TW201200581A - Substrate material for ground grouting and ground grouting method - Google Patents

Abstract

To provide a substrate material which is used for ground grouting, can easily adjust gelation time even under the condition of not using phosphoric acid or under the condition of lowering the composition of usage quantity and has excellent permeability, durability and high bonding strength, and to provide a ground grouting method thereof. The substrate material for ground grouting uses colloidal silicon dioxide and silicon soda as main materials, contains inorganic acid and organic acid as gelling agent and has a pH of 2 to 7 at 25DEG C, preferably containing an inorganic acid and a pH buffer solution of organic acid whose logarithm of the reciprocal of acid dissociation constant (pKa) is 1.0 to 7.0 at 25DEG C, wherein the buffering range is pH 7 to 9.

Description

201200581 六、發明說明： 【發明所屬之技術領域】 本發明係關於含有膠態二氧化矽之二氧化矽粒子的地 盤注入用基盤材料及地盤注入工法’詳言之係關於使用於 軟弱地盤或防止地盤液化、基礎地盤的補強工程等的地盤 改良之地盤注入用基盤材料及地盤注入工法。 【先前技術】 注入軟弱地盤等使該地盤固結之地盤注入材，先前已 知有’石夕酸蘇打作為主材的注入材、以石夕酸蘇打與酸所組 成的酸性活性矽酸水溶液作為主材的注入材、或以中性膠 態二氧化料為主材的注入材等（專利文獻1及2)。 彳是該等的主入材均含有許多的驗或鹽類。驗或越 類的含量多’則長期間之中驗或鹽類由固結體游離脫逸： 發生固結體的收縮破壞，而產生固結體的強度下降等的耐 :性惡化。為改良如此的缺點，⑪幾年’提案有藉由陽離 子乂換樹脂或離子交換膜處理錢蘇打，去除㈣蘇打中 的驗的酸性活性料水溶液的藥液，…步並用膠態二 氧化石夕的地盤注人材（參照例如，專利文獻3〜5)。 專利文獻3所此載的地盤注入材係由酸性 矽與矽酸蘇打所組成，可得古故电、 ^軋化 材料調合的些微的差显使2』注入材之點優良，但 有所困難。- ”使凝膠化時聞的變動大而在實用上 專利文獻4所記載的地盤注入材，係於活性石夕酸加入 201200581 無機酸或酒石酸等的酸性劑而改善活㈣酸的敎性的注 入材，但只是將凝膠化時間延長數日，很難說在施工場所 的操作谷易。再者’亦有記载添加驗劑使凝膠化時間更長 而改良儲存穩定性的方法，但以該方法在材料調合的些微 的差異使凝膠化時聞的變動大而在實用上有所困難。 專利文獻5所記載的地盤注入材，係由活性矽酸與矽 酉文蘇打（無機酸或檸檬酸、葡糖酸等的有機酸、實施例只有 磷酸）所組成的注入材，活性矽酸水溶液，由於二氧化矽濃 度疋數重量％，故由製造地（工場）到施工地的運輸費變貴， 此外，由於數日就會凝膠化而無法在工程地大量儲存等的 問題尚未解決。 如上所述，使用活性矽酸的地盤注入材的使用僅限定 於一部分’而將膠態二氧化矽與矽酸蘇打的二成分作為主 材’調合凝膠化劑的地盤注入材被廣用。二成分之中凝膠 化時間主要是藉由矽酸蘇打與凝膠化劑的調合比率所調 節’作為凝膠化劑使用碌酸、硫酸或硫酸氫納。其中磷酸 係具有三階段的pKa值（酸解離常數的倒數的對數值， pKal = l. 83 ’ pKa2 = 6. 43，pKa3 = l 1.46)是容易調節凝膠化時 間的酸。但是，在湖泊或河川等有因磷的蓄積而造成優養 化的疑慮。另一方面，硫酸、硫酸氫鈉的pKa2為1. 74而 較小是較難調節凝膠化時間酸。 然而，上述膠態二氧化矽，係一般被稱為二氧化石夕溶 膠市售的商品，通常是對離子交換樹脂通過石夕酸蘇打而得 的活性矽酸藉由加熱等穩定化濃縮之二氧化矽濃度2〇〜50 201200581 重量％的產品，平均粒子徑為l〇_2〇nm左右。以該等膠態二 氧化石夕作為主材的地盤注入材是滲透性高的注人材’而耐 久性等亦優良。 [先行技術文獻] [專利文獻] [專利文獻1 ]特開昭54-73407號公報 [專利文獻2]特開平3_66794號公報 [專利文獻3]特開平4-136088號公報 [專利文獻4]特開平u_181425號公報 [專利文獻5ί特開2〇〇〇-1 09835號公報 【發明内容】 [發明所欲解決的課題] 因此，本發明係以提供，即使完全不使用磷酸，或減 夕使用置的組成，亦可容易調節凝膠化時間，對地盤的滲 透生優良’财久性或固結強度高的地盤注入用基盤材料及 使用其之地盤注入工法為目標。 [用以解決課題的手段] 本發明者們為解決如此之問題專心'進行研究的結果 發現以膠態二氧切與料蘇打作為主材，含有特定的g 作為凝膠化劑之地盤注人用基盤材料，凝膠化時間的⑹ 容易’對地盤的渗透性優良，且耐久性及固結強度高。 即本發明係-種地盤注人用基盤材料，其係、以膠態」 201200581 氧化矽與矽酸蘇打作為主材，含有無機酸與有機酸作為凝 膠化劑，並且在於25°C的pH在2~7。 更佳的是，包含無機酸及在於25t：的酸解離常數的倒 數的對數值（pKa)為1.〇~7.〇的有機酸的pH緩衝溶液，並 且在pH2〜7之間具有緩衝作用之地盤注入用基盤材料。 上述無機酸，以硫酸、磷酸或硫酸與磷酸的混合酸為 佳。 上述有機酸，以選自由草酸、馬來酸、酒石酸、蘋果 酸、檸檬酸及乳酸所組成之群為佳。 最佳的、.且α，备、無機酸為硫酸，有機酸為草酸或檸檬 酸0 再者，本發明亦提供將上述地盤注入用基盤材料注入 地盤的地盤注入工法。 [發明效果] .跟據本發明’可提供凝膠化時間的調節容易，對地盤 的〜透!·生優良且耐久性及固結強度高的地盤注入用基盤材 料。藉由將本發明的地盤注入用基盤材料注入地盤，可顯 著地提升地盤的穩定性。 以下’將本發明以其較佳的實施型態詳細地說明。 本發明的地盤注入用基盤材料之主材的膠態二氧 矽，並無特別限定’可使用市售的產品。此外，第二主 的矽酸蘇打亦無特別限定，可使用市售的產品。 201200581 本發明的地盤注入用基盤材料，含有無機酸及有機酸 作為凝膠化劑。無機酸’以硫酸、磷酸或硫酸與璃酸的混 合酸為佳，亦可使用該等的酸性鹽。如鹽酸或硝酸可完全 解離之強酸難以調節凝膠化時間而不佳。再者，使用硫酸 與磷酸之混合酸作為無機酸時，地盤注入用基盤材料中的 磷酸濃度以0. 4mo 1 / L以下為佳。 有機酸，以於25°C的酸解離常數的倒數的對數值（pKa) 在1·〇〜7.0的有機酸為佳，如此之有機酸，可舉天門冬胺 酸、丙胺酸、甘胺酸等胺基酸類；蟻酸、檸檬酸、醋酸、 草酸、酒石酸、乳酸、苯二甲酸、丙酸、馬來酸、酪酸、 頻果酸等的缓酸等。其中，以草酸（pKal = 1. 〇4， pKa2=3.82)、馬來酸（pKai=1.84 , pKa2=5.83)、酒石酸 (pKal = 2. 87，pKa2 = 3. 97)、蘋果酸（pKa = 3. 23，pKa=4. 77)、 酸（pKal = 2. 90’ pKa2 = 4. 35’ PKa3 = 5. 69)、乳酸（pKal = 3. 64) 更佳。由於草酸的分子量小，故重量當量的酸量大而最佳。 本發明的地盤注入用基盤材料的必要條件在於，以膠態二 氧化石夕及梦酸穌打為主材，含有上述的無機酸及有機酸作 為凝膠化劑，並且在於託^的邱在2〜7。 更佳的是本發明的地盤注入用基盤材料，包含組合無 、夂〆、在力25 C的酸解離常數的倒數的對數值（pKa)為 ^ 的有機酸的邱緩衝溶液，並且在邱之間具有 :衝作用為佳。於本發明者們的見識，凝膠化時間對注入 & pH的依存性很大，藉由將地盤注入用基盤材料的液組 成pH緩衝冷液’可使材料調合的些微的差異對pH的 201200581 變動很小，即使注入材的濃度因地下水而降低pH的變動很 小，因此凝膠化時間的變動變的些微，可容易地實質性地 實現既定的凝膠化時間。 本發明的地盤注入用I盤材肖的主#的膠態二氣化 石夕，並無特別限定，可使用市售的產品n第二主材 的石夕酸蘇打亦無特別限定，可使用市售的產品，以3號石夕 酸蘇打或4號矽酸蘇打為佳，3號矽酸蘇打有大量生產， 故廉價而佳。 使用於本發明的膠態二氧化石夕，係以石夕酸蘇打作為原 料而製造。矽酸蘇打係預先稀釋成二氧化矽濃度3〜7重量 %，使之與強酸性陽離子交換樹脂接觸去除納作成活性石夕酸 水溶液。活性碎酸水溶液係邱約2〜4，對活性碎酸水溶液 添加鹼劑成pH9~1G·5,加熱為6(M〇(TC使粒子進行成長 (成熟）’或對加熱為6{M00t的鹼劑添加活性矽酸水溶液 成pH9〜10.5’保持6〇〜1〇〇。(：的溫度使粒子進行成長（成 熟）。作成粒徑5〜2〇nm之後，以逆滲透濃縮使二氧化矽濃 度為ίο重量％以上。於本發明粒徑以5〜2〇nm為佳。 該膠態二氧化矽’至少含有！。重量%的二氧化矽粒子 為佳。再者，二氧化矽濃度以1〇〜3〇重量％的範圍内為佳。 為使簡化運輸、降低運輸成本，以高二氧化矽濃度的產品 為佳。 本發明的地盤注入用基盤材料，可進一步組合其他的 添加劑，例如，調合凝膠化時間調整劑使用。例如，使凝 膠化時間變短者，可使用消石灰、氣化妈、氣化鎮、氣氧 201200581 化鎂等。或併用水泥（波特蘭水泥、礬土水泥、高爐水泥） 及炫潰調整凝膠化時間或初期的凝膠強度。 本發明的地盤注入用基盤材料，係分別製作將膠態二 氧化石夕、無機酸、有機酸及水混合溶解的A液，以水稀釋 矽酸蘇打的B液，於注入時將A液及B液混合使用。 該地盤注入工法之1，有對不安定地盤（改良地盤）， 經由藥液注入管，將本發明的地盤注入用基盤材料加壓注 入，使之固結強化該地盤或止水使地盤穩定化的方法。此 外’該地盤改良工法，係將2種以上本發明的地盤注入用 基盤材料，例如溶膠粒徑或反應劑不同的地盤注入用基盤 材料以多相注入’使之固結強化該地盤或止水使地盤穩定 化方法。 再者本發明的地盤注人用基盤材料的凝膠化時 調整可為任意，最好是桶播A 、 疋根據其目的由數秒〜數十小 為佳。按照有無地下水、土質 、已 「κ 土負的種類、土砂堆積構造、、 入處周邊的狀態，可$彳> /主 此外，可使用1發模式、" J限制。 發模式、2發模式等。 [實施例] 惟本發明並非受 以下，藉由實施例詳細說明本發明 限於該等者。 (使用材料） 膠態二氧化矽：Silicad〇1 3〇 社製、二氧化矽濃度=30重量％ 曰本化學工 業株式會 201200581 矽酸蘇打：特殊矽酸蘇打、日太 + 1匕學工業换 二氧化矽濃度=26重量％、Na2〇 = ?曹、 武會社製 量X、比重1 3?201200581 VI. Description of the Invention: [Technical Field] The present invention relates to a substrate for injecting a substrate and a method for injecting a ground plate of a cerium oxide particle containing colloidal cerium oxide, in particular, for use in a weak site or prevention Site plating materials and site injection methods for the site improvement of site liquefaction and foundation site reinforcement projects. [Prior Art] Injecting materials into a site where the site is consolidated, such as a weak ground plate, is known as an injection material of the main material of the sulphuric acid soda, and an acidic active citric acid aqueous solution composed of soda ash and acid. An injection material of a main material or an injection material mainly composed of a neutral colloidal dioxide material (Patent Documents 1 and 2).