TW491912B

TW491912B - Conditioning liquid and conditioning process used in pretreatment for formation of phosphate layer on the metallic surface

Info

Publication number: TW491912B
Application number: TW088112333A
Authority: TW
Inventors: Takaomi Nakayama; Yasuhiko Nagashima; Kensuke Shimoda; Hirokastu Bannai
Original assignee: Nihon Parkerizing
Priority date: 1998-07-21
Filing date: 1999-07-20
Publication date: 2002-06-21
Also published as: KR20000011838A; MY129412A; ID23566A; KR100609482B1; CN1242436A; CN1265024C

Abstract

Novel conditioning liquid used in pretreatment for formation of phosphate layer, being suitable for efficiently produce finly crystalized phosphate layer, also being durable of its excellent properties are disclosed. The conditioning liquid of the invention contains phosphate particles of bivalent and or trivalent metal, also contains a accelerating component. As for the accelerating component, saccharides, phosphoric acid compounds, polymer of acetic acid vinyl and designated aqueous high molecular compounds are favorable. The size of the phosphate particles are preferable to be less than 5 μm. And the concentration of the accelerating component are preferable to ba 1 to 2000 ppm. Before a process of formation of phosphate layer, the metallic surface is made to contact with the conditioning solution. Cleaning effect is possible to give to the conditioning liquid.

Description

491912 A7 B7 五、發明說明（i ) 發明範疇 (請先閱讀背面之注意事項再填寫本頁) 本發明有關一種供表面調理使用之處理液及該表面調理方法’其係用以於金屬表面上化學性地形成磷酸鹽層，可應用於諸如鋼、鍍鋅鋼板、鋁與鎂合金等以促進並加速該化學反應，而使磷酸鹽層中之磷酸鹽結晶變細。背景技藝近來’有一種於磷酸鹽層中形成細密之磷酸鹽結晶之需求’用以改善塗佈後之抗腐蝕性，並降低該金屬於冷操作下之摩擦。因此經常於化學性地形成磷酸鹽層之前先使用表面調理方法，以活化金屬表面，並製造適於產生細密之磷酸鹽結晶之晶核。下文係例示習用以得到細密之磷酸鹽結晶之方法。磷酸鹽層係根據以下步驟產製。 (1 )去除脂油 (2 )水洗（多階式）經濟部智慧財產局員工消費合作社印製 (3 )表面調理 (4 )化學性地形成磷酸鹽層 (5 )水洗（多階式） (6 )於純水中漂洗。表面調理方法適於使磷酸鹽結晶變得細密。傳統上使用之化學複合材料係揭示於美國專利第2 8 7 4 0 8 1 號、第2322349號及第2310 239號中，出示一種調理溶液，含有鈦、焦磷酸離子、原磷酸離子及鈉離子等。該複合材料係稱爲傑特鹽Uernstedt salt )，而該複 -4- 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐）經濟部智慧財產局員工消費合作社印製 491912 A7 B7 五、發明說明（2 ) 合材料之水溶液含有鈦離子及鈦膠體。當一金屬浸漬於或噴灑上前述調理溶液時，該金屬表面吸附鈦膠體。所吸附之鈦膠體將於化學性地形成磷酸鹽 •層的方法中成爲晶核，促進該化學反應，而產生細密之結晶。目前，所有工業上應用之表面調理複合材料皆係使用傑特鹽（Jernstedt salt )。然而’傑特鹽（Jernstedt salt )之工業應用產生各式各樣之問題。 /第一個問題是該表面調理溶液隨著時間的經過而降解。施加習用表面調理溶液時，針對在製備該水溶液之後立即使磷酸鹽結晶變得細密而言，該鹽顯示了相當明顯之效果。但製備數日後，不管是否經過使用，皆喪失該種效果，而所得之磷酸鹽結晶因爲調理溶液中之鈦膠體凝結而變粗。是故，JP63-76883A已揭示一種方法，其係配置一部分該表面調理液並連續地添加新的表面調理液，以藉著定期測量而使鈦膠體之平均直徑保持夠小之値。雖然此種方法可定量地控制該表面調理液，但需配置該部分之表面調理液以保持該種效果。因此，此方法需要配置大量該表面調理液及具有大容量之水配置設備。第二個問題係爲該表面調理液之功效及壽命與用以製備之水的品質有極大關係。通常，使用自來水以製備該表面調理液。但已知自來水通常含有陽離子諸如鈣、鎂等。而該陽離子之含量係視水源而定。此情況下，已知鈦膠體係藉著陰離子中之電荷的電斥力以保持分散而不沉澱。因 lrrl.-------·裝--------訂----I----線Φ- (請先閱讀背面之注意事項再填寫本頁) 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -5- 491912 Α7 Β7 五、發明說明（3 ) 此，若自來水含有過量之陽離子性成分，則鈦膠體會被該陽離子性成分中和，而喪失其排斥力以致凝結並沉澱。 (請先閱讀背面之注意事項再填寫本頁) 有人提出於該表面調理液中添加縮合之磷酸鹽諸如焦 _磷酸鹽，以封阻陽離子性成分，並保持鈦膠體之安定性。但該表面調理液中添加過量之縮合磷酸鹽時，可能因該縮合磷酸與該調理液中之金屬表面實施例而產生惰性塗層’ 使得後續處理方法中於金屬上化學性地形成磷酸鹽層之過程產生問題。當自來水中含有過量鈣或鎂時，需使用純水以製造該調理液，導致經濟上之缺點。第三個問題爲施加時之溫度及P Η。例如，該鈦膠體於對於3 5 °C之溫度及超出ρ Η 8 · 0〜9 . 5之範圍即凝結而喪常表面調理效果。因此，習用之表面調理液而於窄幅之特定溫度及窄幅之特定Ρ Η範圍下使用。因此無法如同單液型般地使該表面調理液產生淸潔效果。經濟部智慧財產局員工消費合作社印製第四個問題爲磷酸鹽結晶之小型化受到限制。該磷酸鹽之小型化係始自吸附於該金屬表面上之鈦膠體晶核形成，有助於磷酸鹽結晶之細致化。因此，金屬表面上吸附之鈦膠體愈多，可得到愈細密之磷酸鹽結晶。爲了解決此項問題，簡易方式係建議增加調理液中之鈦膠體之數目。但密度愈高，鈦膠體於該調理液中彼此撞擊之頻率愈高，導致愈多之凝結及沉降。目前使用之鈦膠龜體之上限係低於百萬分之1 0 〇份數’無法使用較高密度鈦膠體之調理液。 JP56 — 156778 及 JP57 — 23066Α -6 - 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐）經濟部智慧財產局員工消費合作社印製 491912 A7 _____B7 五、發明說明（4 ) 已揭示一種於加壓下將含有二價或三價金屬之不可溶磷酸鹽之懸浮液噴射於該鋼面上之方法。但僅於加壓下噴射該懸浮液時顯示效果，故此方法無法應用於使該金屬浸漬或 •噴灑該調理液之一般調理方法。 J P40 - 1 0 9 5B2已揭示另一種表面調理方法’其係將鍍鋅鋼板浸漬於二價或三價金屬之不可溶磷酸鹽之懸浮液中。但此方法之應用實例僅侷限於鍍鋅鋼板，且需使用至少高達3 0克/升之高密度不可溶磷酸鹽。如則文所說明，與傑特鹽（Jernstedt salt )有關之方法已呈現出如此繁多之問題。然而，目前仍未有可取代該傑特法（Jernstedt method )之方法。發明揭示本發明之目的係解決前述習用技術之問題，提供一種新穎之調理液及新穎之調理方法，其促進及加速化學反應，使磷酸鹽結晶變得更細，而保持長時間之安定性。本發明者等人針對解決前述問題而進行徹底硏究，最後得到一種可進一步改善磷酸鹽層品質之新穎的表面調理液及調理方法。即’本發明爲（1 ):一種供於金屬表面上形成磷酸鹽層之預處理使用之調理液，其特徵爲其含有一或多於一種二價或三價金屬之磷酸鹽粒子，且含有一或多於一種加速成分，選自單醣、多醣及其衍生物。而且，本發明係爲（2 ):—種供於金屬表面上形成本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） ------------馨裳--------訂---------線· (請先閲讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 491912 Α7 Β7 五、發明說明（5 ) 磷酸鹽層之預處理使用之調理液，其特徵爲其含有一或多於一種二價或三價金屬之磷酸鹽粒子，且含有一或多於一種加速成分，選自原磷酸鹽、多磷酸鹽及有機膦酸化合 •物。而且，本發明係爲（3 ):—種供於金屬表面上形成磷酸鹽層之預處理使用之調理液，其特徵爲其含有一或多於一種二價或三價金屬之磷酸鹽粒子，且含有一或多於一種水溶性高聚物化合物，選自乙酸乙烯基之聚合物、其衍生物、及乙酸乙烯基與其他單體之共聚物。而且，本發明係爲（4 ):一種供於金屬表面上形成磷酸鹽層之預處理使用之調理液，其特徵爲其含有一或多於一種二價或三價金屬之磷酸鹽粒子，且含有一或多於一種加速成分，選自藉著聚合下述單體i )及低於5 0重量百分比之下述單體1 i )所得之聚合物或共聚物。單體1 )下式（1 )所示之單體或選自α -、/5 -不飽和碳酸單體。單體i i )可與前述單體i )共聚之單體。 R1 H2C = C-COOR2...............式（1 ) (R1 : Η或CH3，R2 : Η或具有C 1〜5之烷基或具有C 1〜5之羥烷基）於前述（1 )〜（4 )中，該磷酸鹽粒子應有利地含有直徑小於5微米之粒子，總濃度應以〇 . 0 0 1〜3 0 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） • I--------訂-------！線· (請先閱讀背面之注意事項再填寫本頁) , ’ -8 - 491912 Α7 Β7 經濟部智慧財產局員工消費合作社印製五、發明說明（6 ) 克/升爲佳，而該二價或三價金屬以至少一種選自Ζ η， Fe ，Mn，Ni ，Co，Ca及Α1爲佳。而該加速成分之總濃度應爲百萬分之1〜2 0 〇〇份數較佳。 '此外，該調理液以含有其他鹼金屬鹽或銨鹽或其混合物爲佳。此等鹼金屬鹽或銨鹽以原磷酸鹽、偏磷酸鹽、原矽酸鹽、偏矽酸鹽、碳酸鹽、碳酸氫鹽、硝酸鹽、亞硝酸鹽、硫酸鹽、硼酸鹽及有機酸鹽，較佳總濃度係〇 · 5〜 2〇克/升。本發明之調理方法係於形成磷酸鹽層之前先使該金屬表面與前述調理液接觸。因爲本發明調理液於高P Η範圍及高溫下具有較習用技術中之鈦膠體高之安定性。是故，本發明調理液可另外含有鹼組份及一或多於一種添加劑，選自非離子性界面活性劑及陰離子性界面活性劑。此種調理液亦可具有淸潔金屬表面之另一效果。經此調理液處理之金屬具有淸潔之表面，亦具有適於形成磷酸鹽層之性質。如前文所說明，於習用方法中，在化學性地形成磷酸鹽層之前，需先進行（1 )去除脂油，（2 )水洗及 (3 )表面調理等三個步驟。藉著使用本發明兼具淸潔 (脫脂）效果及表面調理效果之調理液，此三步驟可簡化成單一步驟，結合脫脂及表面調理之方法，如下文第 (1 )項所述。即，可減少兩步驟。本發明調理液可有效地提供適於在較習用Ρ Η範圍寬幅之Ρ Η範圍下形成磷酸鹽層之表面。是故，本發明可另 (請先閱讀背面之注音？事項再填寫本頁) -裝 ----訂---- 線本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -9- 491912 A7 _____ B7 五、發明說明（7 ) 外於該調理溶液中添加鹼金屬鹽，而且本發明可得到兼具有淸潔及表面調理效果之調理液。 (請先閱讀背面之注意事項再填寫本頁) (1 )脫脂及表面調理之結合方法 ‘ （2 )化學性地形成磷酸鹽層 (3 )水洗（多階式） (4 )於純水中漂洗進行本發明之最佳模式二價或三價金屬之磷酸鹽粒子及加速成分係本發明之必要成分。如前文所述，本發明之目的係提供一種表面調理液’其係於形成磷酸鹽層之前活化該金屬表面，並產生供磷酸鹽結晶沉澱所使用之晶核。本發明者等人發現具有較佳直徑之二價或三價金屬之磷酸鹽粒子係於較佳含量下吸附於欲於含有加速成分之水溶液中處理之金屬表面上，產生供磷酸鹽層結晶使用之晶核，並加速磷酸鹽層之形成。經濟部智慧財產局員工消費合作社印製本發明二價或三價金屬之磷酸鹽粒子係爲固體而不可溶。然而，其於化學上係爲用以形成磷酸鹽層之化學物質的類似成分，其亦於化學上類似所形成之磷酸鹽層。其對於用以形成磷酸鹽層之溶液不會有負面影響，即使將該調理液之一部分置入容裝有用'以形成磷酸鹽層之溶液的後續浸浴中，亦不會對於該磷酸鹽層產生負面影響。本發明二價或三價金屬之磷酸鹽粒子有例如下列者。491912 A7 B7 V. Description of the invention (i) The scope of the invention (please read the precautions on the back before filling this page) The present invention relates to a treatment liquid for surface conditioning and the surface conditioning method 'It is used on a metal surface The phosphate layer is chemically formed and can be applied to steels, galvanized steel sheets, aluminum and magnesium alloys to promote and accelerate the chemical reaction, and to make the phosphate crystals in the phosphate layer finer. BACKGROUND ART Recently, there is a "requirement for forming fine phosphate crystals in a phosphate layer" to improve the corrosion resistance after coating and reduce the friction of the metal under cold operation. Therefore, surface conditioning methods are often used before chemically forming the phosphate layer to activate the metal surface and to produce nuclei suitable for producing fine phosphate crystals. The following is an example of the method used to obtain fine phosphate crystals. The phosphate layer is produced according to the following steps. (1) Degreasing (2) Washing (multi-stage) Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs (3) Surface conditioning (4) Chemically forming a phosphate layer (5) Washing (multi-stage) (6 ) Rinse in pure water. The surface conditioning method is suitable for making phosphate crystals fine. Traditionally used chemical composites are disclosed in U.S. Patent Nos. 2874, 081, 2322349, and 2310 239, showing a conditioning solution containing titanium, pyrophosphate ions, orthophosphate ions, and sodium ions Wait. The composite material is called Uernstedt salt, and the size of this paper is applicable to China National Standard (CNS) A4 (210 X 297 mm). Printed by the Employees ’Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs 491912 A7 B7 V. Description of the Invention (2) The aqueous solution of the composite material contains titanium ions and titanium colloids. When a metal is impregnated or sprayed with the aforementioned conditioning solution, the titanium surface is adsorbed on the metal surface. The adsorbed titanium colloid will become a crystal nucleus in the method of chemically forming a phosphate layer, which promotes the chemical reaction and produces fine crystals. At present, all industrially used surface conditioning composites use Jernstedt salt. However, the industrial application of 'Jernstedt salt' has caused various problems. / The first problem is that the surface conditioning solution degrades over time. When a conventional surface conditioning solution is applied, the salt shows a fairly significant effect for making the phosphate crystals fine immediately after the aqueous solution is prepared. However, this effect is lost after several days of preparation, whether or not it is used, and the resulting phosphate crystals become coarse due to the coagulation of the titanium colloid in the conditioning solution. Therefore, JP63-76883A has disclosed a method of disposing a part of the surface conditioning liquid and continuously adding a new surface conditioning liquid to keep the average diameter of the titanium colloid sufficiently small by periodic measurement. Although this method can control the surface conditioning liquid quantitatively, it is necessary to configure the surface conditioning liquid in this part to maintain the effect. Therefore, this method needs to be equipped with a large amount of the surface conditioning liquid and a water disposition device with a large capacity. The second problem is that the efficacy and longevity of the surface conditioning liquid have a great relationship with the quality of the water used to prepare it. Usually, tap water is used to prepare the surface conditioning liquid. But it is known that tap water usually contains cations such as calcium, magnesium and the like. The content of the cations depends on the water source. In this case, it is known that the titanium colloid is kept dispersed without precipitation by the electric repulsive force of the charge in the anion. Due to lrrl .------- · installation -------- order ---- I ---- line Φ- (Please read the precautions on the back before filling this page) This paper size applies China National Standard (CNS) A4 (210 X 297 mm) -5- 491912 Α7 B7 V. Description of the Invention (3) Therefore, if the tap water contains an excessive amount of cationic components, the titanium colloid will be neutralized by the cationic components , And lose its repulsive force so that it condenses and precipitates. (Please read the precautions on the back before filling out this page) Some people have proposed adding condensed phosphates such as pyrophosphate to the surface conditioning solution to block cationic components and maintain the stability of titanium colloids. However, when an excessive amount of condensed phosphate is added to the surface conditioning solution, an inert coating may be generated due to the embodiment of the condensed phosphoric acid and the metal surface in the conditioning solution. The process creates problems. When the tap water contains an excessive amount of calcium or magnesium, pure water is required to make the conditioning solution, resulting in economic disadvantages. The third problem is the temperature and PΗ at the time of application. For example, the titanium colloid will condense at a temperature of 3 5 ° C and beyond the range of ρ Η 8 · 0 to 9.5, and it will lose its surface conditioning effect. Therefore, the conventional surface conditioning liquid is used in a narrow range of a specific temperature and a narrow range of a specific pH. Therefore, the surface conditioning liquid cannot produce a cleaning effect like the single-liquid type. Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs The fourth problem is that the miniaturization of phosphate crystals is limited. The miniaturization of the phosphate is started from the formation of titanium colloidal crystal nuclei adsorbed on the metal surface, which contributes to the refinement of phosphate crystals. Therefore, the more titanium colloids adsorbed on the metal surface, the finer phosphate crystals can be obtained. To solve this problem, a simple method is to increase the number of titanium colloids in the conditioning solution. However, the higher the density, the more frequently the colloids collide with each other in the conditioning liquid, resulting in more coagulation and sedimentation. The upper limit of the currently used titanium colloid is less than 100 parts per million, and it is not possible to use a higher density titanium colloid conditioning solution. JP56 — 156778 and JP57 — 23066A -6-This paper size applies to the Chinese National Standard (CNS) A4 (210 X 297 mm) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 491912 A7 _____B7 V. Description of Invention (4) A method for spraying a suspension of insoluble phosphate containing a divalent or trivalent metal on the steel surface under pressure is disclosed. However, the effect is exhibited only when the suspension is sprayed under pressure, so this method cannot be applied to the general conditioning method of dipping the metal or spraying the conditioning liquid. J P40-1 0 9 5B2 has disclosed another surface conditioning method 'which involves immersing a galvanized steel sheet in a suspension of a divalent or trivalent metal insoluble phosphate. However, the application examples of this method are limited to galvanized steel, and high-density insoluble phosphates of at least 30 g / l need to be used. As explained in the article, the methods related to Jernstedt salt have presented so many problems. However, there is currently no method that can replace the Jernstedt method. DISCLOSURE OF THE INVENTION The object of the present invention is to solve the problems of the aforementioned conventional technology, and provide a novel conditioning liquid and a novel conditioning method, which promote and accelerate chemical reactions, make phosphate crystals finer, and maintain stability for a long time. The inventors of the present inventors have thoroughly studied to solve the foregoing problems, and finally obtained a novel surface conditioning liquid and conditioning method that can further improve the quality of the phosphate layer. That is, the present invention is (1): a conditioning liquid for pretreatment for forming a phosphate layer on a metal surface, which is characterized in that it contains phosphate particles of one or more than one divalent or trivalent metal, and contains One or more accelerating ingredients selected from monosaccharides, polysaccharides and derivatives thereof. Moreover, the present invention is (2): a kind of paper for forming the paper on a metal surface, applicable to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) ------------ Xin Clothes -------- Order --------- Line · (Please read the precautions on the back before filling this page) Printed by the Employees' Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 491912 Α7 Β7 V. Invention Explanation (5) The conditioning liquid used for the pretreatment of the phosphate layer is characterized in that it contains one or more than one kind of divalent or trivalent metal phosphate particles, and contains one or more than one acceleration component, selected from orthophosphoric acid Salts, polyphosphates and organic phosphonic acid compounds. Furthermore, the present invention is (3): a conditioning liquid for pretreatment for forming a phosphate layer on a metal surface, which is characterized in that it contains one or more phosphate particles of a divalent or trivalent metal, It also contains one or more than one water-soluble polymer compound selected from polymers of vinyl acetate, derivatives thereof, and copolymers of vinyl acetate and other monomers. Moreover, the present invention is (4): a conditioning liquid for pretreatment for forming a phosphate layer on a metal surface, which is characterized in that it contains phosphate particles of one or more than one divalent or trivalent metal, and Containing one or more acceleration components selected from polymers or copolymers obtained by polymerizing the following monomer i) and less than 50 weight percent of the following monomer 1 i). Monomer 1) A monomer represented by the following formula (1) or selected from α-, / 5-unsaturated carbonic acid monomers. The monomer i i) is a monomer copolymerizable with the aforementioned monomer i). R1 H2C = C-COOR2 .................. Formula (1) (R1: Η or CH3, R2: Η or an alkyl group having C 1 ~ 5 or having C 1 ~ 5 Hydroxyalkyl) In the aforementioned (1) ~ (4), the phosphate particles should advantageously contain particles with a diameter of less than 5 microns, and the total concentration should be in the range of 0.0 0 1 to 3 0. This paper size applies to Chinese national standards (CNS) A4 specification (210 X 297 mm) • I -------- Order -------! Line (Please read the precautions on the back before filling out this page), '-8-491912 Α7 Β7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 5. The invention description (6) g / liter is better, and the two price Or the trivalent metal is preferably at least one selected from the group consisting of Zη, Fe, Mn, Ni, Co, Ca, and A1. And the total concentration of the accelerated component should be 1 to 2000 parts per million. 'In addition, the conditioning liquid preferably contains other alkali metal or ammonium salts or a mixture thereof. These alkali metal or ammonium salts include orthophosphate, metaphosphate, orthosilicate, metasilicate, carbonate, bicarbonate, nitrate, nitrite, sulfate, borate, and organic acid salts. The preferred total concentration is from 0.5 to 20 g / l. In the conditioning method of the present invention, the metal surface is brought into contact with the aforementioned conditioning liquid before a phosphate layer is formed. This is because the conditioning liquid of the present invention has higher stability in the high PP range and high temperature than the titanium colloid in the conventional technology. Therefore, the conditioning solution of the present invention may further contain an alkali component and one or more additives selected from nonionic surfactants and anionic surfactants. This conditioning fluid can also have another effect of cleaning the metal surface. The metal treated with this conditioning liquid has a clean surface and has properties suitable for forming a phosphate layer. As explained above, in the conventional method, before the phosphate layer is chemically formed, three steps (1) to remove fatty oil, (2) to wash and (3) surface conditioning are required. By using the conditioning liquid of the present invention that has both a degreasing effect and a surface conditioning effect, these three steps can be simplified into a single step, combining the method of degreasing and surface conditioning, as described in item (1) below. That is, two steps can be reduced. The conditioning liquid of the present invention can effectively provide a surface suitable for forming a phosphate layer in a wider range of P 较 than the conventional P Η range. Therefore, the present invention can be another (please read the note on the back? Matters and then fill out this page)-binding-ordering-thread size paper size applies to China National Standard (CNS) A4 specifications (210 X 297) (Centi) -9- 491912 A7 _____ B7 V. Description of the invention (7) In addition, an alkali metal salt is added to the conditioning solution, and the invention can obtain a conditioning liquid with both cleaning and surface conditioning effects. (Please read the precautions on the back before filling in this page) (1) Method of combining degreasing and surface conditioning '(2) Chemically forming a phosphate layer (3) Washing (multi-stage) (4) in pure water The best mode for rinsing the present invention is that the phosphate particles of the divalent or trivalent metal and the acceleration component are essential components of the present invention. As mentioned above, the object of the present invention is to provide a surface conditioning solution 'which activates the metal surface before forming a phosphate layer, and generates crystal nuclei for the precipitation of phosphate crystals. The inventors have found that phosphate particles of a bivalent or trivalent metal having a better diameter are adsorbed on a metal surface to be treated in an aqueous solution containing an accelerated component at a preferable content, and are generated for crystallization of a phosphate layer Crystal nuclei and accelerate the formation of phosphate layers. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs The phosphate particles of the divalent or trivalent metal of the present invention are solid and insoluble. However, it is chemically similar to the chemical substance used to form the phosphate layer, and it is also chemically similar to the formed phosphate layer. It will not have a negative effect on the solution used to form the phosphate layer. Even if a part of the conditioning solution is placed in a subsequent immersion bath containing a solution for forming a phosphate layer, it will not affect the phosphate layer. have negative impacts. Examples of the phosphate particles of the divalent or trivalent metal of the present invention include the following.

