JP2007077040A - Method for producing aminomethylenephosphonic acid - Google Patents
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Abstract
Description
本発明は、高純度アミノメチレンホスホン酸の製造方法に関するものであり、アミノメチレンホスホン酸類は、多くの金属に配位するキレート剤として周知であり、過酸化物の分解防止安定剤等多種多様な用途に用いられている。 The present invention relates to a method for producing high-purity aminomethylene phosphonic acid, and aminomethylene phosphonic acids are well known as chelating agents that coordinate to many metals, and are used in a wide variety of ways such as peroxide decomposition prevention stabilizers. Used for applications.
近年、半導体産業では工程の微細化が進んでおり、シリコンウエハ清浄度の向上、工程簡略化を目的とするシリコンウエハの洗浄液として用いられている過酸化水素水、アンモニア水等にアミノメチレンホスホン酸を添加し、キレート能を付加してウエハ上の金属を除去する手法が用いられている。 In recent years, in the semiconductor industry, process miniaturization has progressed, and aminomethylenephosphonic acid has been added to hydrogen peroxide water, ammonia water, etc. used as a silicon wafer cleaning solution for the purpose of improving the cleanliness of silicon wafers and simplifying processes. And adding a chelating ability to remove metal on the wafer.
アミノメチレンホスホン酸の製造法としては、塩酸酸性下、アンモニア、アンモニウム化合物又はアミン及びアルデヒド又はケトンおよびホスホン酸と反応させてアミノアルキレンホスホン酸を得る方法などが知られている(特許文献1、非特許文献1参照)。 As a method for producing aminomethylene phosphonic acid, there is known a method in which aminoalkylenephosphonic acid is obtained by reacting with ammonia, ammonium compound or amine and aldehyde or ketone and phosphonic acid under acidic conditions of hydrochloric acid (Patent Document 1, Non-patent Document 1). Patent Document 1).
半導体産業向けのシリコンウエハ洗浄液は、その性格上高純度である必要があり、アミノメチレンホスホン酸は未反応の原材料、副生物等の有機不純分、装置材質例えばステンレスからの溶出、環境、原材料からの持ち込みに等よる金属不純物を極力減らす必要がある。このうち、金属不純分に関しては装置材質、高純度の原材料の選定等で低レベルにすることが可能であるが、有機不純分に関しては、一般に、反応収率を上げるために原材料の一部を過剰に仕込むことが多く、反応後の未反応および過剰分の除去が重要となる。 Silicon wafer cleaning solution for the semiconductor industry needs to be highly pure in character, and aminomethylene phosphonic acid is an unreacted raw material, organic impurities such as by-products, equipment materials such as elution from stainless steel, environment and raw materials. It is necessary to reduce metal impurities such as by bringing in as much as possible. Of these, metal impurities can be reduced to low levels by selecting equipment materials and high-purity raw materials, etc., but organic impurities are generally part of the raw materials to increase the reaction yield. In many cases, an excessive amount is charged, and it is important to remove unreacted and excessive components after the reaction.
アミノメチレンホスホン酸残存原料の内、特にホルムアルデヒドは還元力が高く、過酸化水素等の酸化剤への添加を目的とする場合には極力除去する必要がある。その残存量は、アミノメチレンホスホン酸の使用形態、添加量により異なるが、一般的には、水容液で使用する場合、0.3重量%以下、好ましくは0.2重量%以下が望まれる。単離した固体状等で使用する場合には1重量%以下、好ましくは0.8重量%以下が望まれる。 Of the aminomethylene phosphonic acid remaining raw materials, formaldehyde has a high reducing power, and it is necessary to remove it as much as possible when it is added to an oxidizing agent such as hydrogen peroxide. The residual amount varies depending on the use form and addition amount of aminomethylene phosphonic acid, but generally 0.3% by weight or less, preferably 0.2% by weight or less is desired when used in an aqueous solution. . When used in the form of an isolated solid or the like, 1% by weight or less, preferably 0.8% by weight or less is desired.