彳 These are the main ingredients that contain many tests or salts. If the content of the test or the more is large, the salt or the salt is freely detached from the solid body during the long period of time: the shrinkage failure of the solid body occurs, and the strength of the solid body is deteriorated. In order to improve such shortcomings, in the past 11 years, it has been proposed to treat the soda by means of a cation exchange resin or an ion exchange membrane, and to remove the liquid of the acidic active material solution in the test of the soda, and to use colloidal silica. The site is filled with human materials (see, for example, Patent Documents 3 to 5). The site injecting material contained in Patent Document 3 is composed of acid strontium and strontium soda, and it is possible to obtain a slight difference in the combination of the ancient electricity and the rolled material, so that the point of the injection material is excellent, but it is difficult. . - "In the case of the site injecting material which is described in the patent document 4, the active material is added to the acidic agent such as inorganic acid or tartaric acid to improve the enthalpy of the active (tetra) acid. Injecting materials, but only extending the gelation time for several days, it is difficult to say that it is easy to operate in the construction site. In addition, there is also a method of adding a test agent to make the gelation time longer and improve the storage stability, but In this method, the slight difference in the blending of the materials makes the fluctuation of the gelation large and practically difficult. The site injecting material described in Patent Document 5 is composed of active tannic acid and scorpion soda (inorganic acid). Or an organic acid such as citric acid or gluconic acid, and only phosphoric acid in the example, and an active aqueous solution of citric acid, which is transported from the manufacturing site (worksite) to the construction site due to the concentration of cerium oxide. The cost becomes expensive, and the problem that it is gelled in a few days and cannot be stored in a large amount in engineering has not been solved. As described above, the use of the site injecting material using active tannic acid is limited to only a part of The two components of colloidal cerium oxide and strontium soda are widely used as the main material for the infusion of the gelling agent. The gelation time of the two components is mainly caused by the soda citrate and the gelling agent. The blending ratio is adjusted as 'gelling agent' using citric acid, sulfuric acid or sodium hydrogen sulfate. The phosphoric acid system has a three-stage pKa value (the logarithm of the reciprocal of the acid dissociation constant, pKal = l. 83 ' pKa2 = 6. 43 , pKa3 = l 1.46) is an acid which is easy to adjust the gelation time. However, there are doubts about the eutrophication caused by the accumulation of phosphorus in lakes or rivers. On the other hand, the pKa2 of sulfuric acid and sodium hydrogen sulfate is 1. 74 is smaller and it is more difficult to adjust the gelation time acid. However, the above colloidal cerium oxide is generally commercially available as a commercial product of the dioxide dioxide, usually for the ion exchange resin by the soda The obtained active citric acid is stabilized by heating or the like to concentrate the concentrated cerium oxide concentration of 2〇~50 201200581% by weight of the product, and the average particle diameter is about 1〇_2〇nm. The colloidal silica stone is used as the main The material of the site is a highly permeable material. In the case of the Japanese Patent Publication No. JP-A No. Hei. No. Hei. [Patent Document 4] Japanese Laid-Open Patent Publication No. Hei No. Hei. No. Hei. No. Hei. Phosphoric acid, or the composition of the use of the eve, can also easily adjust the gelation time, and the target of the site for injecting the substrate with good permeation or high consolidation strength and the site injection method using the same. [Means for Solving the Problem] The inventors have concentrated on 'solving such problems' and found that colloidal dioxo and soda are used as main materials, and a specific g is used as a gelling agent. With the base material, the gelation time (6) is easy to 'perfect to the ground plate, and the durability and the consolidation strength are high. That is, the present invention relates to a substrate material for a human dish, which is a colloidal state of 201200581 cerium oxide and cinnamic acid soda, containing a mineral acid and an organic acid as a gelling agent, and is at a pH of 25 ° C. In 2~7. More preferably, the logarithmic value (pKa) of the inorganic acid and the reciprocal of the acid dissociation constant at 25t: is a pH buffer solution of the organic acid of 〇~7.〇, and has a buffering effect between pH 2 and 7. The ground plate is filled with the base material. The above inorganic acid is preferably a mixed acid of sulfuric acid, phosphoric acid or sulfuric acid and phosphoric acid. The above organic acid is preferably selected from the group consisting of oxalic acid, maleic acid, tartaric acid, malic acid, citric acid, and lactic acid. Preferably, the α, the preparation, the inorganic acid is sulfuric acid, and the organic acid is oxalic acid or citric acid. Furthermore, the present invention also provides a method for injecting the above-mentioned site for injecting the substrate material into the ground. [Effect of the Invention] According to the present invention, it is easy to adjust the gelation time, and the base material for the site for injecting the ground is excellent in durability and high in consolidation strength. By injecting the substrate material for injecting the ground of the present invention into the ground plate, the stability of the ground plate can be remarkably improved. Hereinafter, the present invention will be described in detail with reference to preferred embodiments thereof. The colloidal dioxin of the main material for the substrate for injecting the substrate of the present invention is not particularly limited. A commercially available product can be used. Further, the second main succinic soda is not particularly limited, and a commercially available product can be used. 201200581 The base material for in-situ injection of the present invention contains a mineral acid and an organic acid as a gelling agent. The inorganic acid ' is preferably a mixed acid of sulfuric acid, phosphoric acid or sulfuric acid and glacial acid, and such an acidic salt can also be used. A strong acid such as hydrochloric acid or nitric acid which is completely dissociable is difficult to adjust the gelation time. The concentration of phosphoric acid in the ground material for the ground plate is preferably 0.4 mol / liter or less, in the case of using a mixed acid of sulfuric acid and phosphoric acid as the inorganic acid. The organic acid, the logarithmic value (pKa) of the reciprocal of the acid dissociation constant at 25 ° C is preferably 1. 