Zn3(P〇4)2，Zn2Fe(P〇4)2，本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -10- 491912 A7 B7 五、發明說明（8 ) Ζ η 2 Ν 1 ( Ρ 〇 4 )2，，Ν i 3( Ρ 〇 4 )2， Ζ η 2 Μ η ( Ρ 〇 4 )2，Μ η 3( Ρ 〇 4 )2， Μη 2 F e ( Ρ 〇 4 )2，，C a 3( Ρ 〇 4 )2， Ζ η 2 C a ( Ρ 〇 4 )2，，F e Ρ〇 4 ， A 1 Ρ 〇 4， Co Ρ〇 4 ， C 〇 3 (Ρ〇4 ) 2及此等化合物之水合物 (請先閱讀背面之注咅3事項再填寫本頁) 磷酸鹽層結晶之粒徑隨著反應開始時沉澱之結晶數目的增加而變小。因爲當相鄰結晶彼此接觸時，結晶即停止生長。而反應開始時之結晶數目愈高，結晶間之距離愈小，故該金屬表面可於較短時間內被較小之結晶所覆蓋。因此，爲了於短時間內沉澱較細之磷酸鹽結晶，以於形成磷酸鹽層之前先製造較多晶核爲佳。就穩定地分散於該水溶液中之觀點而言，本發明二價或三價金屬之粒徑亦以小於5微米爲佳。即使本發明調理液中可能含有直徑大於5微米之二價或三價金屬之磷酸鹽，但當該液體亦含有足量之小於5微米之磷酸鹽粒子時，並不破壞本發明效果。經濟部智慧財產局員工消費合作社印製本發明二價或三價金屬之磷酸鹽粒子本身亦具有促進沉澱之效果。即，該二價或三價金屬之磷酸鹽粒子可於調理過程中吸附於該金屬表面上，而其中有些本身可溶解於後續步驟之磷酸鹽層形成浴中，於金屬表面附近對該磷酸鹽層提供磷酸鹽成分，而大幅促進磷酸鹽層之沉澱。期望二價或三價金屬之磷酸鹽粒子總量係介於 0 · 00 1〜30克/升之間。二價或三價金屬之磷酸鹽粒子總量低於〇 · 0 0 1克/升時，吸附於金屬表面上之本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） · 1 ] _ 經濟部智慧財產局員工消費合作社印製 491912 A7 r-, ____ B7 五、發明說明（9 ) 一價或二價金屬之磷酸鹽粒子量降低，而無法促進磷酸鹽結晶之沉澱’而較少量之粒子亦無法促進該化學反應。二價或三價金屬之磷酸鹽粒子量高於3 〇克/升時僅 ’產生不利之成本因素，而無法再進一步磷酸鹽之形成。下文將描述本發明調理液所包含之加速成分。如前文所述’於習用技術中，二價或三價金屬之不可溶磷酸鹽係於加壓下噴射以供表面調理使用。於加壓下噴射之理由爲藉著使該不可溶磷酸鹽硬性碰撞於該金屬表面或如噴射鎚頭般地切削該金屬表面，可使之反應。而且，使用習用方法得到表面調理效果時，二價或三價金屬之不可溶磷酸鹽之密度需極度地增加。本發明者已發現當本發明之加速成分存在時，即使於較低密度之二價或三價金屬磷酸鹽粒子且不使用將其噴射於金屬表面之物理力的情況下，仍可得到表面調理效果。因此，於本發明中，使該金屬表面與該調理液接觸即已足夠。本發明加速成分（以下簡稱爲促進劑）可改善二價或三價金屬之磷酸鹽粒子的分散安定性，並促進二價金屬或三價金屬之磷酸鹽粒子於該金屬表面上之吸附。該促進劑係吸附於二價或三價金屬之各個磷酸鹽粒子的表面上，藉著賦予該磷酸鹽粒子電荷排斥力及固體阻礙效應而破壞二價或三價金屬之磷酸鹽粒子的彼此碰撞，並防止磷酸鹽粒子凝結及沉降。而且，該促進劑本身具有吸附於金屬表面之能力，並藉著被吸附於該磷酸鹽粒子表面而促進磷酸鹽 -----------裳--------訂---------線 (請先閱讀背面之注意事項再填寫本頁) 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -12- 491912 A7 B7 五、發明說明（10 ) 粒子吸附於該金屬表面。僅藉著使該金屬與該調理液接觸即可達成調理效果。 (請先閱讀背面之注音？事項再填寫本頁) 促進劑用量以百萬分之1〜2 0 0 0份數爲佳。若低 ’於百萬分之1份數，則該表面調理液無法達到表面調理效果。若高於百萬分之2 0 0 0份數，則無法進一步改善其效果，而產生金屬表面被促進劑覆蓋且該磷酸鹽粒子可能變成難以吸附於該金屬表面之危險。於本發明調理液（1 )中，應含有選自單醣、多醣及其衍生物之促進劑。單醣、多醣及其衍生物之基本醣成分可選自下列物質：果糖、塔格糖、阿洛酮糖、沙伯糖 (sulbose )、赤蘚酮糖、海藻糖、核糖、***糖、木糖、地衣糖（lichetose )、異構糖、阿卓糖、葡萄糖、甘露糖、古洛糖、艾杜糖、半乳糖、塔羅糖等。經濟部智慧財產局員工消費合作社印製因此，若使用單醣，則可應用前述基本醣基。若欲使用多醣，則使用同多醣或異多醣。亦可使用其衍生物，諸如使用置換基團諸如N〇2、C Η 3、C 2 Η 4〇Η、 CH2CH (〇H) CH3、CH2C〇〇H等使該基本醣基之羥基進行醚化而製得之單醣，或含有使用前述基團置換所得之單醣之同醣及異醣。亦可使用單醣、多醣及其衍生物之組合物。醣基亦可根據其水解而分成單醣、寡醣及多醣。於本發明中，其分成經由水解產生多於兩個單醣之多醣及無法進一步水解之單醣。因爲本發明與生化反應無關，故該效果與該基本單醣本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -13- 經濟部智慧財產局員工消費合作社印製 491912 • A7 B7 五、發明說明（11 ) 成分之三維結構或旋光性無關，而D -單醣、L -單醣及旋光（+，一）之任何組合物皆可使用。而且，爲了提高水溶性，毫無問題地可使用該單醣、多醣及其衍生物之鈉鹽及銨鹽。而且，若涉及溶解困難之問題，則其可先溶於有機溶劑中。於本發明調理液（2 )中，應含有一或多於一個加速成分，選自原磷酸、多磷酸或有機膦酸。就多磷酸而言，可使用焦磷酸、三磷酸、三偏磷酸、四偏磷酸、六偏磷酸及其鈉鹽及銨鹽。就有機膦酸而言，可使用胺基三亞甲基膦酸、1 一羥基亞乙基一1、1 一二膦酸、乙二胺四亞甲基膦酸、二伸乙基三胺五亞甲基膦酸、及其鈉鹽。可毫無問題地個別或組合使用該原磷酸、多磷酸及有機膦酸。於本發明調理液（3 )中，應含有一或多於一種加速成分，選自乙酸乙烯基及其衍生物之水性聚合物及乙酸乙烯基與可與乙酸乙烯基共聚之單體之共聚物。就乙酸乙烯基及其衍生物之聚合物而言，可使用乙酸乙烯基之聚合物之皂類形式的聚乙烯醇、藉著使用丙烯腈將聚乙烯醇氰乙基化所得之經氰乙基化-聚乙烯醇、藉著使用甲醛水溶液使聚乙烯醇縮醛化所得之經甲醛化-聚乙烯醇、藉著使用脲使聚乙烯醇經胺基甲酸乙酯化所得之經胺基甲酸乙酯化 -聚乙烯醇、及藉著導入羧基、硕基、醯胺基於聚乙烯醇所得之水性巨分子化合物。就與乙酸乙烯基共聚之單體而言，可使用丙烯酸、巴豆酸、無水順丁烯二酸等。前述乙酸乙烯基或其衍生物之聚合物、或乙酸乙烯基本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -14- -----------裝--------訂----------線 (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 491912 A7 — B7 五、發明說明（12) 與可與乙酸乙烯基共聚之單體之共聚物若具有水性，則完全發揮本發明之效用。該效用不受聚合度或官能基之導A 程度所影響，該單體或共聚物可毫無問題地個別或結合使 .用。於本發明調珲液（4 )中，應含有一或多於一種促進成分，選自藉著聚合下述單體i )及低於5 〇百分比之下述單體i i )所得之聚合物或共聚物。單體i ):下式（1 )所不之單體或選自^ 一、/3 -不飽和碳酸單體之單體。單體i i )可與前述單體i )共聚之單體。 R1Zn3 (P〇4) 2, Zn2Fe (P〇4) 2, this paper size applies Chinese National Standard (CNS) A4 specification (210 X 297 mm) -10- 491912 A7 B7 V. Description of the invention (8) Z η 2 Ν 1 (Ρ〇4) 2,, Νi 3 (Ρ〇4) 2, Z η 2 Μ η (Ρ〇4) 2, Μ η 3 (Ρ〇4) 2, Μη 2 F e (Ρ〇) 4) 2,, Ca 3 (PO4) 2, Zη2Ca (PO4) 2, FePO4, A1PO4, CoPO4, Co3 (PO3) 〇4) 2 and the hydrates of these compounds (please read Note 3 on the back before filling out this page) The particle size of the phosphate layer crystals becomes smaller as the number of crystals precipitated at the beginning of the reaction decreases. This is because when adjacent crystals contact each other, the crystals stop growing. The higher the number of crystals at the beginning of the reaction, the smaller the distance between crystals, so the metal surface can be covered by smaller crystals in a shorter time. Therefore, in order to precipitate finer phosphate crystals in a short time, it is better to make more crystal nuclei before forming the phosphate layer. From the viewpoint of stably dispersing in the aqueous solution, the particle diameter of the divalent or trivalent metal of the present invention is also preferably less than 5 m. Even though the conditioning liquid of the present invention may contain phosphate salts of divalent or trivalent metals having a diameter of more than 5 m, the effect of the present invention is not impaired when the liquid also contains a sufficient amount of phosphate particles of less than 5 m. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs The phosphate particles of the divalent or trivalent metal of the present invention also have the effect of promoting precipitation. That is, the phosphate particles of the divalent or trivalent metal can be adsorbed on the surface of the metal during the conditioning process, and some of them can be dissolved in the phosphate layer forming bath in the subsequent step, and the phosphate is near the metal surface. The layer provides a phosphate component and greatly promotes precipitation of the phosphate layer. The total amount of phosphate particles of the divalent or trivalent metal is desirably between 0.001 and 30 g / liter. When the total number of phosphate particles of the divalent or trivalent metal is less than 0.001 g / L, the paper size adsorbed on the metal surface applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm). 1] _ Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 491912 A7 r-, ____ B7 V. Description of the invention (9) The amount of phosphate particles of monovalent or divalent metals is reduced, which cannot promote the precipitation of phosphate crystals. Smaller amounts of particles also fail to promote the chemical reaction. When the amount of the phosphate particles of the divalent or trivalent metal is higher than 30 g / l, only a disadvantageous cost factor is caused, and no further phosphate formation is possible. The acceleration component contained in the conditioning liquid of the present invention will be described below. As described above, 'In conventional techniques, the insoluble phosphate of a divalent or trivalent metal is sprayed under pressure for surface conditioning. The reason for spraying under pressure is to make the insoluble phosphate react by hardly striking the metal surface or cutting the metal surface like a spray hammer. Moreover, when the conventional method is used to obtain the surface conditioning effect, the density of the insoluble phosphate of the divalent or trivalent metal needs to be extremely increased. The present inventors have discovered that when the acceleration component of the present invention is present, surface conditioning can be obtained even in the case of lower density bivalent or trivalent metal phosphate particles without using the physical force that sprays them onto the metal surface effect. Therefore, in the present invention, it is sufficient to bring the metal surface into contact with the conditioning liquid. The acceleration component (hereinafter referred to as an accelerator) of the present invention can improve the dispersion stability of phosphate particles of a divalent or trivalent metal, and promote the adsorption of phosphate particles of a divalent or trivalent metal on the surface of the metal. The accelerator is adsorbed on the surface of each phosphate particle of the divalent or trivalent metal, and destroys the collision of the phosphate particles of the divalent or trivalent metal with each other by giving the phosphate particles a charge repulsive force and a solid barrier effect. , And prevent the phosphate particles from coagulating and settling. In addition, the accelerator itself has the ability to adsorb on the metal surface, and promotes phosphate by being adsorbed on the surface of the phosphate particles. --------- Line (Please read the precautions on the back before filling this page) This paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm) -12- 491912 A7 B7 V. DESCRIPTION OF THE INVENTION (10) Particles are adsorbed on the metal surface. The conditioning effect can be achieved simply by bringing the metal into contact with the conditioning liquid. (Please read the note on the back? Matters before filling out this page.) Accelerator dosage is preferably 1 to 2000 parts per million. If it is lower than 1 part per million, the surface conditioning liquid cannot achieve the surface conditioning effect. If it is more than 2000 parts per million, the effect cannot be further improved, and there is a danger that the metal surface is covered with an accelerator and the phosphate particles may become difficult to be adsorbed on the metal surface. The conditioning liquid (1) of the present invention should contain an accelerator selected from the group consisting of monosaccharides, polysaccharides, and derivatives thereof. The basic sugar components of monosaccharides, polysaccharides and their derivatives can be selected from the following substances: fructose, tagatose, allosene, sulbose, erythrulose, trehalose, ribose, arabinose, xylose Sugar, lichetose, isomerized sugar, altose, glucose, mannose, gulose, idose, galactose, talose, and the like. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs Therefore, if monosaccharides are used, the aforementioned basic sugar bases can be applied. If polysaccharides are to be used, homopolysaccharides or isopolysaccharides are used. Derivatives such as etherification of the basic glycosyl hydroxyl group using substitution groups such as No. 2, C Η 3, C 2 Η 4〇Η, CH2CH (〇H) CH3, CH2COOH etc. The prepared monosaccharides may contain the same sugars and isomers of the monosaccharides obtained by substituting the aforementioned groups. Combinations of monosaccharides, polysaccharides and their derivatives can also be used. Glycans can also be divided into monosaccharides, oligosaccharides and polysaccharides according to their hydrolysis. In the present invention, it is divided into a polysaccharide that produces more than two monosaccharides by hydrolysis and a monosaccharide that cannot be further hydrolyzed. Because the present invention has nothing to do with biochemical reactions, the effect and the size of the basic monosaccharide paper are subject to the Chinese National Standard (CNS) A4 specification (210 X 297 mm). A7 B7 5. Description of the invention (11) The three-dimensional structure or optical rotation of the ingredients is not relevant, and any combination of D-monosaccharide, L-monosaccharide, and optical rotation (+, one) can be used. Further, in order to improve the water solubility, the sodium salt and ammonium salt of the monosaccharide, polysaccharide and its derivative can be used without any problem. Furthermore, if it is difficult to dissolve, it can be dissolved in an organic solvent first. The conditioning liquid (2) of the present invention should contain one or more acceleration components selected from orthophosphoric acid, polyphosphoric acid or organic phosphonic acid. As for polyphosphoric acid, pyrophosphate, triphosphate, trimetaphosphate, tetrametaphosphate, hexametaphosphate, and their sodium and ammonium salts can be used. As for the organic phosphonic acid, aminotrimethylenephosphonic acid, 1-hydroxyethylidene-1, 1-diphosphonic acid, ethylenediaminetetramethylenephosphonic acid, and diethylenetriaminepentaimine can be used. Methylphosphonic acid, and its sodium salt. The orthophosphoric acid, polyphosphoric acid, and organic phosphonic acid can be used individually or in combination without any problem. In the conditioning liquid (3) of the present invention, it should contain one or more than one accelerating component, which is selected from the group consisting of aqueous polymers of vinyl acetate and its derivatives and copolymers of vinyl acetate and monomers copolymerizable with vinyl acetate . For polymers of vinyl acetate and its derivatives, polyvinyl alcohol in the form of soaps of vinyl acetate polymers can be used, and cyanoethyl obtained by cyanoethylating polyvinyl alcohol by using acrylonitrile Formaldehyde-polyvinyl alcohol, formaldehyde-polyvinyl alcohol obtained by acetalizing polyvinyl alcohol using an aqueous formaldehyde solution, ethyl carbamic acid ester obtained by subjecting polyvinyl alcohol to urethane using urea Esterification-Polyvinyl alcohol, and water-based macromolecular compounds based on polyvinyl alcohol by introduction of carboxyl, sulfonyl, amidine. As the monomer copolymerized with vinyl acetate, acrylic acid, crotonic acid, anhydrous maleic acid, and the like can be used. The aforementioned polymer of vinyl acetate or its derivative, or vinyl acetate This paper is sized to the Chinese National Standard (CNS) A4 (210 X 297 mm) -14- ----------- pack- ------- Order ---------- line (Please read the notes on the back before filling out this page) Printed by the Consumers' Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 491912 A7 — B7 V. Description of Invention (12) If the copolymer with a monomer copolymerizable with vinyl acetate is water-based, the effect of the present invention is fully exerted. This effect is not affected by the degree of polymerization or the degree of A-functionality of the functional group, and the monomer or copolymer can be used individually or in combination without any problem. In the tincture adjusting liquid (4) of the present invention, one or more than one accelerating component should be selected from a polymer obtained by polymerizing the following monomer i) and less than 50% of the following monomer ii) or Copolymer. Monomer i): a monomer not represented by the following formula (1) or a monomer selected from the group consisting of ^, / 3 -unsaturated carbonic acid monomer. The monomer i i) is a monomer copolymerizable with the aforementioned monomer i). R1

