibrid has excellent properties as a binder, so that the catalyst particles are efficiently complemented. For the heat fiber and other added components, the raw material yield is good in the manufacture of the heat-resistant sheet of the present invention. The heat-resistant sheet thus obtained can be, for example, by a pair of flat plates or a metal drum at a high temperature and a high pressure. The hot pressing is carried out to increase the density and the mechanical strength. The conditions of the hot pressing, for example, in the case of using a metal drum, can be exemplified as having a temperature of 100 to 350 ° C and a line pressure of 50 to 3000 kg / cm. But not It is limited to these. It is also possible to simply press at normal temperature without heating. In the case of hot pressing, a plurality of pairs of hot sheets may be laminated. The above-mentioned hot pressing may be carried out in any order. The heat-resistant sheet of the present invention has the following excellent characteristics: (1) excellent properties such as heat resistance and flame retardancy; and (2) inclusion of an aromatic polyamine fiber strip which is difficult to be thermally melted, and moderately maintaining the sheet. The porosity is so as not to impair the mobility of the fluid to be treated; (3) the amount of catalyst particles retained by the aromatic polyamine fibrids is large; (4) aromatic poly The specific gravity of guanamine is about 1.4, which is small and light, so it can be used as a catalyst for modifying or decomposing liquid or gaseous fluids in various chemical reactions. The present invention will be more specifically described by the following examples, but the examples are merely illustrative and are not intended to limit the scope of the invention. 135221.doc •12 · 200925192 (Measurement method) (1 The basis weight and thickness of the sheet were measured in accordance with JIS C2111. (2) Tensile strength was measured using a TENSILON tensile tester with a width of 15 mm, a disc loss interval of 50 mm, and a tensile speed of 50 mm/ (3) Air permeability The air permeability measured by the Wang Yan type air permeability meter is converted into the Gore type air permeability. For a series of sheets, the shorter the time, the more porous it is. (4) Heat resistance Observed after heating for 1 minute at 250 ° C. (5) Catalyst performance was introduced from one side of the sheet at a flow rate of L0 NL/min. Ν〇χ: 120 ppm, ΝΗ3: 120 ppm and 〇2: 12 ν〇1% of 2 〇〇β (: mixture gas 10 胄, measured by NOx concentration from the single-sided lead gas mixture by the NQX automatic measuring instrument, through the sheet # from the opposite side The NOx concentration of the mixed gas from the surface was calculated by the following equation, and the catalytic properties of the sheet were evaluated. NOx reduction rate (%M (Ν〇χ concentration of the mixed gas) _ (Ν〇Χ concentration of the gas passed through) / (NOx concentration of the mixed gas introduced)] χ 100 Reference Example 1 (Preparation of raw materials) Japanese Patent Publication No. Sho 35_11851 discloses a method for producing poly-m-phenylene benzene-n-fiber nitrite using a wet shovel machine, and 135221.doc -13-200925192 is treated with a fiber separator and a beater. The aromatic polyamide fiber strip was obtained by adjusting the Canadian standard freeness to 100 ml. On the other hand, as a