1 ~ ~ 7.0 of organic acids, such organic acids, such as aspartic acid, alanine, glycine Amino acids; acid acids such as formic acid, citric acid, acetic acid, oxalic acid, tartaric acid, lactic acid, phthalic acid, propionic acid, maleic acid, butyric acid, and frequency acid. Among them, oxalic acid (pKal = 1. 〇4, pKa2=3.82), maleic acid (pKai=1.84, pKa2=5.83), tartaric acid (pKal = 2.87, pKa2 = 3.97), malic acid (pKa = 3. 23, pKa = 4.77), acid (pKal = 2. 90' pKa2 = 4. 35' PKa3 = 5. 69), lactic acid (pKal = 3. 64) is better. Since the molecular weight of oxalic acid is small, the amount of acid equivalent by weight is large and optimum. The necessary condition for the substrate for injecting the ground plate of the present invention is that the colloidal silica stone and the monic acid are used as the main material, and the above-mentioned inorganic acid and organic acid are contained as a gelling agent, and 2 to 7. More preferably, the substrate material for in-situ injection of the present invention comprises a combined buffer solution of an organic acid having a logarithmic value (pKa) of no reciprocal of the acid dissociation constant at a force of 25 C, and Between: has a good effect. As far as the inventors have discovered, the gelation time has a great dependence on the injection & pH. By injecting the ground disk into the liquid material of the substrate material, the pH buffer cold liquid can make a slight difference in the material to the pH. The variation of 201200581 is small, and even if the concentration of the injection material is small due to the groundwater, the fluctuation of the pH is small, so that the variation of the gelation time becomes small, and the predetermined gelation time can be easily substantially realized. The colloidal two-gas fossil of the main disk of the I disk material for the surface of the present invention is not particularly limited, and the commercially available product n, the second main material, is also not particularly limited, and the city can be used. For the products sold, it is better to use No. 3 soda ash soda or No. 4 citrate soda. No. 3 citrate soda is produced in large quantities, so it is cheap and good. The colloidal silica dioxide used in the present invention is produced by using ascorbic acid soda as a raw material. The soda citrate is preliminarily diluted to a concentration of cerium oxide of 3 to 7% by weight, and is contacted with a strongly acidic cation exchange resin to remove an aqueous solution of active oxalic acid. The active aqueous acid solution is about 2 to 4, and the alkaline agent is added to the active aqueous acid solution to pH 9~1G·5, and the heating is 6 (M〇(TC makes the particles grow (mature)' or the heating is 6{M00t). The alkaline agent is added with an active aqueous solution of citric acid to a pH of 9 to 10.5' to maintain 6 〇 to 1 〇〇. (The temperature of the particles is allowed to grow (mature). After the particle size is 5 to 2 〇 nm, the cerium oxide is concentrated by reverse osmosis. The concentration is ίο% by weight or more. The particle diameter of the present invention is preferably 5 to 2 Å. The colloidal cerium oxide contains at least 9% by weight of cerium oxide particles. Further, the concentration of cerium oxide is In the range of 1 〇 to 3 〇% by weight, in order to simplify transportation and reduce transportation cost, it is preferable to use a product having a high cerium oxide concentration. The substrate material for the site for injecting of the present invention may further be combined with other additives, for example, For blending gelation time adjuster, for example, if the gelation time is shortened, slaked lime, gasification mother, gasification town, gas oxygen 201200581 magnesium, etc., or cement (portal cement, bauxite) can be used. Cement, blast furnace cement) In the initial or initial gel strength. The substrate material for the site for injecting in the present invention is a liquid A which is prepared by mixing colloidal silica, inorganic acid, organic acid and water, and diluting the liquid B of soda citrate with water. The liquid A and the liquid B are mixed and used at the time of injection. The site is filled with a method of injecting the ground plate (improved site), and the substrate for injecting the substrate of the present invention is pressurized and injected through the chemical injection pipe. The method of solidifying and strengthening the ground plate or stopping the water to stabilize the ground plate. Further, the method for improving the ground plate is to inject two or more kinds of the base material for the ground plate of the present invention, for example, a substrate for injecting the ground having different sol diameters or reactants. The material is injected in a multi-phase manner to strengthen the ground plate or stop the water to stabilize the ground plate. Further, the gelation of the base material for the ground plate of the present invention can be adjusted at any time, preferably barrel A,疋 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 In the one-shot mode, the "J limit, the hair mode, the two-shot mode, etc. [Examples] The present invention is not limited by the following, and the present invention is not limited by the examples. (Materials used) Colloidal dioxide oxidation矽:Silicad〇1 3〇 system, cerium oxide concentration=30% by weight 曰本化学工业工会会201200581 矽 苏 soda: special citrate soda, 日太+ 1 匕学工业换2 dioxide concentration = 26% by weight , Na2〇 = ? Cao, Wuhui Society's production X, specific gravity 1 3?