I H2C = C 一 C〇〇R2 ............式（1 ) (式中R1 : Η或CH3，R2 : Η或具有C 1〜5之烷基或具有C1〜5之羥烷基）就式（1 )所示之單體而言，可使用丙烯酸甲酯、丙烯酸乙酯、丙烯酸丙酯、丙烯酸丁酯、丙烯酸戊酯、甲基丙烯酸甲酯、甲基丙烯酸乙酯、甲基丙烯酸丙酯、甲基丙烯酸丁酯、甲基丙烯酸戊酯、丙烯酸羥甲酯、丙烯酸羥乙酯、丙烯酸羥丙酯、丙烯酸羥丁酯、丙烯酸羥戊酯、甲基丙烯酸羥甲酯、甲基丙烯酸羥乙酯、甲基丙烯酸羥丙酯、甲基丙烯酸羥丁酯、甲基丙烯酸羥戊酯。而且，就α -，/? 一不飽和碳酸單體而言，可使用丙烯酸、甲基丙烯酸、順丁烯二酸。就單體i i )而言，可本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公爱） ------------裝--------訂---------線 (請先閱讀背面之注音3事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 491912 Α7 Β7 五、發明說明（13 ) 使用乙酸乙烯基、苯乙烯、氯化乙烯、乙烯基磺酸。可毫無問題地使用藉著聚合其中一單體所得之聚合物、及藉著同時聚合其中數種單體所得之共聚物。 * 本發明調理液可含有鹼金屬鹽或銨鹽或此兩鹽之組合物。就鹼金屬鹽及銨鹽而言，可使用原磷酸鹽、偏磷酸鹽、原矽酸鹽、偏矽酸鹽、碳酸鹽、碳酸氫鹽、硝酸鹽、亞硝酸鹽、硫酸鹽、硼酸鹽、及有機酸之鹽。亦可毫無問題地組合使用多於兩種之鹽。使用於本發明之鹼金屬鹽及銨鹽可作爲鹼組份，可具有與工業淸潔劑所含者相同之功效。其可使該調理液具有水軟化效果及脫脂效果，而改善調理液之液體安定性，並賦予淸潔劑效果。鹼金屬鹽或銨鹽之期望用量係0·5〜20克/升。低於0 . 5克/升時，水軟化效果及淸潔效果不足’高於 2 0克/升時則不經濟。與習用液體不同地，本發明調理液可於許多環境下保持效果。即，本發明調理液體與習用者比較之下具有以下優點： (1 )長期安定性高。 (2)即使導入含高濃度Ca ，Mg之硬水，仍不降低該效果。 (3 )可於高溫下施加。 (4)可添加各式各樣之鹼金屬鹽。 (5 )於寬幅p Η範圍內具安定性。 -----------•裝--------訂--------- (請先閱讀背面之注意事項再填寫本頁) 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -16- 491912 A7 一 B7 五、發明說明（14 ) (請先閱讀背面之注意事項再填寫本頁) 習用調理液可因添加淸潔劑而降低其性質，難以應用於同時需要淸潔效果及調理效果之方法。於本發明中，可毫無問題地添加淸潔劑諸如鹼金屬鹽及銨鹽。可毫無問題 '地另於本發明調理液中添加其他鹼組份諸如無機鹼組份、有機鹼組份及界面活性劑。而且，於本發明中，可添加鉗合劑及縮合之磷酸鹽於該液體中，以消除添加於液體中之陽離子性成分的效果。本發明方法僅需使該金屬表面與該調理液體接觸，而對調理液之接觸時間或溫度並無確實之限制。而且，本發明調理液可應用於所有類型之金屬諸如鋼、鑛鋅之鋼板、鋁或鋁合金及鎂或鎂合金。就本發明調理之後所進行之磷酸鹽層形成方法而言，可使用任何類型之方法，包括浸漬、噴灑、電解等。而且’就磷酸鹽層而言，可毫無問題地提供任何類型之磷酸鹽諸如磷酸鋅、磷酸鎂或磷酸鈣-鋅。具體實例及對照例經濟部智慧財產局員工消費合作社印製下文將藉著出示具體實例及對照例而更詳細地說明本發明。於此等實施例中，以磷酸鋅層作爲磷酸鹽層之實例，而本發明可應用於其他類型之磷酸鹽層。〔試驗部分〕 SPC:(冷軋鋼板：JIS — G— 3141) EG:(兩側面電鍍鋅之鋼板：鍍鋅體積2 0克/ 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -17- 經濟部智慧財產局員工消費合作社印製 491912 A7 B7 五、發明說明（15 ) 米2 ) 、 G A ：(鋼板，兩側面熱浸塗鋅：鍍鋅體積4 5克/ 米2 ) • Ζ η - N i :(兩側面電鍍鎳一鋅合金之鋼板··電鍍體積2 0克/米2 ) A 1 ：(鋁板：JIS — 5052) MP:(鎂合金板：J IS— Η— 4201)。〔試片之處理〕 •鹼脫脂係使用 FINE CLEANER 14460(Nihon Parkerizing Co.Ltd之商標）進彳了，以自來水稀釋至2百分比，於4 2 °C下噴灑於試樣上歷經1 2 0秒。 •表面調理液係使用不同種類之溶液。而試樣係浸漬於溶液中。 •磷酸鹽層之形成係使用PALBOND L 3 0 2 〇 (Nihon Parkerizing Co.Ltd之商標）進行，以自來水稀釋至4 · 8百分比。試樣係於4 2 °C下浸漬1 2 0秒。 •於水中洗滌及以去離子水漂洗係藉著於室溫下噴灑 3 0秒而進行。〔磷酸鹽層之評估〕針對以下項目評估磷酸鹽層。即測量外觀、薄層重量 (C . W )、薄層晶粒大小（C · s )及P -比例。 •外觀一一一 ◎:良好而均句，〇：部分不均句， -----------裝-------^訂--------- (請先閱讀背面之注意事項再填寫本頁) 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -18- 491912I H2C = C-C〇〇R2 ............ Formula (1) (where R1: Η or CH3, R2: Η or an alkyl group having C 1 ~ 5 or C1 ~ As the monomer represented by the formula (1), methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, pentyl acrylate, methyl methacrylate, and methacrylic acid can be used. Ethyl ester, propyl methacrylate, butyl methacrylate, amyl methacrylate, hydroxymethyl acrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, hydroxypentyl acrylate, hydroxymethacrylate Methyl ester, hydroxyethyl methacrylate, hydroxypropyl methacrylate, hydroxybutyl methacrylate, hydroxypentyl methacrylate. Further, as for the α-, /?-Unsaturated carbonic acid monomer, acrylic acid, methacrylic acid, and maleic acid can be used. As for monomer ii), this paper size can apply Chinese National Standard (CNS) A4 specification (210 X 297 public love) ------------ install -------- order --------- Line (Please read the note on the back 3 before filling out this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 491912 Α7 Β7 V. Description of the invention (13) Use of vinyl acetate, benzene Ethylene, vinyl chloride, vinyl sulfonic acid. A polymer obtained by polymerizing one of the monomers and a copolymer obtained by polymerizing several of the monomers at the same time can be used without any problem. * The conditioning liquid of the present invention may contain an alkali metal salt or an ammonium salt or a combination of the two salts. For alkali metal salts and ammonium salts, orthophosphate, metaphosphate, orthosilicate, metasilicate, carbonate, bicarbonate, nitrate, nitrite, sulfate, borate, And organic acid salts. It is also possible to use more than two salts in combination without any problem. The alkali metal salt and ammonium salt used in the present invention can be used as an alkali component and can have the same effects as those contained in industrial detergents. It can make the conditioning liquid have water softening effect and degreasing effect, improve the liquid stability of the conditioning liquid, and give a detergent effect. The desired amount of alkali metal or ammonium salt is from 0.5 to 20 g / L. When it is lower than 0.5 g / liter, the water softening effect and cleaning effect are insufficient. When it is higher than 20 g / liter, it is uneconomical. Unlike conventional liquids, the conditioning liquids of the present invention can maintain their effects in many environments. That is, the conditioning liquid of the present invention has the following advantages compared with the user: (1) Long-term stability. (2) Even if hard water containing high concentration of Ca and Mg is introduced, the effect is not reduced. (3) Can be applied at high temperatures. (4) Various alkali metal salts can be added. (5) Stability in a wide range of p Η. ----------- • Installation -------- Order --------- (Please read the notes on the back before filling this page) This paper size is applicable to China Standard (CNS) A4 specification (210 X 297 mm) -16- 491912 A7-B7 V. Description of the invention (14) (Please read the precautions on the back before filling this page) The conventional conditioning liquid can be added with detergent Reducing its properties is difficult to apply to methods that require both cleaning and conditioning effects. In the present invention, detergents such as alkali metal salts and ammonium salts can be added without problems. It is possible to add other base components such as an inorganic base component, an organic base component and a surfactant to the conditioning liquid of the present invention without any problem. Moreover, in the present invention, a clamping agent and a condensed phosphate may be added to the liquid to eliminate the effect of the cationic component added to the liquid. The method of the present invention only needs to bring the metal surface into contact with the conditioning liquid, and there is no exact limit on the contact time or temperature of the conditioning liquid. Moreover, the conditioning liquid of the present invention can be applied to all types of metals such as steel, steel plate of ore zinc, aluminum or aluminum alloy, and magnesium or magnesium alloy. As for the method for forming the phosphate layer after the conditioning of the present invention, any type of method may be used, including dipping, spraying, electrolysis, and the like. And, as far as the phosphate layer is concerned, any type of phosphate such as zinc phosphate, magnesium phosphate or calcium-zinc phosphate can be provided without any problem. Specific Examples and Comparative Examples Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs The present invention will be explained in more detail by showing specific examples and comparative examples. In these embodiments, a zinc phosphate layer is taken as an example of the phosphate layer, and the present invention can be applied to other types of phosphate layers. [Experimental part] SPC: (Cold-rolled steel sheet: JIS — G — 3141) EG: (Electro-galvanized steel sheet on both sides: Galvanized volume 20 g / This paper size applies to China National Standard (CNS) A4 (210 X 297) (Mm) -17- Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 491912 A7 B7 V. Description of the invention (15) m 2), GA: (steel plate, hot dip galvanized on both sides: galvanized volume 4 5 g / m 2) • Z η-N i: (Steel plated nickel-zinc alloy plated on both sides ·· Plating volume 20 g / m 2) A 1: (Aluminum plate: JIS — 5052) MP: (Magnesium alloy plate: J IS— Η— 4201). [Treatment of test piece] • Alkali degreasing was performed using FINE CLEANER 14460 (trademark of Nihon Parkerizing Co. Ltd), diluted with tap water to 2%, and sprayed on the sample at 4 2 ° C for 120 seconds. . • The surface conditioning solution uses different kinds of solutions. The sample was immersed in the solution. • The formation of the phosphate layer was performed using PALBOND L 3 0 2 0 (trademark of Nihon Parkerizing Co. Ltd.) and diluted with tap water to 4 · 8%. The samples were immersed at 4 2 ° C for 120 seconds. • Washing in water and rinsing with deionized water are performed by spraying at room temperature for 30 seconds. [Evaluation of Phosphate Layer] The phosphate layer was evaluated for the following items. That is, the appearance, the weight of the thin layer (C.W), the grain size of the thin layer (C · s), and the P-ratio are measured. • Appearance one by one ◎: Good and even sentence, 〇: Partial uneven sentence, ----------- install ------- ^ order --------- ( Please read the precautions on the back before filling out this page.) This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) -18- 491912