heat-resistant fiber, a meta-aramid fiber (NOMEX (registered trademark)) manufactured by DuPont was cut. On the other hand, for comparison, a polyethylene pulp (manufactured by Mitsui Chemicals Co., Ltd., SWP (registered trademark) E620, melting point of 135 was used for comparison. After dispersing in water, the fiber was used. The separator and the beater are treated, and the standard filtration degree of the crucible is adjusted to 300 ml. Examples 1 to 3 (manufacture of sheet) Aromatic polystyrene fibrids, meta-aromatic polyamines Fiber and as The granules of the medium were dispersed in water to prepare a slurry, and the slurry was mixed to make the aromatic polyamine fibrid, the meta-aramid fiber and platinum into a blending ratio as shown in Table 1. A sheet material is produced by a TAPPI type hand-laid machine, and then hot-pressed by a metal-made light roller in the condition shown in the watch to obtain a heat-resistant sheet. The main characteristic values of the sheets are shown in Table 1. 135221.doc 14- 200925192
特性 單位 實施例1 實施例2 實施例3 原料組成 重量％ 芳香族聚醯胺纖條體 16 16 11 間位芳香族聚醯胺纖維 14 14 19 始 70 70 70 纖維之纖度 dtex 2.2 2.2 2.2 熱廢條件 溫度 °C 295 未熱壓 295 線壓 kg 沒 cm 100 100 基重 g/m2 185 185 185 厚度 μιη 230 300 230 密度 g/m3 0.80 0.62 0.80 體積分率 Vol% 芳香族聚醯胺纖條體 9.4 7.2 6.3 間位芳香族聚醯胺纖維 7.9 6 11 銘 2.7 2.1 2.7 空隙 80 84.7 80 透氣度 秒/100 cm3 350 340 50 透氣度/厚度 秒/100 cm3/pm 1.5 1.1 0.2 抗拉強度 kgf/15 mm 3.43 3.13 3.27 抗拉強度/厚度 gf/15 mm/μιη 14.9 10.4 14.2 外觀250°C10分鐘 無變化 無變化 無變化 NOx減少率 % ^95 90 81 實施例1〜3之耐熱片材的NOx減少率非常大，可認為觸 媒功能很充分，進而，即使於250°C、10分鐘之處理後外 135221.doc -15- 200925192 觀亦未發現變化，因此可用作汽車排氣用觸媒片材。 比較例1、2(片材之製造） 將芳香族聚醯胺纖條體、間位芳香族聚醯胺纖維、聚乙 烯紙漿以及作為觸媒之鉑粒子分別於水中分散而製作漿 料。將其等漿料進行混合以使芳香族聚酿胺纖條體、間位 芳香族聚醯胺纖維、聚乙烯纖維以及翻成為表2中所示之 調配比率，藉由TAPPI式手抄機製作片材狀物。繼而，藉 由金屬製石牙光輥於表2中所示之條件下對其進行熱壓加 工，獲得耐熱片材。Characteristic Unit Example 1 Example 2 Example 3 Raw Material Composition Weight % Aromatic Polyamine Fibrid 16 16 11 Meta-Aromatic Polyamide Fiber 14 14 19 Start 70 70 70 Fiber Denier dtex 2.2 2.2 2.2 Hot Waste Condition temperature °C 295 Unheated 295 Line pressure kg No cm 100 100 Basis weight g/m2 185 185 185 Thickness μιη 230 300 230 Density g/m3 0.80 0.62 0.80 Volume fraction Vol% Aromatic polyamide fiber 9.4 7.2 6.3 meta-aramid fiber 7.9 6 11 2.7 2.1 2.7 void 80 84.7 80 air permeability seconds / 100 cm3 350 340 50 air permeability / thickness seconds / 100 cm3 / pm 1.5 1.1 0.2 tensile strength kgf / 15 mm 3.43 3.13 3.27 Tensile strength/thickness gf/15 mm/μιη 14.9 10.4 14.2 Appearance 250°C for 10 minutes No change No change No change NOx reduction rate % ^95 90 81 The heat-resistant sheets of Examples 1 to 3 have a very low NOx reduction rate. Large, it can be considered that the catalyst function is sufficient, and even if it is not changed after the treatment at 250 ° C for 10 minutes, it can be used as a catalytic sheet for automobile exhaust. Comparative Examples 1 and 2 (Production of Sheet) Aromatic polyamine fibrids, meta-aramid fibers, polyethylene pulp, and platinum particles as a catalyst were dispersed in water to prepare a slurry. The slurry was mixed to make the aromatic polyamine fiber, the meta-aramid fiber, the polyethylene fiber, and the blending ratio shown in Table 2, and was produced by a TAPPI type hand-held machine. Sheet material. Then, it was subjected to hot press working under the conditions shown in Table 2 by a metal stone tooth roller to obtain a heat-resistant sheet.