磷酸：75%磷酸、日本化學工紫址a L 呆株式會社製Phosphoric acid: 75% phosphoric acid, manufactured by Nippon Chemical Chemicals Co., Ltd.

硫酸：75%硫酸、日本化學工章灶4, A 呆株式會社製 草酸二水和物、檸檬酸一水和物、民水私 馬來酸、DL-蘋果酸 乳酸、酒石酸：試藥 〈實施例1 >Sulfuric acid: 75% sulfuric acid, Japan Chemical Industry Co., Ltd. 4, A chloric acid dihydrate and citric acid, citric acid monohydrate, DL-malic acid lactic acid, tartaric acid: test drug Example 1 >

將B液的材料配方示於表1，A液係草酸濃度以 0. 1 mol/L，改變硫酸的調合量的材料配方，將a液的材料 配方記載於表2。二液的混合’係在攪拌下將B液迅速地 加入Λ液。測定混合液（注入材）的PH與凝膠化時間，將結 果記載於表3、圖1及®卜於PH測定使用麵電極式pH 計0The material formulation of the liquid B is shown in Table 1, and the liquid oxalic acid concentration of the liquid A is 0.1 mol/L, and the material formulation of the sulfuric acid is changed. The material formulation of the liquid a is shown in Table 2. The mixture of the two liquids was quickly added to the mash by stirring. The pH and gelation time of the mixed solution (injected material) were measured, and the results are shown in Table 3, Fig. 1 and Fig. 1 for pH measurement using a surface electrode type pH meter.

轰 1 __--T 7Q 9Π 妙酸蘇打(g)- 小記。）___- ίϋ. CK) 140 B液 '219.20 9ΠΠ ZUUBoom 1 __--T 7Q 9Π Soy soda (g) - small note. )___- ϋ. CK) 140 B liquid '219.20 9ΠΠ ZUU

表2.使用草酸之配方表（混合液中的草酸濃度 〇·lmol/1) 10 201200581Table 2. Formulation table using oxalic acid (oxalic acid concentration in the mixture 〇·lmol/1) 10 201200581

註）* 1 : G T為凝勝化時間（分 〈實施例2> 於Β液使用與實施例丨相同 的材枓，A液係草酴、潘 以0. 0 5mol/L，改變硫酸的調合量 次艰度 載於表4。測定混合液（注入材）的 -方s己 PH的凝膠化拉 果記載於表5、圖1及圖2。 "化時間’將結 表4.使用草酸之配方表r 酸濃度 衣匕t合液中的草Note) * 1 : GT is the time of condensing (see Example 2). The same material as in Example 枓 is used in the sputum, and the liquid A of the A liquid is 0. 0 5 mol/L, and the blending of sulfuric acid is changed. The difficulty of the measurement is shown in Table 4. The gelatinization of the measured liquid (injected material) - the pH of the hexa hexanol is shown in Table 5, Figure 1 and Figure 2. The "chemical time" will be used in Table 4. Oxalic acid formula table r acid concentration

No丁 No. 2 〜-- 18.15 膠態二氧化鈦(g) 18.15 18.15 75%硫酸(g) 7. 50 8. 50 9.00 A液 草酸2水和物(g) 2.52 2. 52 2. 52 水(g) 178.98 178.38 178. 09 小計(g)_ 207· 16 207. 56 207776 (ml) 200 200 2.52No Ding No. 2 ~-- 18.15 Colloidal Titanium Dioxide (g) 18.15 18.15 75% Sulfuric Acid (g) 7. 50 8. 50 9.00 A Liquid Oxalic Acid 2 Water and (g) 2.52 2. 52 2. 52 Water (g 178.98 178.38 178. 09 Subtotal (g)_ 207· 16 207. 56 207776 (ml) 200 200 2.52

一 177. 49 | 176, 208.56 200 表5.草酸濃度0.05mol/L的注入材 No. 1 No. 2 No. 3 5.77 混合液 (注入材） 註）*1 ·· GT為凝膠化時間（分） 〈比較例1&gt; 於B液使用與實施例 相同的材料 A液係不使用草 201200581 酸，^1堇 ϋί pjf- ύ^-L· . 文變硫酸的調合量的材料配方，將A液的材料配 方°己載於表6。測定混合液（注入材）的pH的凝膠化時間， 將結果記載於表7、圖1及圖2。 如圖1明瞭地表示，僅以硫酸（未添加草酸）則在於 __ U Q A » » 勺區域對硫酸調合量的pH變化急峻而非常難以控制 PH可推測凝膠化時間的控制也很困難。隨著草酸濃度的 增加’曲線的傾斜變的和緩，於草酸濃度〇 〇5m〇1/L以上 在pH3~4的範圍大致呈直線變化，pH的控制相對較容易， 可推測凝膠化時間的控制也變的容易。 良使用草酸的配方表177. 49 | 176, 208.56 200 Table 5. Injection material No. 1 No. 2 No. 3 5.77 Mixed liquid (injected material) Note) *1 ·· GT is the gelation time ( <Comparative Example 1> The same material as the liquid was used in the liquid B. The liquid A system was not used. 201200581 acid, ^1堇ϋί pjf- ύ^-L·. The material formulation of the blending amount of sulfuric acid, A The material formulation of the liquid is shown in Table 6. The gelation time of the pH of the mixed solution (injected material) was measured, and the results are shown in Table 7, FIG. 1 and FIG. As is clear from Fig. 1, only sulfuric acid (without adding oxalic acid) is located in the __ U Q A » » spoon region. The pH of the sulfuric acid blending amount changes sharply and is extremely difficult to control. It is also difficult to control the gelation time. As the concentration of oxalic acid increases, the slope of the curve becomes gentler, and the oxalic acid concentration 〇〇5m〇1/L or more changes substantially linearly in the range of pH 3~4, and the pH control is relatively easy, and the gelation time can be estimated. Control is also easy. Good use of oxalic acid formula table