附件：第88112333號專利申請案中文說明書修正頁 Α7 Β7 五、發明説明（16) 〜 △:不均勻而有某些稀薄區域，X:有許多稀薄區域，X X :無磷酸鹽層 (請先閱讀背面之注意事項再填寫本頁) • C .W.(克/米2 ):磷酸鹽層重量---W1 (克）：形成之磷酸鹽層之後的試樣重量，W 2 (克）：剝除磷酸鹽層之後之試樣重量。C . W .(克/米2 )= (W 1 - W 2 )(表面積米2)。若爲鋼板，則磷酸鹽層之剝除係藉著將該試樣浸漬於絡酸溶液中而進fr ’石爲鑛錄鋼板’則係將該試樣浸漬於含有重鉻酸銨及氨之剝除溶液中。若爲鋁及鎂板，則磷酸鋅層中之P含量係藉螢光X -射線測定，而C , W .係基於前述P含量計算。 • C · S (微米）：磷酸鹽層之晶粒大小---於藉著掃描式電子顯微鏡（S E Μ )所得之1 5 0 0倍放大影像上評估晶粒大小。Attachment: Revised page of Chinese specification of patent application No. 88112333 A7 B7 V. Description of the invention (16) ~ △: Non-uniform with some thin areas, X: Many thin areas, XX: No phosphate layer (please read first Note on the back page, please fill in this page again) • C .W. (G / m 2): weight of phosphate layer --- W1 (g): weight of the sample after formation of phosphate layer, W 2 (g): The weight of the sample after stripping the phosphate layer. C. W. (G / m 2) = (W 1-W 2) (surface area m 2). In the case of a steel plate, the stripping of the phosphate layer is performed by immersing the sample in a complex acid solution, and the frost is a mineral recording steel plate. The sample is immersed in a solution containing ammonium dichromate and ammonia. Peel off the solution. In the case of aluminum and magnesium plates, the P content in the zinc phosphate layer is measured by fluorescent X-rays, and C, W. is calculated based on the aforementioned P content. • C · S (micron): the grain size of the phosphate layer-the grain size was evaluated on a 1 500-times magnified image obtained by a scanning electron microscope (SEM).

• Ρ -比例（百分比）---此實驗値係僅於S P C 鋼板上進行。根據Ρ (磷酸鐵酸鹽之X -射線強度）及Η (磷鋅礦之X -射線強度），由下式得到Ρ -比例。經濟部智慧財產¾員工消f合作社印奴 Ρ —比例=P / ( Ρ + Η ) 表1列出申請專利範圍第1項之具體實例所使用之調理液的成分。表2列出對照例所使用之調理液。表1及2 所使用之單醣、多醣及衍生物係得自市售產品。置換基團中，以下化學式係例示基本結構單醣之葡萄糖。 -19- 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐）經濟部智慧財產局員工消費合作社印製 491912 A7 -^_____B7 五 '發明說明（17 )• P-Proportion (Percentage) --- This experiment is performed on SPC steel plate only. Based on P (X-ray intensity of ferric phosphate) and ytterbium (X-ray intensity of zinc phosphate rock), a P- ratio is obtained from the following formula. Intellectual property of the Ministry of Economic Affairs, staff, cooperatives, and slaves. P — Proportion = P / (Ρ + Η) Table 1 lists the components of the conditioning solution used in the specific example of the first scope of the patent application. Table 2 lists the conditioning solutions used in the comparative examples. The monosaccharides, polysaccharides and derivatives used in Tables 1 and 2 were obtained from commercially available products. Among the substitution groups, the following chemical formulas exemplify glucose with a basic structure of a monosaccharide. -19- This paper size applies Chinese National Standard (CNS) A4 specification (210X297 mm) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economy 491912 A7-^ _____ B7 Five 'Explanation of invention (17)