ホルムアルデヒドを除去するためのアミノメチレンスルホン酸の精製方法としては、再結晶で精製する手法、貧溶媒へ投入して固形化し精製する手法、蒸留により精製する手法が挙げられる。再結晶で精製する手法はアミノメチレンホスホン酸に結晶性が良好なことが必要であり、また、収率が低下する欠点がある。 Examples of the purification method of aminomethylene sulfonic acid for removing formaldehyde include a method of purification by recrystallization, a method of solidifying by introducing into a poor solvent, and a method of purification by distillation. The method of purification by recrystallization requires that aminomethylene phosphonic acid has good crystallinity and has the disadvantage that the yield decreases.
貧溶媒へ投入して固形化する手法は固形化後の固体性状が粘張とならない様な貧溶媒の選定が難しく、また、収率および精製効率が低いことが欠点である。加えて、融点またはガラス転移温度が比較的低いものが多く、結晶もしくは固形化固体濾過後に貧溶媒を除去する作業で、乾燥温度によっては溶融して飴状になってしまい、それ以後のプロセスでのハンドリングが非常に悪くなるという問題も存在する。 The method of solidifying by introducing into a poor solvent is disadvantageous in that it is difficult to select a poor solvent such that the solid state after solidification does not become viscous, and the yield and purification efficiency are low. In addition, many of them have a relatively low melting point or glass transition temperature, and the poor solvent is removed after filtration of crystals or solidified solids. There is also a problem that the handling of the system becomes very bad.
蒸留で精製する場合、ホルムアルデヒドは水に対する親和性が大きく、常圧、減圧での実施では水の蒸気圧がホルムアルデヒドより大きく、系中に水を添加して多量の水と同時に留去する必要があり蒸留効率が悪い。また、加圧条件ではホルムアルデヒドの蒸気圧は水より大きくなるものの、加圧対応の高額な設備投資が必要となる。
本発明の目的は、背景技術における上記したように、半導体工業用途のシリコンウエハ洗浄液の成分として使用するアミノメチレンホスホン酸中の未反応のホルムアルデヒドを収率良く、簡便な設備、簡便な操作で高度に除去することを目的とする。 As described above in the background art, the object of the present invention is to obtain unreacted formaldehyde in aminomethylene phosphonic acid used as a component of a silicon wafer cleaning solution for semiconductor industry in a high yield with simple equipment and simple operation. It aims to be removed.
本発明者らは、塩酸酸性下、アンモニアまたはアミンをホルムアルデヒド、ホスホン酸と反応させアミノメチレンホスホン酸溶液を得る方法において、未反応ホルムアルデヒドをアルコールと反応させ、除去が容易なホルマールとして系外へ蒸発除去して容易に精製しうることを見出し本発明に到達した。 In the method of obtaining an aminomethylenephosphonic acid solution by reacting ammonia or amine with formaldehyde or phosphonic acid under acidic hydrochloric acid, the present inventors reacted unreacted formaldehyde with alcohol to evaporate out of the system as a formal that can be easily removed. The present invention has been found out that it can be easily removed and purified.
すなわち、本発明は、塩酸酸性下、アンモニアまたはアミンをホルムアルデヒド、ホスホン酸と反応させてアミノメチレンホスホン酸を製造する方法において、反応液にアルコールを添加して、未反応ホルムアルデヒドとアルコールにより生成するホルマールを反応蒸留により除去することを特徴とするアミノメチレンホスホン酸の製造方法に関するものである。 That is, the present invention relates to a process for producing aminomethylenephosphonic acid by reacting ammonia or amine with formaldehyde and phosphonic acid under acidic conditions of hydrochloric acid, and adding formal to the reaction liquid to form formal which is produced from unreacted formaldehyde and alcohol. The present invention relates to a process for producing aminomethylene phosphonic acid, characterized in that is removed by reactive distillation.
本発明により、アミノメチレンホスホン酸をロスすることなく容易に高効率で未反応ホルムアルデヒドを除去し、高純度アミノメチレンホスホン酸を得ることが可能となり、半導体のシリコンウエハ洗浄液の成分として、過酸化水素水、及びアンモニア水等へ添加しその機能を向上する目的などに使用可能となる。また、本発明のアミノメチレンホスホン酸は半導体関連用途以外にも、その必要とされるスペックを満たせば使用可能である。 According to the present invention, it is possible to easily remove unreacted formaldehyde with high efficiency without losing aminomethylenephosphonic acid to obtain high-purity aminomethylenephosphonic acid, and hydrogen peroxide as a component of a semiconductor silicon wafer cleaning solution. It can be used for the purpose of adding to water, ammonia water or the like to improve its function. Further, the aminomethylene phosphonic acid of the present invention can be used as long as it meets the required specifications in addition to the semiconductor-related applications.