No.l …Λ/私 No. 2 No. 3 No. 4 No. 5 No. 6 No. 7 二氧化鈦(g) 18.15 18.15 18.15 18.15 18.15 18.15 18.15 —硫酸(g) 9. 00 11.00 11.40 11.60 11.80 12.00 14. 00 A液 一2水和物(g) 0 0 0 0 0 0 0 水(g) 179. 61 178.41 178.17 178. 05 177.93 177.81 176.62 小計(g) 206.76 207. 56 207. 72 207. 80 207. 88 207. 96 208.77 (ml) 200 200 200 200 200 200 200 表7.不使用草酸的注入材 混合液 (注入材） No. 1 No. 2 No. 3 No. 4 No. 5 No. 6 No. 7 pH 8. 3 6.84 6 4. 93 2. 89 2. 53 1. 64 GT*1 0. 17 0. 17 1 15 2346 6335 12870 註: GT為凝膠化時間（分） 〈實施例3&gt; 表示使用各種有機酸、鱗酸及硫酸的注入材之例。B 液使用與實施例1相同的材料，A液係有機酸與磷酸的調 合量為一定，改變硫酸的調合量的材料配方，將A液的材 12 201200581 料配方記載於表8-1〜3。測定混合液（注入材）的pH的凝膠 化時間，將結果記載於表9 -1 ~ 3、圖3及圖4。 表8-1.使用草酸的配方表 A液 No. 1 No. 2 No. 3 No. 4 No. 5 No. 6 膠態二氧化鈦(g) 18.15 18.15 18.15 18.15 18.15 18.15 75%碟酸(g) 5.22 5. 22 5. 22 5.22 5. 22 5.22 75%硫酸(g) 3.50 5.00 6.00 7. 00 8.00 9.00 草酸2水和物(g) 5.00 5.00 5.00 5.00 5. 00 5.00 水(g) 176.97 176.07 175.47 174.87 174. 27 173.68 小計(g) 208.34 209. 44 209. 84 210.24 210. 64 211.05 (ml) 200 200 200 200 200 200 表8-2.使用檸檬酸的配方表 A液 No. 1 No. 2 No. 3 No. 4 No. 5 No. 6 膠態二氧化鈦(g) 18.15 18.15 18.15 18.15 18.15 18.15 75%填酸(g) 5. 22 5.22 5. 22 5.22 5.22 5. 22 75%硫酸(g) 4. 00 5.00 6. 00 7.00 8.00 9.00 草酸1水和物(g) 8.40 8.40 8. 40 8.40 8.40 8.40 水(g) 174. 26 173.66 173.06 172.46 171.86 171.26 小計(g) 210.03 210.43 210.83 211.23 211.63 212. 03 (ml) 200 200 200 200 200 200 表8-3.使用酒石酸的配方表 A液 No. 1 No. 2 No. 3 No. 4 No. 5 No. 6 膠態二氧化鈦(g) 18.15 18.15 18.15 18.15 18.15 18.15 75%鱗酸(g) 5. 22 5.22 5.22 5. 22 5. 22 5.22 75%硫酸(g) 4.00 5.00 6. 00 7. 00 8.00 9.00 酒石酸(g) 6. 00 6.00 6.00 6. 00 6.00 6. 00 水(g) 175.89 175.29 174. 69 174.10 173.50 172.90 小計(g) 209. 26 209. 66 210.06 210.47 210.87 211.27 (ml) 200 200 200 200 200 200 13 201200581 表9-1.不使用草酸的注入材 混合液 (注入材） No. 1 No. 2 No. 3 No. 4 No. 5 No. 6 pH 5.77 3. 90 3.28 2. 63 2. 20 1.94 GT*丨 3.9 176 620 2330 5600 9500 註）*1 : GT為凝膠化時間（分） 表9-2.不使用檸檬酸的注入材 混合液 (注入材） No. 1 No. 2 No. 3 No. 4 No. 5 No. 6 pH 4.72 4. 27 3.80 3.31 2.89 2.51 Gf 33.1 82. 7 215 580 1370 3000 註）*1 : GT為凝膠化時間（分） 表9 - 3.不使用酒石酸的注入材 混合液 (注入材） No.l No. 2 No. 3 No. 4 No. 5 No. 6 pH 5.13 4.08 3.58 3.18 2. 82 2.49 GT*1 14.4 122 337 760 1580 3100 註）*1 : GT為凝膠化時間（分） 〈比較例2&gt; 表示不使用有機酸’僅使用磷酸與硫酸的注入材之 例。於B液使用與實施例1相同的材料，A液係磷 5量為一定，改變硫酸的調合量的材料配方，將A液 叶配方記載於表1 〇-卜2。測定混合液（注入材）的pH的 膠化時間，將結果記載於表11-1〜2、圖3及圖4。认疑 士 Λχ. &gt;7^ 圖 ρΗ3〜4的區域，於添加有機酸的試料ρΗ對硫酸濃声 4、加量）呈直線變化。此外，相較於不使用有機酸I / 地抑制其變化的大小。 者很強 14 201200581 表1 0 -1.不使用有機酸的配方表（混合液中的鱗酸漢度 0 1 mo 1/L)No.l No. 2 No. 3 No. 4 No. 5 No. 6 No. 6 No. 6 No. 7 No. 7 No. 7 No. 7 No. 7 No. 7 No. 7 No. 7 No. 7 No. 7 No. 7 No. 7 No. 7 No. 7 No. 7 No. 7 No. 7 No. 7 No. 7 No. 7 No. 7 No. 7 No. 7 No. 7 No. 7 No. 7 No. 7 No. 7 No. 7 No. 00 A liquid- 2 water and substance (g) 0 0 0 0 0 0 0 water (g) 179. 61 178.41 178.17 178. 05 177.93 177.81 176.62 Subtotal (g) 206.76 207. 56 207. 72 207. 80 207. 88 207. 96 208.77 (ml) 200 200 200 200 200 200 200 Table 7. Infusion material mixture (injection material) without oxalic acid No. 1 No. 2 No. 3 No. 4 No. 5 No. 6 No. 6 No. 7 pH 8. 3 6.84 6 4. 93 2. 89 2. 53 1. 64 GT*1 0. 17 0. 17 1 15 2346 6335 12870 Note: GT is the gelation time (minutes) <Example 3> Examples of various organic acid, scalylic acid and sulfuric acid injection materials are used. The liquid B is the same as that of the first embodiment, the blending amount of the organic acid and the phosphoric acid of the liquid A is constant, and the material formulation for changing the blending amount of the sulfuric acid is described in Table 8-1 to 3 of the material of the liquid 12 201200581. . The gelation time of the pH of the mixed solution (injected material) was measured, and the results are shown in Tables 9 -1 to 3, Figs. 3 and 4. Table 8-1. Formulation using oxalic acid Table A Liquid No. 1 No. 2 No. 3 No. 4 No. 5 No. 6 Colloidal titanium dioxide (g) 18.15 18.15 18.15 18.15 18.15 18.15 75% dish acid (g) 5.22 5. 22 5. 22 5.22 5. 22 5.22 75% sulfuric acid (g) 3.50 5.00 6.00 7. 00 8.00 9.00 Oxalic acid 2 water and substance (g) 5.00 5.00 5.00 5.00 5. 00 5.00 Water (g) 176.97 176.07 175.47 174.87 174 27 173.68 Subtotal (g) 208.34 209. 44 209. 84 210.24 210. 64 211.05 (ml) 200 200 200 200 200 200 Table 8-2. Formulation using citric acid Table A Liquid No. 1 No. 2 No. 3 No. 4 No. 5 No. 6 Colloidal titanium dioxide (g) 18.15 18.15 18.15 18.15 18.15 18.15 75% acid filling (g) 5. 22 5.22 5. 22 5.22 5.22 5. 22 75% sulfuric acid (g) 4. 00 5.00 6. 00 7.00 8.00 9.00 Oxalic acid 1 water and substance (g) 8.40 8.40 8. 40 8.40 8.40 8.40 Water (g) 174. 26 173.66 173.06 172.46 171.86 171.26 Subtotal (g) 210.03 210.43 210.83 211.23 211.63 212. 03 (ml) 200 200 200 200 200 200 Table 8-3. Formulation using tartaric acid Table A Liquid No. 1 No. 2 No. 3 No. 4 No. 5 No. 6 Colloidal titanium dioxide (g) 18.15 18.15 18.15 18.15 18.15 18.15 75% scale Acid (g) 5. 22 5.22 5.22 5. 2 2 5. 22 5.22 75% sulfuric acid (g) 4.00 5.00 6. 00 7. 00 8.00 9.00 Tartaric acid (g) 6. 00 6.00 6.00 6. 00 6.00 6. 00 Water (g) 175.89 175.29 174. 69 174.10 173.50 172.90 Subtotal (g) 209. 26 209. 66 210.06 210.47 210.87 211.27 (ml) 200 200 200 200 200 200 13 201200581 Table 9-1. Infusion material mixture (injection material) without oxalic acid No. 1 No. 2 No. 3 No. 4 No. 5 No. 6 pH 5.77 3. 90 3.28 2. 63 2. 20 1.94 GT*丨3.9 176 620 2330 5600 9500 Note)*1 : GT is gelation time (minutes) Table 9-2. Injectable material mixture (injection material) without using citric acid No. 1 No. 2 No. 2 No. 4 No. 5 No. 6 No. 6 No. 6 No. 6 No. 6 No. 6 No. 6 No. 6 No. 6 No. 6 No. 6 No. 6 No. 6 No. 6 *1 : GT is the gelation time (minutes). Table 9 - 3. Injection material mixture (injection material) without tartaric acid No.1 No. 2 No. 3 No. 4 No. 5 No. 6 No. 5 pH 5.13 4.08 3.58 3.18 2. 82 2.49 GT*1 14.4 122 337 760 1580 3100 Note) *1 : GT is the gelation time (minutes) <Comparative Example 2> Indicates that no organic acid is used'. Only phosphoric acid and sulfuric acid are used. example. In the case of the liquid B, the same material as in the first embodiment was used, and the amount of phosphorus in the liquid A was constant, and the material formulation in which the amount of sulfuric acid was adjusted was changed. The formula of the liquid A was described in Table 1 〇-b. The gelation time of the pH of the mixed solution (injected material) was measured, and the results are shown in Tables 11-1 to 2, Fig. 3 and Fig. 4 .认士 Λχ. &gt;7^ Figure ρΗ3~4 area, the sample added with organic acid ρΗ to the sulfuric acid thick sound 4, the amount) changes linearly. In addition, the magnitude of the change is suppressed compared to the use of the organic acid I / ground. Very strong 14 201200581 Table 1 0 -1. Formulation table without organic acid (salt acid in mixture 0 1 mo 1/L)