若爲葡萄糖，則位置R 1、R 2及R 3上之羥基可經醚化。於具體實例中，改變置換基團及置換度（每一單位基本醣結構由置換基團所置換之羥基的數目）以觀察效果。低水溶性之單醣、多醣及衍生物係使用鈉鹽。所製備之調理液之耐久性試驗（放置試驗）係使該調理液於室溫下保持1 0日之後進行。〔具體實例1〕 1 0 0毫升1莫耳/升之硫酸鋅溶液及1 〇〇毫升1 莫耳/升1 -磷酸氫鈉溶液於5 0 °C下交替添加於1升〇 · 5莫耳/升硫酸亞鐵（Π )溶液中，以產生沉降物。含有沉降物之溶液於9 0 °C下保持1小時以使沉降物成熟，之後傾斜漂洗1 0次。過濾並乾燥之後，由X -射線繞射分析發現該沉降物係爲磷酸千枚巖（Z η 2 F e ( P Ο 4 ) 2 · 4 Η 2 Ο )，部分含有磷酸鐵。於1公斤該磷酸千枚巖中添加5 0克藉著以異丙醇及水稀釋表1所列之單醣、多醣及衍生物所製備之1 0重量百分比溶液，於球磨機中使用0 · 5毫米直徑二氧化锆珠粒硏磨約1小時。 -----------裝—----訂--------- (請先閱讀背面之注音3事項再填寫本頁) 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -20- 491912 A7 B7 五、發明説明（18) 〜一 (請先閱讀背面之注意事項再填寫本頁) 硏磨之後’使用自來水將懸浮液中之磷酸千枚巖密度調至 1克/升而製備此具體實例所使用之調理液。以雷射繞射射粒徑分佈分析器（L A — 9 2 0 : HoribaSeisakusho 製造）測定，懸浮於該液體中之平均粒徑係爲〇 . 5微米。〔具體實例2〕 1 〇 0毫升1莫耳//升之硫酸鋅溶液及1 〇〇毫升i 莫耳/升1 -磷酸氫鈉溶液於5 0 °C下交替添加於1升〇· 5莫耳/升硫酸亞鐵（π )溶液中，以產生沉降物。含有沉降物之溶液於9 0 °C下保持1小時以使沉降物成熟’之後傾斜漂洗1 〇次。過濾並乾燥之後，由X -射線繞射分析發現該沉降物係爲磷酸千枚巖（Ζ η 2 F e ( P 〇 4 ) 2 · 4 Η 2 0 )，部分含有磷酸鐵。於1公斤藉著以異丙醇及水稀釋表1所列之單醣、多醣及衍生物所製備之1 0重量百分比溶液中添加1 〇〇克該磷酸千枚巖，於球磨機中使用0 · 5毫米直徑二氧化锆珠粒硏磨約1小經濟部智慧財產笱g(工消費合作社印製時。硏磨之後，使用自來水將懸浮液中之磷酸千枚巖密度調至1克/升而製備此具體實例所使用之調理液。以前述雷射繞射/漫射粒徑分佈分析器測定，懸浮於該液體中之平均粒徑係爲0 . 5微米。〔具體實例3〕 1 0 0毫升1莫耳/升之硫酸鋅溶液及1 0 0毫升1 •21 - 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） 491912 A7 B7 修正In the case of glucose, the hydroxyl groups at positions R 1, R 2 and R 3 may be etherified. In a specific example, change the substitution group and the degree of substitution (the number of hydroxyl groups replaced by the substitution group per unit of the basic sugar structure) to observe the effect. Monosaccharides, polysaccharides and derivatives with low water solubility use sodium salts. The durability test (storage test) of the prepared conditioning liquid was performed after the conditioning liquid was kept at room temperature for 10 days. [Specific Example 1] 100 ml of 1 mole / liter of zinc sulfate solution and 1000 ml of 1 mole / liter of 1-sodium hydrogen phosphate solution were alternately added to 1 liter of 0.5 mole at 50 ° C. Per liter of ferrous sulfate (Π) solution to produce sediment. The sediment-containing solution was kept at 90 ° C for 1 hour to allow the sediment to mature, and then rinsed 10 times with tilting. After filtering and drying, X-ray diffraction analysis revealed that the sedimentary system was Phosphate Phosphite (Z η 2 F e (P 〇 4) 2 · 4 Η 2 〇), and partly contained iron phosphate. 50 grams of a solution prepared by diluting the monosaccharides, polysaccharides, and derivatives listed in Table 1 with isopropyl alcohol and water was added to 50 grams of 1 kilogram of Phosphate Phosphorite. Use 0.5 · 5 in a ball mill. The millimeter diameter zirconia beads were honed for about 1 hour. ----------- Packing -------- Order --------- (Please read the Note 3 on the back before filling out this page) This paper size applies to Chinese National Standards (CNS ) A4 specification (210 X 297 mm) -20- 491912 A7 B7 V. Description of the invention (18) ~ 1 (Please read the precautions on the back before filling this page) After honing, use tap water to remove phosphoric acid from the suspension Thousands of rocks were adjusted to a density of 1 g / liter to prepare the conditioning liquid used in this specific example. It was measured with a laser diffraction particle size distribution analyzer (L A-920: manufactured by Horiba Seisakusho), and the average particle size suspended in the liquid was 0.5 micrometers. [Specific Example 2] 1000 ml of 1 mol // liter of zinc sulfate solution and 1000 ml of I mol / liter of 1-sodium hydrogen phosphate solution were alternately added to 1 liter of 0.5 mol at 50 ° C. Ear / liter of ferrous sulfate (π) solution to produce sediment. The sediment-containing solution was held at 90 ° C for 1 hour to allow the sediment to mature, and then rinsed 10 times with a tilt. After filtration and drying, X-ray diffraction analysis revealed that the sedimentary system was Phosphate Phosphite (Z η 2 F e (P 〇 4) 2 · 4 Η 2 0), and partially contained iron phosphate. Add 1000 g of the Phosphite Phosphate to 1 kg of a 10 weight percent solution prepared by diluting the monosaccharides, polysaccharides and derivatives listed in Table 1 with isopropanol and water, and use 0 · in a ball mill. 5 mm diameter zirconium dioxide beads honing approximately 1 g of intellectual property of the Ministry of Economic Affairs (printed by the Industrial and Consumer Cooperative). After honing, use tap water to adjust the density of the phoenite phosphate in the suspension to 1 g / liter and The conditioning liquid used in the preparation of this specific example was measured by the laser diffraction / diffuse particle size distribution analyzer described above, and the average particle size suspended in the liquid was 0.5 micron. [Specific Example 3] 1 0 0 1 mol / L zinc sulfate solution and 100 ml 1 • 21-This paper size is applicable to China National Standard (CNS) A4 specification (210X297 mm) 491912 A7 B7 Amendment

It 隻0 五、發明説明（19) 莫耳/升1 -磷酸氫鈉溶液於5 0 °C下交替添加於1升〇 · 5莫耳/升硫酸亞鐵（Π )溶液中，以產生沉降物。含有沉降物之溶液於9 0 °C下保持1小時以使沉降物成熟，之後傾斜漂洗1 0次。過濾並乾燥之後，由X -射線繞射分析發現該沉降物係爲磷酸千枚巖（Z η 2 F e ( P 〇 4 ) 2 · 4 Η 2 Ο )，部分含有磷酸鐵。於1公斤該磷酸千枚巖中添加1 0 0克藉著以水稀釋表1所列之單醣、多醣及衍生物所製備之1 0重量百分比溶液，於球磨機中使用0 · 5微米直徑二氧化锆珠粒硏磨約1小時。硏磨之後，使用自來水將懸浮液中之磷酸千枚巖密度調至1克/ 升而製備此具體實例所使用之調理液。以前述雷射繞射/ '漫射粒徑分佈分析器測定，懸浮於該液體中之平均粒徑係爲0 · 5微米。另外，添加〇 . 5克/升亞硝酸鈉試劑以作爲鹼鹽，得到欲施加之調理液。〔具體實例4〕 1 0 0毫升1莫耳/升之硫酸鋅溶液及1 0 0毫升1 莫耳/升1 一磷酸氫鈉溶液於5 0 °C下交替添加於1升〇.5莫耳/升硫酸亞鐵（Π )溶液中，以產生沉降物。含有沉降物之溶液於9 0 °C下保持1小時以使沉降物成熟，之後傾斜漂洗1 0次。過濾並乾燥之後，由X -射線繞射分析發現該沉降物係爲磷酸千枚巖（Ζ η 2 F e ( P〇4 ) 2 · 4 Η 2〇），部分含有鱗酸鐵。於1公斤藉著以水稀釋表1所列之單醣、多醣及衍生物所製備之1 0重 (請先閱讀背面之注意事項再填寫本頁) 一裝· 訂經濟部智慈財產局a(工消f合作Ti印製本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -22 491912 A7 B7 五、發明说明（20) 量百分比溶液中添加5 0克該磷酸千枚巖，於球磨機中使用〇 · 5毫米直徑二氧化锆珠粒硏磨約1小時。硏磨之後，使用自來水將懸浮液中之磷酸千枚巖密度調至1克/ 升而製備此具體實例所使用之調理液。以前述雷射繞射/ 漫射粒徑分佈分析器測定，懸浮於該液體中之平均粒徑係爲〇 · 5微米。另外，.添加〇 · 5克/升硫酸鎂7水合物試劑以作爲鹼鹽，得到欲施加之調理液。〔具體實例5〕 1 0 0毫升1莫耳/升之硫酸鋅溶液及1 〇〇毫升1 莫耳/升1 -磷酸氫鈉溶液於5 0 °C下交替添加於1升〇· 5莫耳/升硫酸亞鐵（Π )溶液中，以產生沉降物。含有沉降物之溶液於9 0 °C下保持1小時以使沉降物成熟，之後傾斜漂洗1 0次。過濾並乾燥之後，由X -射線繞射分析發現該沉降物係爲磷酸千枚巖（Ζ η 2 F e ( Ρ Ο 4 ) 2 · 4 Η 2 Ο )，部分含有磷酸鐵。於1公斤藉著以水稀釋表1所列之單醣、多醣及衍生物所製備之1 0重量百分比溶液中添加5 0克該磷酸千枚巖，於球磨機中使用0 . 5毫米直徑二氧化锆珠粒硏磨約1小時。硏磨之後，使用自來水將懸浮液中之磷酸千枚巖密度調至1克/ 升而製備此具體實例所使用之調理液。以前述雷射繞射/ 漫射粒徑分佈分析器測定，懸浮於該液體中之平均粒徑係爲〇· 5微米。 (請先閲讀背面之注意事項再填寫本頁) £· 經濟部智慈財產笱員工消费合作社印製本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -23 -It only 0. V. Description of the invention (19) Moore / liter of 1-sodium hydrogen phosphate solution was alternately added to 1 liter of 0.5 Moule / liter of ferrous sulfate (Π) solution at 50 ° C to cause sedimentation. Thing. The sediment-containing solution was kept at 90 ° C for 1 hour to allow the sediment to mature, and then rinsed 10 times with tilting. After filtration and drying, X-ray diffraction analysis revealed that the sedimentary system was Phosphate Phosphite (Z η 2 F e (P 〇 4) 2 · 4 Η 2 〇), and partly contained iron phosphate. Add 100 grams of 1 kilogram of this phosphorous phyllite to a 10 weight percent solution prepared by diluting the monosaccharides, polysaccharides and derivatives listed in Table 1 with water, and use a 0.5 micron diameter in a ball mill. The zirconia beads were honed for about 1 hour. After honing, the density of the phyllite phosphate in the suspension was adjusted to 1 g / liter using tap water to prepare the conditioning solution used in this specific example. As measured by the laser diffraction / diffuse particle size distribution analyzer, the average particle size suspended in the liquid was 0.5 micrometers. In addition, 0.5 g / L of sodium nitrite reagent was added as an alkali salt to obtain a conditioning solution to be applied. [Specific Example 4] 100 ml of 1 mole / liter of zinc sulfate solution and 100 ml of 1 mole / liter of 1 sodium hydrogen phosphate solution were alternately added to 1 liter of 0.5 mole at 50 ° C. Per liter of ferrous sulfate (Π) solution to produce sediment. The sediment-containing solution was kept at 90 ° C for 1 hour to allow the sediment to mature, and then rinsed 10 times with tilting. After filtration and drying, X-ray diffraction analysis revealed that the sedimentary system was Phosphate Phosphite (Z η 2 F e (P0 4) 2 · 4 Η 2 0), and partially contained iron scaly acid. 10 kilograms prepared by diluting the monosaccharides, polysaccharides and derivatives listed in Table 1 with water at 1 kg (please read the precautions on the back before filling this page) (Industrial and collaborative printing of Ti printed on this paper applies the Chinese National Standard (CNS) A4 specification (210X297 mm) -22 491912 A7 B7 V. Description of the invention (20) Add 50 grams of the Phosphite Phosphate to the solution in percentage , Honed in a ball mill with 0.5 mm diameter zirconia beads for about 1 hour. After honing, the density of the phoenite phosphate in the suspension was adjusted to 1 g / l using tap water to prepare this specific example. Conditioning liquid. Measured by the laser diffraction / diffuse particle size distribution analyzer, the average particle size suspended in this liquid is 0.5 micrometers. In addition, 0.5 g / L of magnesium sulfate 7 is added to hydrate The chemical reagent is used as an alkali salt to obtain a conditioning solution to be applied. [Specific Example 5] 100 ml of 1 mol / L of zinc sulfate solution and 1000 ml of 1 mol / L of 1-sodium hydrogen phosphate solution in 5 Alternately add 1 liter of 0.5 mol / L ferrous sulfate (Π) solution at 0 ° C The sediment containing solution was kept at 90 ° C for 1 hour to mature the sediment, and then rinsed by tilting 10 times. After filtering and drying, it was found by X-ray diffraction analysis that the sediment system was Phenolite Phosphate (Z η 2 F e (Ρ Ο 4) 2 · 4 Η 2 〇), partly contains iron phosphate. Prepared by diluting the monosaccharides, polysaccharides and derivatives listed in Table 1 with water at 1 kg. Add 50 grams of the Phosphate Phosphite to a 10% by weight solution, and use a 0.5 millimeter diameter zirconia beads in a ball mill for honing for about 1 hour. After honing, tap the Phosphate Phosphate in suspension with tap water The density of the opalite was adjusted to 1 g / liter to prepare the conditioning liquid used in this specific example. The average particle size suspended in the liquid was determined by the laser diffraction / diffuse particle size distribution analyzer as described above. (Please read the notes on the back before filling this page) £ · Printed on the paper by the Intellectual Property of the Ministry of Economic Affairs and the Employees' Cooperatives. The paper size is applicable to China National Standard (CNS) A4 (210X297 mm) -23-