本発明は、塩酸酸性下、アンモニアまたはアミンをホルムアルデヒド、ホスホン酸と反応させアミノメチレンホスホン酸を得る方法で用いられる。アミノメチレンホスホン酸には、アミノトリメチレンホスホン酸、エチレンジアミンテトラ(メチレンホスホン酸)、1,2−プロピレンジアミンテトラ(メチレンホスホン酸)、ヘキサメチレンジアミンテトラ(メチレンホスホン酸)、ジエチレントリアミンペンタ(メチレンホスホン酸)およびこれらの塩、並びに酸化体が挙げられる。 The present invention is used in a method for obtaining aminomethylene phosphonic acid by reacting ammonia or amine with formaldehyde or phosphonic acid under acidic conditions of hydrochloric acid. Aminomethylene phosphonic acid includes aminotrimethylene phosphonic acid, ethylenediaminetetra (methylenephosphonic acid), 1,2-propylenediaminetetra (methylenephosphonic acid), hexamethylenediaminetetra (methylenephosphonic acid), diethylenetriaminepenta (methylenephosphonic acid). ) And their salts, as well as oxidants.
まず、一般的なアミノメチレンホスホン酸の製造法を述べる。アミノメチレンホスホン酸を半導体産業用途に用いる場合、ステンレスなどは、金属成分の溶出のある設備は好ましくなく、接液部がグラスライニング(以下GL)など金属成分の溶出がない攪拌機付き反応釜を使用することが好ましい。GL釜を、事前にFeなど金属成分の溶出がない清浄化状態にして使用する。清浄化の方法としては、希塩酸、脱イオン水による洗浄がある。 First, a general method for producing aminomethylene phosphonic acid will be described. When aminomethylene phosphonic acid is used for semiconductor industry applications, stainless steel and other equipment with elution of metal components are not preferred, and the wetted part uses a reaction kettle with a stirrer that does not elute metal components such as glass lining (hereinafter GL). It is preferable to do. The GL kettle is used in a clean state in which there is no elution of metal components such as Fe in advance. Cleaning methods include cleaning with dilute hydrochloric acid and deionized water.
製造手順の一例を挙げるならば、GL釜にまず塩酸を仕込み、次に亜燐酸を仕込む。亜燐酸を仕込むことにより塩酸との反応により吸熱となるため、加熱を行い、温度を5〜15℃に保つ。次に、アミンを反応温度を15〜20℃に保ちながら一定速度で添加する。本反応は発熱となるため、除熱が必要である。アミン添加終了後、反応液を85〜95℃まで加熱する。次に37〜50重量%ホルマリンを一定速度で供給し反応を行う。反応自体は発熱反応であり、反応液の温度は90〜100℃となるように管理する。反応完結後、室温まで冷却し反応終了とする。発生する塩酸蒸気は、還流によるコンタミネーション防止の観点からエジェクター等を通じて系外へ排出し、還流を出来るだけ避け、排気ガス処理設備で処理する。これら、一連の操作において、コンタミネーションを起こさないように注意を払うことが重要である。製造設備のある環境を清浄に保つことも肝要である。 If an example of a manufacturing procedure is given, first, hydrochloric acid will be charged into a GL kettle, and phosphorous acid will be charged next. By adding phosphorous acid, it becomes endothermic by reaction with hydrochloric acid, so heating is performed and the temperature is maintained at 5 to 15 ° C. The amine is then added at a constant rate while maintaining the reaction temperature at 15-20 ° C. Since this reaction is exothermic, heat removal is necessary. The reaction liquid is heated to 85-95 degreeC after completion | finish of amine addition. Next, 37-50% by weight formalin is supplied at a constant rate to carry out the reaction. The reaction itself is an exothermic reaction, and the temperature of the reaction solution is controlled to be 90 to 100 ° C. After completion of the reaction, the reaction is completed by cooling to room temperature. The generated hydrochloric acid vapor is discharged out of the system through an ejector, etc. from the viewpoint of preventing contamination due to recirculation, and treated with exhaust gas treatment equipment to avoid recirculation as much as possible. In these series of operations, it is important to pay attention not to cause contamination. It is also important to keep the environment with manufacturing equipment clean.