No. 1 No. 2 No. 3 No. 4 No. 5 ------ No· 6 一 膠態二氧化鈦(g) 18.15 18.15 18.15 18.15 18.15 J8J5_ 75%磷酸(g) 5.22 5.22 5.22 5. 22 5.22 5.22 --- A液 75%硫酸(g) 8.00 8.50 9. 00 9. 25 9.50 1 有機酸(g) 0 0 0 0 0 0 一 一--- 水(g) 176.91 176.61 176.31 176.16 176.01 J75JL 小計(g) 208. 28 208. 48 208. 68 208. 78 208. 88 209. 08 (ml) 200 200 200 200 200 200 .—二— 表10-2.不使用有機酸的配方表（混合液中的磷酸濃度 0.2mol/L) A液 No. 1 No. 2 No. 3 No. 4 No. 5 膠態二氧化鈦(g) 18.15 18.15 18.15 18.15 」8.15 75%磷酸(g) 10.43 10.43 10.43 10.43 10.43 75%硫酸(g) 5.00 6. 〇〇 6.50 7. 00 」·〇〇 有機酸(g) 0 0 0 0 0 水(g) 175.40 174.81 174.51 174.21 173. 61 小計(g) 203. 77 204.18 204.38 204.58 204.98 (ml) 200 200 200 200 200 表1卜1.不使用有機酸的注入材（混合液中的磷酸濃度 0.lmol/L) 混合液 (注入 材） No.l No. 2 — 一 No. 3 No. 4 No. 5 _No.6 pH 6.20 5.87 5.19 3.85 3. 06 2. 57 GT*' 1.6 3.2 13 195 970 2600 註）*1 : GT為凝膠化時間（分） 15 201200581 表11 -2.不使用檸檬酸的注入材（混合液中的磷酸濃度 0.2mol/L) 混合液（注 入材） No. 1 No. 2 No. 3 No. 4 No. 5 pH 6.10 5.46 4. 64 3.13 2.46 Gf 2.2 7.3 39 842 3300 註）*1 : GT為凝膠化時間（分） 〈實施例4&gt; 表示使用有機酸與磷酸的注入材之例。將B液的配方 表示於表1 2。A液係以表1 3所記载的配方為基礎，改變添 加量調合各種有機酸’最後加水成300ml。測定混合液（注 入材）的pH的凝膠化時間’於表1 4-卜7記載A液的材料配 方。亦實施於有機酸之外對A液進一步追加添加磷酸的配 方。測定AB混合液（注入材）的pH與凝膠化時間，將其結 果記載於圖5及圖6。在於圖中pH3〜4的區域，於添加有 機酸的試料較添加磷酸PH的變化緩和而呈直線變化。其 中，由於草酸（pKal = l. 〇4、pKa2 = 3. 82)由於pKa小而斜率 稍微變抖。 表12. 矽酸蘇打(g) 79.20 B液 水(g) 40 小計(g) 119.20 (ml) 100 表13. A液 — 膠態二氧化鈦(g) 18.2 基礎配方 75%磷酸 5.0 水(g) 250. 0 16 201200581 總量調整分的水 水（追加分） 平衡 小計(ml) 300 表14-1.使用草酸的配方表 A液 No. 1 No. 2 No. 3 No. 4 No. 5 膠態二氧化鈦(g) 18.2 18.2 18.2 18.2 18.2 75%碟酸(g) 5.0 5.0 5.0 5.0 5.0 草酸2水和物(g) 5.2 7.2 9.2 11.2 13.2 水(g) 277.7 276.5 275.3 274.1 272.9 小計(g) 306.1 306.9 307.7 308.5 309.3 (ml) 300 300 300 300 300 表14-2.使用馬來酸的配方表 A液 No. 1 No. 2 No. 3 No. 4 膠態二氧化鈦(g) 18.2 18.2 18.2 18.2 75%填酸(g) 5.0 5.0 5.0 5.0 馬來酸(g) 5.6 7.6 9.6 13.6 水(g) 277.4 276.1 274.9 272.3 小計(g) 306.2 306.9 307.7 309.1 (ml) 300 300 300 300 表14-3.使用檸檬酸的配方表 No. 1 No. 2 No. 3 No. 4 No. 5 No. 6 No. 7 膠態二氧化鈦(g) 18.2 18.2 18.2 18.2 18.2 18.2 18.2 75%鱗酸(g) 5.0 5.0 5.0 5.0 5.0 5.0 5.0 A液 草酸1水和物(g) 6.6 8.6 10.6 12.6 16.6 22.6 30.6 水(g) 276.6 275.3 274.0 272.7 270.1 266.2 261.0 小計(g) 306.4 307.1 307.8 308.5 309.9 312.0 314.8 (ml) 300 300 300 300 300 300 300 17 201200581 表14-4.使用DL-蘋果酸的配方表 A液 No. 1 No. 2 No. 3 No. 4 No. 5 No. 6 膠態二氧化鈦 (g) 18.2 18.2 18.2 18.2 18.2 18.2 75%磷酸(g) 5.0' 5.0 5.0 5.0 5.0 5.0 DL-蘋果酸(g) 4.9 8.9 12.9 16.9 22.9 28.9 水(g) 277.9 275.4 272.9 270.4 266.7 262.9 小計(g) 306.0 307.5 309.0 310.5 312.8 315.0 (ml) 300 300 300 300 300 300 表14-5.使用乳酸的配方表 A液 No. 1 No. 2 No. 3 No. 4 No. 5 膠態二氧化鈦(g) 18.2 18.2 18.2 18.2 18.2 75%碟酸(g) 5.0 5.0 5.0 5.0 5.0 乳酸(g) 13.1 15.1 18.1 23.1 28.1 水(g) 270.1 268.4 265. 9 261.8 257.7 小計(g) 306.4 306.7 307. 2 308.1 309.0 (ml) 300 300 300 300 300 表14-6.使用酒石酸的配方表 A液 No. 1 No. 2 No. 3 No. 4 No. 5 No. 6 膠態二氧化鈦(g) 18.2 18.2 18.2 18.2 18.2 18.2 75%磷酸(g) 5.0 5.0 5.0 5.0 5.0 5.0 酒石酸(g) 4.3 6.3 8.3 10.3 24.3 34.3 水(g) 278.5 277.3 276.2 275.0 267.1 261.4 小計(g) 306.0 306.8 307.7 308.5 314.6 318. 9 (ml) 300 300 300 300 300 300 表14-7.使用磷酸的配方表 A液 No. 1 No. 2 No. 3 No. 4 膠態二氧化鈦(g) 18.2 18.2 18.2 18.2 750/〇 磷酸(g) 19.0 22.1 25.3 28.4 18 201200581 水(g) 270.1 268.4 265.9 261. 8 小計(g) ---------- 306.4 306.7 307.2 308.1 (ml) ' ------ 300 300 300 300 【圖式簡單說明】 圖1係表示地盤注入用基盤材料中的硫酸濃度及pH的 關係之圖。 圖2係表示地盤注入用基盤材料中的硫酸濃度及凝膠 化時間的關係之圖。 圖3係表示地盤注入用基盤材料中的硫酸濃度及pH的 關係之圖。 圖4係表示地盤注入用基盤材料中的硫酸濃度及凝膠 化時間的關係之圖。 圖5係表示地盤注入用基盤材料中的酸濃度（去除基 質的磷酸分）及pH的關係之圖。 圖6係表示盤注入用基盤材料中的酸濃度（去除基質 的碟酸分）及凝膠化時間的關係之圖。 【主要元件符號說明】 無 19No. 1 No. 2 No. 2 No. 4 No. 6 No. 6 No colloidal titanium dioxide (g) 18.15 18.15 18.15 18.15 18.15 J8J5_ 75% phosphoric acid (g) 5.22 5.22 5.22 5. 22 5.22 5.22 --- A liquid 75% sulfuric acid (g) 8.00 8.50 9. 00 9. 25 9.50 1 organic acid (g) 0 0 0 0 0 0 one by one --- water (g) 176.91 176.61 176.31 176.16 176.01 J75JL subtotal ( g) 208. 28 208. 48 208. 68 208. 78 208. 88 209. 08 (ml) 200 200 200 200 200 200 .—two — Table 10-2. Formulation table without organic acid (in the mixture) Phosphoric acid concentration 0.2 mol/L) A liquid No. 1 No. 2 No. 3 No. 4 No. 5 Colloidal titanium dioxide (g) 18.15 18.15 18.15 18.15 "8.15 75% phosphoric acid (g) 10.43 10.43 10.43 10.43 10.43 75% sulfuric acid (g) 5.00 6. 〇〇6.50 7. 00 ”〇〇Organic acid (g) 0 0 0 0 0 Water (g) 175.40 174.81 174.51 174.21 173. 61 Subtotal (g) 203. 77 204.18 204.38 204.58 204.98 (ml ) 200 200 200 200 200 Table 1 1. Injecting material without organic acid (concentration of phosphoric acid in the mixed solution 0.1 mol/L) Mixed solution (injected material) No.l No. 2 — No. 3 No. 4 No. 5 _No.6 pH 6.20 5.87 5.19 3.85 3. 06 2. 57 GT*' 1.6 3. 2 13 195 970 2600 Note) *1 : GT is gelation time (minutes) 15 201200581 Table 11 -2. Injecting material without citric acid (phosphoric acid concentration in mixed solution 0.2 mol/L) Mixed solution (injection material) No. 1 No. 2 No. 3 No. 4 No. 5 pH 6.10 5.46 4. 