將如此而獲得之片材的主要特性值示於表2 ❹ 135221.doc 16- 200925192 表2 特性 單位 比較例1 比較例2 原料組成 重量％ 芳香族聚醯胺纖條體 7 間位芳香族聚醯胺纖維 46 14 聚乙烯紙漿 16 在白 46 70 纖維之纖度 dtex 2.2 2.2 熱壓條件 溫度 °C 295 60 線壓 kgf/cm 100 100 基重 g/m2 185 185 厚度 μπι 230 230 密度 g/m3 0.80 0.80 體積分率 Vol% 芳香族聚醯胺纖條體 3.2 間位芳香族聚醯胺纖維 20.5 7.9 聚乙烯紙漿 13.9 在白 1.3 2.7 空隙 75 75.5 透氣度 秒/100 cm3 120 500 透氣度/厚度 秒/100 cm3/pm 0.5 2.2 抗拉強度 kg£^15 mm 2 2.9 抗拉強度/厚度 gf/15 mm/μιη 8.7 12.6 外觀250°Cl〇分鐘 無變化 收縮大 NOx減少率 % 70 不能測定 135221.doc -17- 200925192 比較例1之片材如表2所示，芳香族聚醢胺纖條體之體積 分率較低，因此並不保持鉑，鉑之體積分率變低。該片材 之NOx減少率較低’因此可認為觸媒功能並不充分。 又’比較例2之片材使用聚乙烯紙漿，因此耐熱性較 低’於250。(：、10分鐘之處理後收縮較大，且於通過2〇〇°C 之混合氣體時亦產生收縮。 自以上可知’本發明之耐熱片材由於芳香族聚酿胺纖條 體之較高的觸媒粒子捕獲效果，可較多地填充觸媒粒子， 且由於片材之多孔性可使被處理流體與觸媒粒子效率良好 接觸 ，g 且耐熱性亦較高，因此可較好地使用為汽車排氣 處理用觸媒等。 135221.doc 18-The main characteristic values of the sheet thus obtained are shown in Table 2 ❹ 135221.doc 16- 200925192 Table 2 Characteristic Unit Comparative Example 1 Comparative Example 2 Raw Material Composition Weight % Aromatic Polyamine Fibrid 7 Interstitial Aromatic Poly Indole fiber 46 14 Polyethylene pulp 16 in white 46 70 fiber denier dtex 2.2 2.2 hot pressing condition temperature °C 295 60 line pressure kgf/cm 100 100 basis weight g/m2 185 185 thickness μπι 230 230 density g/m3 0.80 0.80 Volume fraction Vol% Aromatic Polyamide Fibrid 3.2 Meta-Aromatic Polyamide Fiber 20.5 7.9 Polyethylene Pulp 13.9 in White 1.3 2.7 Void 75 75.5 Air Permeability Second / 100 cm3 120 500 Air Permeability / Thickness Second / 100 cm3/pm 0.5 2.2 Tensile strength kg£^15 mm 2 2.9 Tensile strength/thickness gf/15 mm/μιη 8.7 12.6 Appearance 250°Cl〇 min No change Shrinkage Large NOx reduction rate % 70 Cannot be measured 135221.doc - 17-200925192 As shown in Table 2, the sheet of the comparative example 1 has a low volume fraction of the aromatic polyamine fibrids, so platinum is not retained, and the volume fraction of platinum becomes low. The sheet has a low NOx reduction rate. Therefore, it is considered that the catalyst function is insufficient. Further, the sheet of Comparative Example 2 used polyethylene pulp, so that the heat resistance was as low as 250. (:, after 10 minutes of treatment, the shrinkage is large, and shrinkage also occurs when passing through a mixed gas of 2 ° C. From the above, it is known that the heat-resistant sheet of the present invention is higher due to the aromatic polystyrene fiber strip. The catalyst particle trapping effect can fill the catalyst particles more, and the porous material of the sheet can efficiently contact the catalyst fluid and the catalyst particles, and the heat resistance is also high, so that the catalyst particles can be used well. It is used as a catalyst for automobile exhaust treatment, etc. 135221.doc 18-