アンモニアおよびアミンの内、アミンはエチレンジアミン、1,2−プロパンジアミン、エキサメチレンジアミン、ジエチレントリアミン等が挙げられる。亜燐酸はアミンが1級アミン場合N原子に対して2〜4倍モル、2級アミンの場合N原子に対して1〜2倍モルを使用する。アミンが1分子中に1級および2級のアミン部位を有する場合は先の1級、2級アミンそれぞれに対する使用量の合計で使用する。 Among ammonia and amine, examples of the amine include ethylenediamine, 1,2-propanediamine, excamethylenediamine, and diethylenetriamine. Phosphorous acid is used in an amount of 2 to 4 moles relative to the N atom when the amine is a primary amine, and 1 to 2 moles relative to the N atom when the amine is secondary. When the amine has primary and secondary amine sites in one molecule, it is used in the total amount used for the primary and secondary amines.
ホルムアルデヒドはアンモニアに対してはN原子に対して3〜9倍モル、アミンに対しては1級アミン場合N原子に対して2〜6倍モル、2級アミンの場合N原子に対して1〜3倍モルを使用する。アミンが1分子中に1級および2級のアミン部位を有する場合は先の1級、2級アミンそれぞれに対する使用量の合計で使用する。酸には硫酸、塩酸、燐酸、硝酸等が挙げられる。 Formaldehyde is 3 to 9 moles per mole of N for ammonia, and 2 to 6 moles per mole of N for primary amines for amines and 1 to N for secondary amines. Use 3 moles. When the amine has primary and secondary amine sites in one molecule, it is used in the total amount used for the primary and secondary amines. Examples of the acid include sulfuric acid, hydrochloric acid, phosphoric acid, nitric acid and the like.
アルコールはメタノール、エタノール、n−プロパノール、イソプロパノール等が挙げられ、好ましくはメタノールである。添加量は、残存する未反応ホルムアルデヒドに対して2〜10倍モル量である。アルコール添加により、反応液中の酸が触媒となりホルマールが生成する。生成するホルマールは水との親和力が低く、また、蒸気圧が高く容易に蒸留除去できる。過剰分のアルコールも蒸留により容易に除去できる。 Examples of the alcohol include methanol, ethanol, n-propanol, isopropanol and the like, preferably methanol. The amount added is 2 to 10 times the amount of the remaining unreacted formaldehyde. By adding alcohol, the acid in the reaction solution becomes a catalyst to form formal. The produced formal has a low affinity with water and has a high vapor pressure and can be easily removed by distillation. Excess alcohol can also be easily removed by distillation.
ホルマールの生成は、アルコール、ホルムアルデヒド、メチラール及び水の平衡反応により行われる。そのため、ホルムアルデヒドの除去は、メチラールを反応蒸留により留去して、平衡をメチラールの生成に傾かせるだけで進行する。メチラールの生成速度は室温において、20分でほぼ平衡に達するほど速く、生成したメチラールはホルムアルデヒド、メタノールと比較し蒸気圧が高く簡単に留去できるため、簡単な蒸留操作でホルムアルデヒドの除去が可能である。 Formal is produced by an equilibrium reaction of alcohol, formaldehyde, methylal and water. Therefore, the removal of formaldehyde proceeds only by distilling off the methylal by reactive distillation and tilting the equilibrium toward the production of methylal. The production rate of methylal is so fast that it almost reaches equilibrium in 20 minutes at room temperature, and the resulting methylal has a higher vapor pressure than formaldehyde and methanol and can be easily distilled off, so that formaldehyde can be removed by a simple distillation operation. is there.
残存メタノールの留去は、通常の蒸留操作にて簡単に行うことは出来る。ただし、メタノールは水と一緒に留去する必要があるため、単蒸留等では反応液中の塩酸濃度が濃くなって、多量の塩酸蒸気の発生し、結果、蒸留装置に悪影響を与えてしまう。そこで、塩酸の蒸発量を抑えるため、塩酸が濃くならないように水を添加して蒸留を行えば、蒸留装置への影響を少なくしてメタノールの留去を行うことが可能である。 The residual methanol can be easily distilled off by a normal distillation operation. However, since methanol needs to be distilled off together with water, the concentration of hydrochloric acid in the reaction solution becomes high in simple distillation and the like, and a large amount of hydrochloric acid vapor is generated. As a result, the distillation apparatus is adversely affected. Therefore, in order to suppress the evaporation amount of hydrochloric acid, if distillation is performed by adding water so that hydrochloric acid does not become concentrated, it is possible to distill off methanol with less influence on the distillation apparatus.