64 3.13 2.46 Gf 2.2 7.3 39 842 3300 Note) *1 : GT is gelation time (minutes) <Example 4> An example of using an organic acid and phosphoric acid injection material. The formulation of liquid B is shown in Table 12. The liquid A was based on the formulation described in Table 13 and the amount of the organic acid was changed by adding the amount of water to the final addition of 300 ml. The gelation time of the pH of the mixed solution (injection material) was measured. The material formulation of the liquid A is shown in Table 1 - 4b. A compound in which phosphoric acid is further added to the liquid A other than the organic acid is also carried out. The pH and gelation time of the AB mixed solution (injected material) were measured, and the results are shown in Fig. 5 and Fig. 6. In the region of pH 3 to 4 in the figure, the sample to which the organic acid was added changed linearly as compared with the change in the pH of the added phosphoric acid. Among them, the slope is slightly dithered due to the small pKa due to oxalic acid (pKal = l. 〇4, pKa2 = 3.82). Table 12. Soda Citrate (g) 79.20 B Water (g) 40 Subtotal (g) 119.20 (ml) 100 Table 13. Liquid A - Colloidal Titanium Dioxide (g) 18.2 Basic Formulation 75% Phosphoric Acid 5.0 Water (g) 250 0 16 201200581 Water and water (additional points) of the total adjustment amount Balanced subtotal (ml) 300 Table 14-1. Formulation using oxalic acid Table A Liquid No. 1 No. 2 No. 3 No. 4 No. 5 Colloidal state Titanium dioxide (g) 18.2 18.2 18.2 18.2 18.2 75% dish acid (g) 5.0 5.0 5.0 5.0 5.0 Oxalic acid 2 water and substance (g) 5.2 7.2 9.2 11.2 13.2 Water (g) 277.7 276.5 275.3 274.1 272.9 Subtotal (g) 306.1 306.9 307.7 308.5 309.3 (ml) 300 300 300 300 300 Table 14-2. Formulation using maleic acid Table A Liquid No. 1 No. 2 No. 3 No. 4 Colloidal titanium dioxide (g) 18.2 18.2 18.2 18.2 75% acid filling (g) 5.0 5.0 5.0 5.0 Maleic acid (g) 5.6 7.6 9.6 13.6 Water (g) 277.4 276.1 274.9 272.3 Subtotal (g) 306.2 306.9 307.7 309.1 (ml) 300 300 300 300 Table 14-3. Formulation using citric acid Table No. 1 No. 2 No. 3 No. 4 No. 2 No. 6 No. 6 No. 6 No. 6 Colloidal titanium dioxide (g) 18.2 18.2 18.2 18.2 18.2 18.2 18.2 75% scaly acid (g) 5.0 5.0 5.0 5.0 5.0 5.0 5.0 A Liquid oxalic acid 1 Water and substances (g) 6.6 8.6 10.6 12.6 16.6 22.6 30.6 Water (g) 276.6 275.3 274.0 272.7 270.1 266.2 261.0 Subtotal (g) 306.4 307.1 307.8 308.5 309.9 312.0 314.8 (ml) 300 300 300 300 300 300 300 17 201200581 Table 14- 4. Formulation A using DL-malic acid No. 1 No. 2 No. 3 No. 4 No. 5 No. 6 Colloidal titanium dioxide (g) 18.2 18.2 18.2 18.2 18.2 18.2 75% phosphoric acid (g) 5.0' 5.0 5.0 5.0 5.0 5.0 DL-malic acid (g) 4.9 8.9 12.9 16.9 22.9 28.9 Water (g) 277.9 275.4 272.9 270.4 266.7 262.9 Subtotal (g) 306.0 307.5 309.0 310.5 312.8 315.0 (ml) 300 300 300 300 300 300 Table 14- 5. Formulation using lactic acid Table A Liquid No. 1 No. 2 No. 3 No. 4 No. 5 Colloidal titanium dioxide (g) 18.2 18.2 18.2 18.2 18.2 75% dish acid (g) 5.0 5.0 5.0 5.0 5.0 Lactic acid (g 13.1 15.1 18.1 23.1 28.1 Water (g) 270.1 268.4 265. 9 261.8 257.7 Subtotal (g) 306.4 306.7 307. 2 308.1 309.0 (ml) 300 300 300 300 300 Table 14-6. Formulations using tartaric acid Table A Liquid No. 1 No. 2 No. 3 No. 4 No. 5 No. 6 Colloidal titanium dioxide (g) 18.2 18.2 18.2 18.2 18.2 18.2 75% phosphoric acid (g) 5.0 5.0 5.0 5.0 5.0 5.0 Tartaric acid (g) 4.3 6.3 8.3 10.3 24.3 34.3 Water (g) 278.5 277.3 276.2 275.0 267.1 261.4 Subtotal (g) 306.0 306.8 307.7 308.5 314.6 318. 9 (ml) 300 300 300 300 300 300 Table 14-7. Formulation No. A No. 1 No. 2 No. 3 No. 4 Colloidal titanium dioxide (g) 18.2 18.2 18.2 18.2 750/〇phosphoric acid (g) 19.0 22.1 25.3 28.4 18 201200581 Water (g) 270.1 268.4 265.9 261. 8 Subtotal (g) ---------- 306.4 306.7 307.2 308.1 (ml) ' ------ 300 300 300 300 [Simple description of the diagram] Figure 1 shows the sulfuric acid in the base material for the site injection. Diagram of the relationship between concentration and pH. Fig. 2 is a graph showing the relationship between the sulfuric acid concentration and the gelation time in the base material for the ground floor injection. Fig. 3 is a view showing the relationship between the sulfuric acid concentration and the pH in the base material for the ground floor injection. Fig. 4 is a graph showing the relationship between the sulfuric acid concentration and the gelation time in the base material for the ground floor injection. Fig. 5 is a graph showing the relationship between the acid concentration (removal of the phosphate component of the substrate) and the pH in the substrate material for the ground floor injection. Fig. 6 is a graph showing the relationship between the acid concentration (the removal of the acid portion of the substrate) and the gelation time in the substrate material for disk implantation. [Main component symbol description] None 19