491912 A7 __B7 五、發明説明（21) 〔具體實例6〕 1〇0毫升1莫耳/升之硫酸鋅溶液及1 0 0毫升1 莫耳/升1 一磷酸氫鈉溶液於5 0 °C下交替添加於1升〇· 5莫耳/升硫酸亞鐵（Π )溶液中，以產生沉降物。含有沉降物之溶液於9 0 °C下保持1小時以使沉降物成熟，之後傾斜漂洗1 0次。過濾並乾燥之後，由X -射線繞射分析發現該沉降物係爲磷酸千枚巖（Z n 2 F e ( P 0 4 ) 2 · 4 Η 2 0 )，部分含有磷酸鐵。於1公斤藉著以水稀釋表1所列之單醣、多醣及衍生物所製備之1 0重量百分比溶液中添加1公斤該磷酸千枚巖，於球磨機中使用0 . 5毫米直徑二氧化锆珠粒硏磨約1小時。硏磨之後，使用自來水將懸浮液中之磷酸千枚巖密度調至1克/ 升而製備此具體實例所使用之調理液。以前述雷射繞射/ 漫射粒徑分佈分析器測定，懸浮於該液體中之平均粒徑係爲0 . 5微米。〔具體實例7〕於1公斤藉水稀釋之單醣、多醣及衍生物之1 0重量百分比溶液中，添加1公斤Zn3F e (Ρ〇4) 2 · 4 Η 2 Ο，於球磨機中使用〇 · 5毫米直徑二氧化锆珠粒硏磨約1小時。硏磨之後，使用自來水將液體中之 Zn3Fe (Ρ〇4) 2· 4Η2〇密度調至1克/升而製備此應用所使用之調理液。以前述雷射繞射/漫射粒徑分佈分析器測定，懸浮於該液體中之平均粒徑係爲〇 · 6微本紙張尺度適用中國國家標準（CNS ) Α4規格（210X 297公釐） -24 - ---r------衣：訂 (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財/ip-7a (工消費合作社印災 491912491912 A7 __B7 V. Description of the invention (21) [Specific Example 6] 100 ml of 1 mole / liter of zinc sulfate solution and 100 ml of 1 mole / liter of 1 sodium hydrogen phosphate solution at 50 ° C Alternately added to 1 liter of 0.5 mol / liter of ferrous sulfate (Π) solution to produce sediment. The sediment-containing solution was kept at 90 ° C for 1 hour to allow the sediment to mature, and then rinsed 10 times with tilting. After filtering and drying, X-ray diffraction analysis revealed that the sedimentary system was Phosphate Phosphite (Z n 2 F e (P 0 4) 2 · 4 Η 2 0), and partially contained iron phosphate. To 1 kg of the 10 weight percent solution prepared by diluting the monosaccharides, polysaccharides and derivatives listed in Table 1 with water, add 1 kg of the phoenite phosphate, and use a 0.5 mm diameter zirconia in a ball mill. The beads were honed for about 1 hour. After honing, the density of the phyllite phosphate in the suspension was adjusted to 1 g / liter using tap water to prepare the conditioning solution used in this specific example. As measured by the aforementioned laser diffraction / diffuse particle size distribution analyzer, the average particle size suspended in the liquid was 0.5 micron. [Specific Example 7] To 1 kg of a 10 weight percent solution of monosaccharides, polysaccharides, and derivatives diluted with water, add 1 kg of Zn3F e (P〇4) 2 · 4 Η 2 〇 and use it in a ball mill. The 5 mm diameter zirconia beads were honed for about 1 hour. After honing, the density of Zn3Fe (PO4) 2 · 4Η20 in the liquid was adjusted to 1 g / l using tap water to prepare a conditioning liquid for this application. Measured by the aforementioned laser diffraction / diffuse particle size distribution analyzer, the average particle size suspended in the liquid is 0.6 micron. The paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X 297 mm)- 24---- r ------ Clothes: Order (please read the precautions on the back before filling out this page) Ministry of Economic Affairs Smart Money / ip-7a (Industrial and Consumer Cooperatives Printing Disaster 491912

A7 B7 五、發明説明（22) 米。 (請先閱讀背面之注意事項存填寫本買) 〔具體實例8〕於1公斤Zn3Fe (P〇4) 2· 4H2〇試劑中，添加1 0克藉水稀釋表1所列之單醣、多醣及衍生物所得之 1 0重量百分比水溶液，於球磨機中使用1 0毫米直徑二氧化锆珠粒硏磨約1小時。硏磨之後，使用自來水將液體中之Zn3Fe (P〇4) 2· 4H2〇密度調至1克/升。調整之後，液體中之平均粒徑以前述雷射繞射/漫射粒徑分佈分析器測定，懸浮於該液體中之平均粒徑係爲1 · 2 微米。添加5克/升偏矽酸鈉試劑以作爲鹼，得到欲施加之調理液。〔具體寳例9〕 1升0 · 1莫耳/升硝酸鈣溶液於5 0 °C下添加 2 0 0毫升1莫耳/升之硝酸鋅溶液及2 0 0毫升1莫耳 /升1 -磷酸氫鈉，以使之沉降。含有沉降物之溶液於經濟部智慧財/i^M工消費合作社印製 9〇°C下保持1小時以使沉降物成熟，之後傾斜漂洗1 〇次。過濾並乾燥之後，由X -射線繞射分析發現該沉降物係爲磷鋅礦（Zn2Ca (Ρ〇4)2·4Η2〇）。於1 公斤該磷鈣鋅礦中添加1 〇克藉著以水稀釋表1所列之單醣、多醣及衍生物所製備之1 〇重量百分比溶液，於球磨機中使用0 · 5毫米直徑二氧化锆珠粒硏磨約1小時。硏磨之後，使用自來水將懸浮液中之磷鈣鋅礦密度調至1 〇本紙張尺度適用中國國家標準（CNS ) Α4規格（2丨0X297公釐） -25 - 491912A7 B7 5. Description of the invention (22) m. (Please read the precautions on the back and fill in this purchase first) [Specific Example 8] To 1 kg of Zn3Fe (P〇4) 2 · 4H2〇 reagent, add 10 grams of water to dilute the monosaccharides and polysaccharides listed in Table 1 10% by weight of the aqueous solution obtained from the derivative and the derivative were honed in a ball mill using 10 mm diameter zirconia beads for about 1 hour. After honing, the density of Zn3Fe (P04) 2.4H20 in the liquid was adjusted to 1 g / liter using tap water. After the adjustment, the average particle diameter in the liquid was measured with the aforementioned laser diffraction / diffuse particle size distribution analyzer, and the average particle diameter suspended in the liquid was 1.2 micrometers. 5 g / L of sodium metasilicate reagent was added as a base to obtain a conditioning solution to be applied. [Specific Treasure Example 9] 1 liter of 0 · 1 mole / liter of calcium nitrate solution is added at 50 ° C to 200 ml of 1 mole / liter of zinc nitrate solution and 200 ml of 1 mole / liter of 1- Sodium hydrogen phosphate to settle. The solution containing the sediment was printed at 90 ° C for 1 hour to print by the Ministry of Economic Affairs / Intellectual Property Cooperative Cooperative to allow the sediment to mature, and then was rinsed by tilting 10 times. After filtering and drying, it was found by X-ray diffraction analysis that the sedimentary system was amphazite (Zn2Ca (PO4) 2.4.20). To 10 kg of this phosphate calcium zinc ore was added 10 grams of a 10 weight percent solution prepared by diluting the monosaccharides, polysaccharides and derivatives listed in Table 1 with water, and using a 0.5 mm diameter dioxide in a ball mill. The zirconium beads were honed for about 1 hour. After honing, use tap water to adjust the density of the phosphate calcium zinc ore in the suspension to 1 〇 This paper size applies the Chinese National Standard (CNS) A4 specification (2 丨 0X297 mm) -25-491912

五、發明説明（23) 克/升。以前述雷射繞射/漫射粒徑分佈分析器測定，懸浮於該液體中之平均粒徑係爲0 · 4微米。添加1克/升之碳酸鈉試劑，得到欲施加之調理液。〔具體實例1 0〕 1升〇 · 1莫耳/升硝酸鈣溶液於5 0 °C下添加2 0 0毫升1莫耳/升之硝酸鋅溶液及2 0 0毫升1莫耳/升 1 -磷酸氫鈉，以使之沉降。含有沉降物之溶液於9 0 t 下保持1小時以使沉降物成熟，之後傾斜漂洗1 0次。過濾並乾燥之後，由X -射線繞射分析發現該沉降物係爲磷鈣鋅礦（Zn2Ca (Ρ〇4)2·4Η2〇）。於1公斤該磷鈣鋅礦中添加1 0克藉著以水稀釋表1所列之單醣、多醣及衍生物所製備之1 0重量百分比水溶液，於球磨機中使用0 . 5毫米直徑二氧化锆珠粒硏磨約1小時。硏磨之後，使用自來水將懸浮液中之磷鈣鋅礦密度調至5克/ 升。以前述雷射繞射/漫射粒徑分佈分析器測定，懸浮於該液體中之平均粒徑係爲0 . 4微米。另外，添加1 0克 /升之磷酸三鈉試劑以作爲鹼，添加2克/升之聚氧化乙烯-壬酚醚以作爲界面活性劑，得到欲施加之調理液。此情況下，在不脫脂下使用具有油污之試片，同時進行淸潔及調理。〔對照例1〕V. Description of the invention (23) g / l. As measured by the laser diffraction / diffuse particle size distribution analyzer, the average particle size suspended in the liquid was 0.4 µm. Add 1 g / L of sodium carbonate reagent to obtain the conditioning solution to be applied. [Specific Example 10] 1 liter of 0.1 mol / liter of calcium nitrate solution was added at 50 ° C to 200 ml of 1 mol / liter of zinc nitrate solution and 200 ml of 1 mol / liter of 1- Sodium hydrogen phosphate to settle. The sediment-containing solution was kept at 90 t for 1 hour to allow the sediment to mature, and then rinsed 10 times with tilting. After filtration and drying, the sedimentation system was found to be a perovskite (Zn2Ca (PO4) 2.4.20) by X-ray diffraction analysis. 10 grams of a 10% by weight aqueous solution prepared by diluting the monosaccharides, polysaccharides, and derivatives listed in Table 1 with water was added to 1 kg of this phosphate calcium zinc ore. 0.5 mm diameter dioxide was used in a ball mill. The zirconium beads were honed for about 1 hour. After honing, tap water was used to adjust the density of the phosphazite in the suspension to 5 g / l. As measured by the aforementioned laser diffraction / diffuse particle size distribution analyzer, the average particle size suspended in the liquid was 0.4 micrometers. In addition, 10 g / L of trisodium phosphate reagent was added as a base, and 2 g / L of polyethylene oxide-nonyl ether was added as a surfactant to obtain a conditioning solution to be applied. In this case, use the oily test piece without degreasing, and clean and condition at the same time. [Comparative Example 1]

Prepalene ZN(Nihon Parkerizing Co.Ltd.之商標），水溶本紙張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐） -26 —---L--·---裝 — I (請先閱讀背面之注意事項再填寫本瓦) 訂 •麵· 經濟部智慈財產笱a(工消費合作社印製 491912Prepalene ZN (trademark of Nihon Parkerizing Co. Ltd.), water-soluble paper size applies Chinese National Standard (CNS) A4 specification (210X 297 mm) -26 —--- L-- · --- packing — I (Please Read the notes on the back before filling in this tile.) Customs · Intellectual Property of the Ministry of Economy 笱 a (Printed by the Industrial and Consumer Cooperatives 491912

五、發明説明（24) 液習用技術所使用之調理液，係於其標準條件下作爲調理液。〔對照例2〕於前述Prepalene ZN溶液中添加〇 · 5克/升之7 -水合硫酸鎂試劑，得到調理液。〔對照例3〕 10 0毫升1莫耳/升之硫酸鋅溶液及1 〇〇毫升1 莫耳/升1 -磷酸氫鈉溶液於5 0 °C下交替添加於1升 0 · 5莫耳/升硫酸亞鐵（Π )溶液中，以產生沉降物。含有沉降物之溶液於9 0 °C下保持1小時以使沉降物成熟’之後傾斜漂洗1 0次。過濾並乾燥之後，由X -射線繞射分析發現該沉降物係爲磷酸千枚巖（Z η 2 F e ( Ρ Ο 4 ) 2 * 4 Η 2 Ο )，部分含有磷酸鐵。該磷酸千枚巖於球磨機中使用0 · 5毫米直徑二氧化锆珠粒硏磨至使用前述雷射繞射/漫射粒徑分佈分析器測定時，懸浮於該液體中之平均粒徑小於0 . 5微米。硏磨後，該磷酸千枚巖之密度以自來水調至1克/升，以得到調理液。〔對照例4〕 1 0 0毫升1莫耳/升之硫酸鋅溶液及1 〇〇毫升1 莫耳/升1 -磷酸氫鈉溶液於5 0 °C下交替添加於1升 0 . 5莫耳/升硫酸亞鐵（π)溶液中，以產生沉降物。本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） :27 . (請先閱讀背面之注意事項再填寫本育) -装- 訂經濟部智慧財產局員工消費合作社印t 491912 趟 A7 B7 禱充五、發明説明（25) 含有沉降物之溶液於9 0 °C下保持1小時以使沉降物成熟，之後傾斜漂洗1 〇次。過濾並乾燥之後’由x 一射線繞射分析發現該沉降物係爲磷酸千枚巖（z n 2 F e ( P Ο 4 ) 2 · 4 Η 2 0 )，部分含有磷酸鐵。該磷酸千枚巖於硏缽中硏磨約2分鐘。硏磨後，以自來水稀釋’以5微米濾紙過濾，丟棄濾液。所得之沉降物於8 0 °C下乾燥1 小時，於1公斤所乾燥之粉末中添加5 0克藉著以水及異丙醇稀釋表1所列之單醣、多醣及衍生物所得之1 〇重量百分比溶液。以自來水將該乾燥粉末調至密度1克/升而製備調理液。使用前述雷射繞射/漫射粒徑分佈分析器測定時，液體中之平均粒徑係爲6 · 5微米。表3列出具體實例所得之磷酸鹽層之特性’磷酸鹽層於所有具體實例中皆係爲磷酸鋅層。表4列出對照例所得之磷酸鹽層之特性，磷酸鹽層於所有對照例中亦皆係爲磷酸鋅層。根據表3及4，如同表4所列之習用液體具有不足之處，表3所列之本發明調理液的耐久性大幅改善。由對照例3及具體實例1及2，明白顯示單醣、多醣及其衍生物對於表面調理之影響。對照例3之調理液製備後即時測量之性質較具體實例1差，但較對照例1之習用液體佳。然而，於對照例3中，二價或三價金屬之磷酸鹽的粉碎極爲困難，而且，於該液體製備1 0日後，二價或三價金屬之磷酸鹽沉澱。係因不含單醣、多醣或其衍生物，故該二價或三價金屬之磷酸鹽再次凝結。而且，難以產製相 ---.---*---裝-- (請先閱讀背面之注意事項再填寫本頁) 訂經濟部智惡財產苟員工消費合作社印製本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -28- 491912 祖α 1薇…: λ)V. Description of the invention (24) The conditioning liquid used in the conventional liquid technology is used as a conditioning liquid under its standard conditions. [Comparative Example 2] 0.5 g / L of 7-hydrated magnesium sulfate reagent was added to the aforementioned Prepalene ZN solution to obtain a conditioning solution. [Comparative Example 3] 100 ml of 1 mol / L of zinc sulfate solution and 100 ml of 1 mol / L of 1-sodium hydrogen phosphate solution were alternately added to 1 liter of 0.5 M / L at 50 ° C. Liter of ferrous sulfate (Π) solution to produce sediment. The sediment-containing solution was held at 90 ° C for 1 hour to allow the sediment to mature ', and then rinsed with tilting 10 times. After filtering and drying, X-ray diffraction analysis revealed that the sedimentary system was Phosphate Phosphite (Z η 2 F e (P 〇 4) 2 * 4 Η 2 〇), and partly contained iron phosphate. The Phosphate Phosphate was honed in a ball mill using 0.5 mm diameter zirconia beads until the average particle size suspended in the liquid was less than 0 when measured using the aforementioned laser diffraction / diffuse particle size distribution analyzer. .5 microns. After honing, the density of the phoenite phosphate was adjusted to 1 g / l with tap water to obtain a conditioning solution. [Comparative Example 4] 100 ml of 1 mole / liter of zinc sulfate solution and 100 ml of 1 mole / liter of 1-sodium hydrogen phosphate solution were alternately added to 1 liter of 0.5 mole at 50 ° C. Per liter of ferrous sulfate (π) solution to produce sediment. This paper size applies to Chinese National Standard (CNS) A4 specification (210X297 mm): 27. (Please read the notes on the back before filling in this education)-Binding-Ordering of the Intellectual Property Bureau of the Ministry of Economic Affairs, Consumer Consumption Cooperative Stamp 491912 trips to A7 B7 Pray and V. Description of the invention (25) The solution containing the sediment is kept at 90 ° C for 1 hour to mature the sediment, and then rinsed by tilting 10 times. After filtering and drying ', the x-ray diffraction analysis found that the sedimentary system was Phosphate Phosphite (z n 2 F e (P 0 4) 2 · 4 Η 2 0), and partially contained iron phosphate. The Phosphite Phosphate was honed in a mortar for about 2 minutes. After honing, it was diluted with tap water 'and filtered through 5 micrometer filter paper, and the filtrate was discarded. The obtained sediment was dried at 80 ° C for 1 hour, and 50 g of 1 kg of the dried powder was added. 1 was obtained by diluting the monosaccharides, polysaccharides and derivatives listed in Table 1 with water and isopropanol. 0% by weight solution. This dry powder was adjusted to a density of 1 g / liter with tap water to prepare a conditioning solution. As measured by the aforementioned laser diffraction / diffuse particle size distribution analyzer, the average particle size in the liquid was 6.5 µm. Table 3 lists the characteristics of the phosphate layer obtained from the specific examples. The phosphate layer is a zinc phosphate layer in all specific examples. Table 4 lists the characteristics of the phosphate layer obtained in the comparative example. The phosphate layer is also a zinc phosphate layer in all the comparative examples. According to Tables 3 and 4, as the conventional liquids listed in Table 4 have disadvantages, the durability of the conditioning liquid of the present invention listed in Table 3 is greatly improved. From Comparative Example 3 and Specific Examples 1 and 2, the influence of monosaccharides, polysaccharides, and their derivatives on surface conditioning was clearly shown. The properties measured immediately after preparation of the conditioning liquid of Comparative Example 3 were inferior to those of Specific Example 1, but better than the conventional liquid of Comparative Example 1. However, in Comparative Example 3, the crushing of the phosphate of the divalent or trivalent metal was extremely difficult, and after 10 days from the preparation of the liquid, the phosphate of the divalent or trivalent metal precipitated. Because the mono-, poly-, or derivatives are not contained, the phosphate of the divalent or trivalent metal coagulates again. Moreover, it is difficult to produce a photo ---.--- * --- install-(Please read the notes on the back before filling this page) Order the intellectual and evil property of the Ministry of Economy National Standard (CNS) A4 specification (210X297 mm) -28- 491912 ancestor α 1 Wei ...: λ)