精製したアミノメチレンホスホン酸は、塩酸を除去して溶液の状態のまま使用できる。塩酸の除去に関しては、例えば電気透析等の手法が取り得る。さらなる高純度化を望むのであれば、再結晶、貧溶媒による固形化、イオン交換法による精製等を追加実施しても構わない。 The purified aminomethylene phosphonic acid can be used in the form of a solution after removing hydrochloric acid. For removal of hydrochloric acid, for example, a technique such as electrodialysis can be used. If further higher purity is desired, recrystallization, solidification with a poor solvent, purification by ion exchange method, and the like may be additionally performed.
以下に本発明を実施例によって詳細に説明するが、本発明は実施例によって制限されるものではない。なお、実施例、比較例中のホルムアルデヒド濃度分析はガスクロマトグラフィー(島津(株)製GC−14B)により、また、塩化物濃度はイオンクロマトグラフィー(ダイオネックス社DX−500)により実施した。 The present invention will be described in detail below with reference to examples, but the present invention is not limited to the examples. In addition, the formaldehyde concentration analysis in an Example and a comparative example was implemented by the gas chromatography (Shimadzu Co., Ltd. GC-14B), and the chloride density | concentration was implemented by the ion chromatography (Dionex DX-500).
参考例
攪拌機、ジャケット付き1m3GL釜の内部を希塩酸、イオン交換水で洗浄した。GL釜に36重量%ELグレード塩酸260kgを仕込んだ。次に、亜燐酸175kg(2.13kmol)を約30分かけて投入した。投入中の吸熱のためジャケットにスチームを入れ、釜温度を5〜10℃に保った。次いで、ジャケットに冷却水を入れ、反応温度を15〜20℃に調節しながら、ジエチレントリアミン(DETA)30kg(0.29kmol)を定量ポンプにより1時間投入した後、さらに15〜20℃にて1時間反応を行った。その後、スチームにより90℃まで加温した後、37重量%ホルマリン240kg(2.97kmol)を、2時間かけて反応させた。この間、反応温度は90〜95℃に維持した。ホルマリン投入終了後、90〜95℃で1時間保った。室温まで冷却後、GL釜より抜き出した反応液は、690kgであった。反応液を分析したところジエチレントリアミンペンタメチレンホスホン酸(DTPP)を25重量%含有し、残存ホルムアルデヒド濃度は7.0重量%であった。
Reference Example The inside of a 1 m3GL kettle with a stirrer and a jacket was washed with dilute hydrochloric acid and ion-exchanged water. A GL kettle was charged with 260 kg of 36 wt% EL grade hydrochloric acid. Next, 175 kg (2.13 kmol) of phosphorous acid was added over about 30 minutes. Steam was put in the jacket for endothermic heat during charging, and the temperature of the kettle was kept at 5 to 10 ° C. Next, cooling water was put into the jacket, and 30 kg (0.29 kmol) of diethylenetriamine (DETA) was added for 1 hour with a metering pump while adjusting the reaction temperature to 15 to 20 ° C., and then for 1 hour at 15 to 20 ° C. Reaction was performed. Then, after heating to 90 degreeC with steam, 240 kg (2.97 kmol) of 37 weight% formalin was made to react over 2 hours. During this time, the reaction temperature was maintained at 90-95 ° C. After completion of formalin addition, it was kept at 90 to 95 ° C. for 1 hour. After cooling to room temperature, the reaction liquid extracted from the GL kettle was 690 kg. When the reaction solution was analyzed, it contained 25% by weight of diethylenetriaminepentamethylenephosphonic acid (DTPP) and the residual formaldehyde concentration was 7.0% by weight.