Claims (1)

201200581 七、申請專利範圍： _ .種地盤注入用基盤材料，其特徵在於：以膠態二 氧化硬及石夕酿益 穌打作為主材，含有無機酸及有機酸作為凝 膠化並且在於说的阳為2小 2.如專利申請範圍第1項所述的地盤注入用基盤材 料’其中包含組合在於251的酸解離常數的倒數的對數值 (pKa)為1‘〇〜7.〇的有機酸與無機酸的pH緩衝溶液，並且在 於PH2〜7之間具有緩衝作用。 3 如專利申請範圍第1或2項所述的地盤注入用基盤 材料其中上述無機酸係硫酸、磷酸或硫酸與磷酸之混合 酸。 4.如專利申請範圍第1至3項中任一項所述的地盤注 入用基盤材料，其中上述有機酸係選自由草酸、馬來酸、 酒石酸、蘋果酸、檸檬酸及乳酸等所組成之群。 5 ·如專利申請範圍第1或2項所述的地盤注入用基盤 材料，其中上述無機酸係硫酸，上述有機酸係草酸或棒樣 酸。 6. —種地盤注入工法’將專利申請範圍第1至5項中 任一項所述的地盤注入用基盤材料注入地盤。 20201200581 VII. Patent application scope: _. The base material for seeding site is characterized by: colloidal oxidized hard and Shixi brewing Yishen as the main material, containing inorganic acid and organic acid as gelatinization and arguing The cation is 2 small 2. The base material for the site for injecting according to the first aspect of the patent application, wherein the logarithmic value (pKa) of the reciprocal of the acid dissociation constant of 251 is 1'〇~7. A pH buffer solution of an acid and a mineral acid, and has a buffering effect between pH 2 and 7. The substrate material for site injecting according to claim 1 or 2, wherein the inorganic acid is sulfuric acid, phosphoric acid or a mixed acid of sulfuric acid and phosphoric acid. 4. The substrate material for a site for injecting according to any one of claims 1 to 3, wherein the organic acid is selected from the group consisting of oxalic acid, maleic acid, tartaric acid, malic acid, citric acid, and lactic acid. group. The substrate material for site injecting according to the first or second aspect of the invention, wherein the inorganic acid is sulfuric acid, and the organic acid is oxalic acid or bar acid. 6. A method of injecting a ground material into a ground plate according to any one of the first to fifth aspects of the invention. 20