A7 /C , I B7 ί .....‘丄，· · 五、發明説明（26) 當於具體實例之細密結晶。表5列出本發明申請專利範圍第2項之調理液的成分。於本發明中，調理液之ρ η値不重要。然而，當其太酸時，該二價及三價金屬之固體磷酸鹽粒子而溶於該調理液中之危險提高。爲了避免此種情況，當其太酸時，藉著例如添加氫氧化鈉以中和調理液爲佳。耐久性試驗係該調理液於室溫下保持1 〇日之後測定。〔具體實例1 1〕 1 0 0毫升1莫耳/升之硫酸鋅溶液及1 0 0毫升1 莫耳/升1 -磷酸氫鈉溶液於5 0 °C下交替添加於1升〇· 5莫耳/升硫酸亞鐵（Π )溶液中，以產生沉降物。含有沉降物之溶液於9 0 °C下保持1小時以使沉降物成熟，之後傾斜漂洗1 0次。過濾並乾燥之後，由X -射線繞射分析發現該沉降物係爲磷酸千枚巖（z n 2 F e ( P 0 4 ) 2 · 4 Η 2 0 )，部分含有磷酸鐵。於1公斤該磷酸千枚巖中添加2克表5所列之磷化合物之1〇重量百分比稀水溶液，於球磨機中使用0 · 5毫米直徑二氧化锆珠粒硏磨約1小時。硏磨之後，使用自來水將懸浮液中之磷酸千枚巖密度調至5克/升而製備此具體實例所使用之調理液。以前述雷射繞射/漫射粒徑分佈分析器測定，懸浮於該液體中之平均粒徑係爲0 · 5微米。另外’添加〇· 5克/f亞硫酸鎂7 -水合物試劑以作爲驗鹽’得到欲施加之調理液。本紙張又度適用中國國家標準（CNS ) A4規格（210X297公釐） -29 - (請先閲讀背面之注意事項再填寫本頁) 訂經濟部智慧財產苟8工消f合作社印製 491912 A7 B7 五、發明説明（27) m 經濟部智慈財產笱員工消費合作社印製〔具體實例1 2〕 1 0 0毫升1莫耳/升之硫酸鋅溶液及1 0 0毫升1 莫耳/升1 -磷酸氫鈉溶液於5 0 t下交替添加於1升〇 · 5莫耳/升硫酸亞鐵（Π )溶液中，以產生沉降物。含有沉降物之溶液於9 0 t下保持1小時以使沉降物成熟，之後傾斜漂洗1 0次。過濾並乾燥之後，由X -射線繞射分析發現該沉降物係爲磷酸千枚巖（Ζ η 2 F e ( P〇4) 2 ♦ 4H2〇），部分含有磷酸鐵。於1公斤該磷酸千枚巖中添加1公斤表5所列之磷化合物之1 0重量百分比稀水溶液，於球磨機中使用〇 . 5毫米直徑二氧化鉻珠粒硏磨約1小時。硏磨之後，使用自來水將懸浮液中之磷酸千枚巖密度調至1克/升而製備此具體實例所使用之調理液。以前述雷射繞射/漫射粒徑分佈分析器測定，懸浮於該液體中之平均粒徑係爲0 · 5微米。另外，添加1 克/升偏矽酸鈉試劑以作爲鹼鹽，得到欲施加之調理液。〔具體實例1 3〕 1 0 0毫升1莫耳/升之硫酸鋅溶液及1 0 0毫升1 莫耳/升1 一磷酸氫鈉溶液於5 0 t下交替添加於1升 0 · 5莫耳/升硫酸亞鐵（E )溶液中，以產生沉降物。含有沉降物之溶液於9 0 °C下保持1小時以使沉降物成熟，之後傾斜漂洗1 0次。過濾並乾燥之後，由X -射線繞射分析發現該沉降物係爲磷酸千枚巖（Ζ η 2 F e ( (請先閱讀背面之注意事項再填寫本頁) C· 訂加本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -30 491912 A7 B7 fii 五、發明説明（28) P〇4 ) 2 · 4 Η 2〇），部分含有磷酸鐵。於1公斤表5 所列之磷化合物之1 0重量百分比水溶液中添加2 0 0克該磷酸千枚巖，於球磨機中使用1 〇毫米直徑二氧化鉻珠粒硏磨約1小時。硏磨之後，使用自來水將懸浮液中之磷酸千枚巖密度調至1克/升而製備此具體實例所使用之調理液。以前述雷射繞射/漫射粒徑分佈分析器測定，懸浮於該液體中之平均粒徑係爲1·7微米。〔具體實例1 4〕於1公斤Zn3Fe (Ρ〇4) 2· 4Η2〇試劑中，添加1 0 0克表5所列之磷化合物之1 0重量百分比水溶液，於球磨機中使用0 · 5毫米直徑二氧化锆珠粒硏磨約 1小時。硏磨之後，使用自來水將液體中之Ζ η 3 F e ( P〇4 ) 2 · 4 Η 2〇密度調至5克/升。調整之後，液體中之平均粒徑以前述雷射繞射/漫射粒徑分佈分析器測定，懸浮於該液體中之平均粒徑係爲0 . 6微米。添加5 克/升碳酸鈉試劑以作爲鹼，得到欲施加之調理液。〔具體實例1 5〕 1升0 · 1莫耳/升硝酸鈣溶液於5 0 °C下添加 2 0 0毫升1莫耳/升之硝酸鋅溶液及2 0 0毫升1莫耳 /升1 -磷酸氫鈉，以使之沉降。含有沉降物之溶液於 9 0 °C下保持1小時以使沉降物成熟，之後傾斜漂洗1〇次。過濾並乾燥之後，由X -射線繞射分析發現該沉降物本紙張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐） -31 _ (請先閱讀背面之注意事項再填寫本頁)A7 / C, I B7… .. ‘丄, ·· V. Description of the invention (26) The fine crystal of the specific example. Table 5 lists the composition of the conditioning liquid in item 2 of the patent application scope of the present invention. In the present invention, ρ η 値 of the conditioning liquid is not important. However, when it is too acidic, there is an increased risk that the solid phosphate particles of the divalent and trivalent metals dissolve in the conditioning solution. To avoid this, when it is too acidic, it is preferable to neutralize the conditioning solution by, for example, adding sodium hydroxide. The durability test was measured after the conditioning solution was kept at room temperature for 10 days. [Specific Example 1] 100 ml of 1 mol / L of zinc sulfate solution and 100 ml of 1 mol / L of 1-sodium hydrogen phosphate solution were alternately added to 1 liter of 0.5 M at 50 ° C. Ear / liter of ferrous sulfate (Π) solution to produce sediment. The sediment-containing solution was kept at 90 ° C for 1 hour to allow the sediment to mature, and then rinsed 10 times with tilting. After filtering and drying, X-ray diffraction analysis revealed that the sedimentary system was Phosphate Phosphite (z n 2 F e (P 0 4) 2 · 4 Η 2 0), and partially contained iron phosphate. To 1 kg of this phosphoric philite rock, 2 g of a 10% by weight dilute aqueous solution of the phosphorus compound listed in Table 5 was added, and honing was performed in a ball mill using 0.5 mm diameter zirconia beads for about 1 hour. After honing, the density of the Phosphoric Phosphite in the suspension was adjusted to 5 g / l using tap water to prepare the conditioning solution used in this specific example. As measured by the aforementioned laser diffraction / diffuse particle size distribution analyzer, the average particle size suspended in the liquid was 0.5 µm. In addition, '0.5 g / f magnesium sulfite 7-hydrate reagent was added as a test salt' to obtain a conditioning solution to be applied. This paper is again applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) -29-(Please read the notes on the back before filling this page) Order the intellectual property of the Ministry of Economic Affairs, printed by the cooperative, 491912 A7 B7 V. Description of the invention (27) m Printed by the Intellectual Property of the Ministry of Economic Affairs and the Employees' Cooperatives [Specific Example 1 2] 100 ml of 1 mol / L zinc sulfate solution and 100 ml of 1 mol / L 1- The sodium hydrogen phosphate solution was alternately added to a 1 liter of a 0.5 mol / liter ferrous sulfate (Π) solution at 50 t to generate a sediment. The sediment-containing solution was kept at 90 t for 1 hour to allow the sediment to mature, and then rinsed 10 times with tilting. After filtration and drying, X-ray diffraction analysis revealed that the sedimentary system was Phosphite Phosphate (Z η 2 F e (P〇4) 2 ♦ 4H2〇), which partially contained iron phosphate. To 1 kg of this phosphoric philite rock, add 1 kg of a 10% by weight dilute aqueous solution of the phosphorus compound listed in Table 5 and hob the ball mill using 0.5 mm diameter chromium dioxide beads for about 1 hour. After honing, the density of the phyllite phosphate in the suspension was adjusted to 1 g / liter using tap water to prepare the conditioning solution used in this specific example. As measured by the laser diffraction / diffuse particle size distribution analyzer, the average particle size suspended in the liquid was 0.5 µm. In addition, 1 g / liter of sodium metasilicate reagent was added as an alkali salt to obtain a conditioning solution to be applied. [Specific Example 1] 100 ml of 1 mole / liter of zinc sulfate solution and 100 ml of 1 mole / liter of 1 sodium hydrogen phosphate solution were alternately added to 1 litre of 0.5 · 5 moles at 50 t. Per liter of ferrous sulfate (E) solution to produce sediment. The sediment-containing solution was kept at 90 ° C for 1 hour to allow the sediment to mature, and then rinsed 10 times with tilting. After filtering and drying, X-ray diffraction analysis found that the sedimentary system was Phosphate Phosphate (Z η 2 F e ((Please read the precautions on the back before filling this page)) China National Standard (CNS) A4 specification (210X297 mm) -30 491912 A7 B7 fii 5. Description of the invention (28) P04) 2 · 4 · 2〇), part of which contains iron phosphate. Add 200 grams of the Phosphite Phosphite to a 10 kg weight percent aqueous solution of the phosphorus compounds listed in Table 5 and use a ball mill with 10 mm diameter chromium dioxide beads for about 1 hour. After honing, the density of the Phosphoric Phosphite in the suspension was adjusted to 1 g / liter using tap water to prepare the conditioning solution used in this specific example. As measured by the laser diffraction / diffuse particle size distribution analyzer, the average particle size suspended in the liquid was 1.7 m. [Specific Example 1 4] To 1 kg of Zn3Fe (PO4) 2 · 4Η20 reagent, add 100 g of a 10 weight percent aqueous solution of the phosphorus compound listed in Table 5 and use a 0.5 mm diameter in a ball mill. Honed the zirconia beads for about 1 hour. After honing, the density of Z η 3 F e (P〇 4) 2 · 4 Η 20 in the liquid was adjusted to 5 g / l using tap water. After the adjustment, the average particle diameter in the liquid was measured by the aforementioned laser diffraction / diffuse particle size distribution analyzer, and the average particle diameter suspended in the liquid was 0.6 μm. 5 g / L of sodium carbonate reagent was added as a base to obtain a conditioning solution to be applied. [Specific Example 15] 1 liter of 0 · 1 mole / liter of calcium nitrate solution was added at 50 ° C to 200 ml of 1 mole / liter of zinc nitrate solution and 200 ml of 1 mole / liter of 1- Sodium hydrogen phosphate to settle. The sediment-containing solution was held at 90 ° C for 1 hour to allow the sediment to mature, and then rinsed 10 times with tilting. After filtering and drying, the sediment was found by X-ray diffraction analysis. The paper size is applicable to China National Standard (CNS) A4 (210X 297 mm) -31 _ (Please read the precautions on the back before filling this page)