実施例1
参考例で製造したDTPP反応液150gに一級メタノールを50g添加したものを、ロータリーエバポレーターRE111(Buchi製)を用いて、湯浴の温度70℃、圧力101.3〜13.3kPaで留出液が50ml出るまで蒸留した後、釜残液にイオン交換水を50g添加し、温度70℃、圧力1.3kPaで、さらに50mlの留出液がでるまで蒸留した。蒸留後の釜残液中のホルムアルデヒド濃度は0.08重量%で、十分に低いものであった。
Example 1
A distillate is obtained by adding 50 g of primary methanol to 150 g of the DTPP reaction solution produced in the reference example, using a rotary evaporator RE111 (manufactured by Buchi) at a water bath temperature of 70 ° C. and a pressure of 101.3 to 13.3 kPa. After distillation to 50 ml, 50 g of ion-exchanged water was added to the residue in the kettle and distilled at a temperature of 70 ° C. and a pressure of 1.3 kPa until 50 ml of distillate was produced. The formaldehyde concentration in the kettle residue after distillation was 0.08% by weight, which was sufficiently low.
実施例2
参考例で製造したDTPP反応液150gに一級メタノールを50g添加したものを、ロータリーエバポレーターRE111(Buchi製)を用いて、湯浴の温度70℃、圧力101.3〜13.3kPaで留出液が50ml出るまで蒸留した。蒸留後の釜残液中のホルムアルデヒド濃度は0.05重量%で、十分に低いものであった。
Example 2
A distillate is obtained by adding 50 g of primary methanol to 150 g of the DTPP reaction solution produced in the reference example, using a rotary evaporator RE111 (manufactured by Buchi) at a water bath temperature of 70 ° C. and a pressure of 101.3 to 13.3 kPa. Distilled to yield 50 ml. The formaldehyde concentration in the kettle residue after distillation was 0.05% by weight and was sufficiently low.
実施例3
参考例で製造したDTPP反応液7.5kgに一級メタノールを2.5kg添加したものを、ロータリーエバポレーターRE20(SIBATA製)を用いて、油浴の温度100℃、圧力46.7〜8.0kPaで留出液が3.0l出るまで蒸留した後、釜残液にイオン交換水を2.5kg添加し、温度100℃、圧力46.7〜4.7kPaで、さらに2.5lの留出液がでるまで蒸留した。蒸留後の釜残液中のホルムアルデヒド濃度は0.03重量%で、十分に低いものであった。
次に釜残液4kgをイオン交換水でDTPP濃度が10重量%となるように希釈し、旭化成工業株式会社製の「マイクロアシライザーS3」の透析装置を用いて、電気透析を行い、ホルムアルデヒド濃度0.03重量%、塩化物イオン濃度10ppmの液8kgを得た。
Example 3
What added 2.5 kg of primary methanol to 7.5 kg of the DTPP reaction liquid manufactured in the reference example was performed using a rotary evaporator RE20 (manufactured by SIBATA) at an oil bath temperature of 100 ° C. and a pressure of 46.7 to 8.0 kPa. After distillation until 3.0 liters of distillate comes out, 2.5 kg of ion-exchanged water is added to the bottom of the kettle, and at a temperature of 100 ° C. and a pressure of 46.7 to 4.7 kPa, another 2.5 liter of distillate is added. Distilled until left. The formaldehyde concentration in the kettle residue after distillation was 0.03% by weight, which was sufficiently low.
Next, 4 kg of the residue from the kettle is diluted with ion-exchanged water so that the DTPP concentration is 10% by weight, and electrodialysis is performed using a “dialysis device” of “Asahi Kasei Kogyo Co., Ltd.” to formaldehyde concentration. 8 kg of a liquid having 0.03% by weight and a chloride ion concentration of 10 ppm was obtained.
比較例1
メタノール50mlに代え、イオン交換水50mlを使用した以外は実施例1と同様の操作を実施した。得られた精製液にはホルムアルデヒドが1.7%含まれており、残存量が多いものであった。
Comparative Example 1
The same operation as in Example 1 was performed except that 50 ml of ion-exchanged water was used instead of 50 ml of methanol. The resulting purified solution contained 1.7% formaldehyde and had a large residual amount.
比較例2
メタノール50mlに代え、イオン交換水50mlを使用した以外は実施例2と同様の操作を実施した。得られた精製液にはホルムアルデヒドが2.6%含まれており、残存量が多いものであった。
Comparative Example 2
The same operation as in Example 2 was performed except that 50 ml of ion-exchanged water was used instead of 50 ml of methanol. The resulting purified solution contained 2.6% formaldehyde and had a large residual amount.
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