、1T 經濟部智慧財產^員工消費合作社印製 491912 A7 〜〜 B7 r，五、發明説明（29) r 係爲隣15鋅礦（Ζ η 2 C a ( P〇4 ) 2 · 4 Η 2〇）。於1 公斤表5所列之磷化合物之1 0重量百分比水溶液中添加 1公斤該磷鈣鋅礦，於球磨機中使用0.5毫米直徑二氧化锆珠粒硏磨約1小時。硏磨之後，使用自來水將懸浮液中之磷鈣鋅礦密度調至1 0克/升。以前述雷射繞射/漫射粒徑分佈分析器測定，懸浮於該液體中之平均粒徑係爲 0 · 5微米。另外，添加1 0克/升之礙酸三鈉試劑以作爲鹼及2克/升之聚氧化乙烯-壬酚醚以作爲界面活性劑。此情況下，在不脫脂之情況下使用試片，以同時進行淸潔及調理。〔對照例5〕 10 0毫升1莫耳/升之硫酸鋅溶液及1 0 0毫升1 莫耳/升1 -磷酸氫鈉溶液於5 0 °C下交替添加於1升 0 . 5莫耳/升硫酸亞鐵（Π )溶液中，以產生沉降物。含有沉降物之溶液於9 0 °C下保持1小時以使沉降物成熟，之後傾斜漂洗1 0次。過濾並乾燥之後，由X -射線繞射分析發現該沉降物係爲磷酸千枚巖（Z η 2 F e ( P Ο 4 ) a · 4 Η 2 Ο )，部分含有磷酸鐵。該磷酸千枚巖於硏缽中硏磨約2分鐘。硏磨後，以自來水稀釋，以5微米濾紙過濾，丟棄濾液。所得之沉降物於8 0 °C下乾燥1 小時，於1 0 0克此粉末中添加5 0 0克表2所列之磷化合物之1 0重量百分比溶液。以自來水將該乾燥粉末調至密度1克/升而製備調理液。使用前述雷射繞射/漫射粒本紙張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐） -32 - (請先閱讀背面之注意事項再填寫本頁) 一裝. 訂經濟部智慧財產局員工消費合作社印製 491912 經濟部智慈財產苟員工消f合作钍印製 f輒Μ A 7 Β7五、發明説明（30) 徑分佈分析器測定時，液體中之平均粒徑係爲6 . 5微米。表6列出使用具體實例1 1〜1 5之調理液所形成之磷酸鹽層之特性。對照例5所形成之磷酸鹽層特性係列示於表4。根據表6及4，本發明調理液使原來爲習用液體之缺點的耐久性大幅改善。由對照例3及具體實例1 3之結果，明白顯示磷化合物之影響。雖然對照例3之調理液製備後即時測量之性質較具體實例1 1差，但具有較對照例1之習用液體佳或相當之表面調理效果。然而，於對照例3中，二價或三價金屬之磷酸鹽的粉碎極爲困難，而且，於該液體製備1 〇日後，二價或三價金屬之磷酸鹽沉澱。係因不含原磷酸、多磷酸或有機鱗酸之化合物，故該二價或三價金屬之磷酸鹽再次凝結。表7列出本發明申請專利範圍第3項之調理液的成分。於表7及表2中，乙酸乙烯基之聚合物或其衍生物、與乙酸乙烯基聚合之單體及乙酸乙烯基之共聚物的水性高分子化合物係簡單地以水性高分子化合物表示。聚合物及其衍生物係使用過氧化物作爲起始劑以使乙酸乙烯基聚合而產製，官能基係藉著皂或縮醛化學反應添加。而且，與乙酸乙烯基聚合之單體的共聚物係藉著該乙酸乙烯基與個別單體之聚合而合成。耐久性試驗係於該調理液於室溫下保持1 〇日之後進 ^紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐) :33- "1T Intellectual Property of the Ministry of Economic Affairs ^ Printed by employee consumer cooperatives 491912 A7 ~ B7 r. V. Description of the invention (29) r is an adjacent 15 zinc ore (Z η 2 C a (P〇4) 2 · 4 Η 2〇 ). 1 kg of the phosphoro-zincite was added to 1 kg of a 10% by weight aqueous solution of the phosphorus compounds listed in Table 5, and then honed in a ball mill using 0.5 mm diameter zirconia beads for about 1 hour. After honing, tap water was used to adjust the density of the phosphazite in the suspension to 10 g / l. As measured by the laser diffraction / diffuse particle size distribution analyzer, the average particle size suspended in the liquid was 0.5 micrometers. In addition, 10 g / L of trisodium oxyacid reagent was added as a base and 2 g / L of polyethylene oxide-nonyl ether was used as a surfactant. In this case, use the test piece without degreasing to clean and condition at the same time. [Comparative Example 5] 100 ml of 1 mole / liter of zinc sulfate solution and 100 ml of 1 mole / liter of 1-sodium hydrogen phosphate solution were alternately added to 1 liter of 0.5 mole / liter at 50 ° C. Liter of ferrous sulfate (Π) solution to produce sediment. The sediment-containing solution was kept at 90 ° C for 1 hour to allow the sediment to mature, and then rinsed 10 times with tilting. After filtering and drying, X-ray diffraction analysis revealed that the sedimentary system was Phosphate Phosphite (Z η 2 F e (P 〇 4) a · 4 Η 2 〇), and partly contained iron phosphate. The Phosphite Phosphate was honed in a mortar for about 2 minutes. After honing, it was diluted with tap water, filtered through 5 micron filter paper, and the filtrate was discarded. The obtained sediment was dried at 80 ° C for 1 hour, and 100 g of this powder was added with 500 g of a 10 weight percent solution of the phosphorus compound listed in Table 2. This dry powder was adjusted to a density of 1 g / liter with tap water to prepare a conditioning solution. Use the aforementioned laser diffraction / diffuse particles This paper size is applicable to Chinese National Standard (CNS) A4 specification (210X 297 mm) -32-(Please read the precautions on the back before filling this page) One pack. Order the Ministry of Economy Printed by the Intellectual Property Bureau's Consumer Cooperative Cooperative 491912 Printed by the Intellectual Property of the Ministry of Economic Affairs and Co-operation printed by the company F 7 M7. B7. Description of the Invention (30) The average particle size of the liquid when measured by the diameter distribution analyzer is 6.5 microns. Table 6 shows the characteristics of the phosphate layer formed by using the conditioning liquids of specific examples 1 to 15. The characteristic series of the phosphate layer formed in Comparative Example 5 is shown in Table 4. According to Tables 6 and 4, the conditioning liquid of the present invention greatly improves the durability of the conventional defect liquid. The results of Comparative Example 3 and Specific Example 13 clearly show the effect of the phosphorus compound. Although the properties measured immediately after preparation of the conditioning liquid of Comparative Example 3 were inferior to those of Specific Example 11, it had better or equivalent surface conditioning effect than the conventional liquid of Comparative Example 1. However, in Comparative Example 3, pulverization of the divalent or trivalent metal phosphate was extremely difficult, and after 10 days from the preparation of the liquid, the divalent or trivalent metal phosphate was precipitated. Because the compounds do not contain orthophosphoric acid, polyphosphoric acid, or organic scale acid, the phosphate of the divalent or trivalent metal condenses again. Table 7 shows the composition of the conditioning liquid in item 3 of the scope of patent application of the present invention. In Tables 7 and 2, the aqueous polymer compounds of vinyl acetate polymer or its derivative, the monomer polymerized with vinyl acetate, and the copolymer of vinyl acetate are simply expressed as aqueous polymer compounds. Polymers and their derivatives are produced by polymerizing vinyl acetate using peroxide as a starter, and functional groups are added by soap or acetal chemical reaction. Further, a copolymer of a monomer polymerized with vinyl acetate is synthesized by polymerizing the vinyl acetate with an individual monomer. The durability test is carried out after the conditioning solution is kept at room temperature for 10 days. ^ The paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm): 33- "

(請先閲讀背面之注意事項再填寫本頁) _裝· 訂 491912 A7 B7 隊(Please read the notes on the back before filling out this page) _Package · Order 491912 A7 B7 Team

Pai ΐ,ϊ 五、發明説明（31) 行。 (請先閱讀背面之注意事項再填寫本頁) 〔具體實例1 6〕 1 0 0毫升1莫耳/升之硫酸鋅溶液及1 0 0毫升1 莫耳/升1 -磷酸氫鈉溶液於5 0。(：下交替添加於1升〇 · 5莫耳/升硫酸亞鐵（Π )溶液中，以產生沉降物。含有沉降物之溶液於9 0 °C下保持1小時以使沉降物成熟，之後傾斜漂洗1 0次。過濾並乾燥之後，由X -射線繞射分析發現該沉降物係爲磷酸千枚巖（Z η 2 F e ( 經濟部智慈財產苟貸工消費合作社印製 P 〇 4 ) 2 · 4 Η 2 Ο )，部分含有磷酸鐵。於1公斤該磷酸千枚巖中添加2克_表7所列而經水稀釋之水性高分子化合物之1 0重量百分比稀水溶液，於球磨機中使用〇 · 5 毫米直徑二氧化鍩珠粒硏磨約1小時。硏磨之後，使用自來水將懸浮液中之磷酸千枚巖密度調至5克/升而製備此具體實例所使用之調理液。以前述雷射繞射/漫射粒徑分佈分析器測定，懸浮於該液體中之平均粒徑係爲〇 · 5微米。另外，添加0 · 5克/升偏矽酸鈉7 -水合物試劑，得到欲施加之調理液。〔具體實例1 7〕 1 〇 0毫升1莫耳/升之硫酸鋅溶液及1 〇〇毫升1 莫耳/升1 -磷酸氫鈉溶液於5 0°C下交替添加於1升〇· 5莫耳/升硫酸亞鐵（n )溶液中，以產生沉降物。含有沉降物之溶液於9 〇 °C下保持1小時以使沉降物成 -34- 本紙張尺度適用中國國家榡準（CNS ) A4規格（210X297公釐） 491912 A7 B7 五、發明説明（32) 熟，之後傾斜漂洗1 〇次。過濾並乾燥之後，由X 一射線繞射分析發現該沉降物係爲磷酸千枚巖（z n 2 F e ( (請先閱讀背面之注意事項再填寫本頁) Ρ Ο 4 ) 2 · 4 Η 2 Ο )，部分含有磷酸鐵。於100克該磷酸千枚巖添加於5 0 0克表7所列之水性高分子化合物之1 0重量百分比水溶液，於球磨機中使用〇 · 5毫米直徑二氧化鉻珠粒硏磨約1小時。硏磨之後，使用自來水將懸浮液中之磷酸千枚巖密度調至1克/升而製備此具體實例所使用之調理液。以前述雷射繞射/漫射粒徑分佈分析器測定，懸浮於該液體中之平均粒徑係爲0 · 5微米。〔具體實例1 8〕於1公斤表7所列之水性高分子化合物之1 0重量百分比水溶液中添加5 0克Ζ η 3 ( P〇4 ) 2 · 4 Η 2〇試劑，於球磨機中使用0 . 5毫米直徑二氧化锆珠粒硏磨約 1小時。硏磨之後，使用自來水將液體中之Ζ η 3 ( 經濟部智慧財產¾¾工消費合作钍印製 Ρ〇4 ) 2 · 4 Η 2〇密度調至1克/升。調整之後，液體中之平均粒徑以前述雷射繞射/漫射粒徑分佈分析器測定，懸浮於該液體中之平均粒徑係爲0 . 5微米。另外，添加0 · 5克/升硫酸鎂7水合物試劑，得到欲施加之調理液。〔具體實例1 9〕 1升0 · 1莫耳/升硝酸鈣溶液於5 0 °C下添加 2 0 0毫升1莫耳/升之硝酸鋅溶液及2 0 0毫升1莫耳本:紙張尺度適用中國國家標準（ CNS )八4祕（210X297公董):35 - 一 '〜 491912 Λ7 Γ； · B7 ίPai ΐ, ϊ V. Description of invention (31). (Please read the precautions on the back before filling in this page) [Specific Example 16] 100 ml of 1 mole / liter of zinc sulfate solution and 100 ml of 1 mole / liter of 1-sodium hydrogen phosphate solution in 5 0. (: The bottom is alternately added to a 1 liter 0.5 mol / liter ferrous sulfate (Π) solution to produce a sediment. The solution containing the sediment is kept at 90 ° C for 1 hour to mature the sediment, and thereafter Rinse in an inclined direction 10 times. After filtering and drying, it was found by X-ray diffraction analysis that the sedimentary system was Phosphite Phosphate (Z η 2 F e (printed by the Ministry of Economy, Intellectual Property, Consumer Goods Cooperative, P. 0) ) 2 · 4 Η 2 〇), part of which contains iron phosphate. Add 1 g of this phosphorous phyllite to 2 g _ Table 7 diluted water solution of 10% by weight of water-soluble polymer compounds diluted in water, in a ball mill Honed with 0.5 mm diameter hafnium dioxide beads for about an hour. After honing, the density of the phoenite phosphate in the suspension was adjusted to 5 g / l using tap water to prepare the conditioning liquid used in this specific example. Measured by the aforementioned laser diffraction / diffuse particle size distribution analyzer, the average particle size suspended in this liquid was 0.5 micrometers. In addition, 0.5 g / liter of sodium metasilicate 7-hydrate was added. Reagent to obtain the conditioning solution to be applied. [Specific Example 17] 100 ml 1 mol / L of zinc sulfate solution and 1000 ml of 1 mol / L of 1-sodium hydrogen phosphate solution were alternately added to 1 liter of 0.5 mol / L of ferrous sulfate (n) solution at 50 ° C In order to produce sediments, the solution containing sediments is kept at 90 ° C for 1 hour to make the sediments -34- This paper size applies to China National Standard (CNS) A4 (210X297 mm) 491912 A7 B7 V. Description of the invention (32) Cooked, then rinsed obliquely 10 times. After filtering and drying, X-ray diffraction analysis found that the sedimentary system is Phosphate Phosphite (zn 2 F e ((Please read the back Note: Please fill in this page again) Ρ Ο 4) 2 · 4 Η 2 〇), part of which contains iron phosphate. Add 100 grams of this phoenite phosphate to 500 grams of water polymer compounds listed in Table 7 0 A weight percent aqueous solution was honed in a ball mill using 0.5 mm diameter chromium dioxide beads for about 1 hour. After honing, the density of the phoenite phosphate in the suspension was adjusted to 1 g / liter using tap water to prepare this specific Conditioning liquid used in the example. Measured by the aforementioned laser diffraction / diffuse particle size distribution analyzer The average particle size suspended in the liquid was 0.5 micrometers. [Specific Example 18] To 1 kg of a 10 weight percent aqueous solution of the aqueous polymer compound listed in Table 7 was added 50 g of Z η 3 (P 〇 4) 2 · 4 Η 20 reagent, honing in a ball mill using 0.5 mm diameter zirconia beads for about 1 hour. After honing, tap water η η 3 (the intellectual property of the Ministry of Economic Affairs ¾¾) using tap water. Industrial and consumer cooperation (printed Po4) 2 · 4 Η 20 density adjusted to 1 g / liter. After the adjustment, the average particle diameter in the liquid was measured with the aforementioned laser diffraction / diffuse particle size distribution analyzer, and the average particle diameter suspended in the liquid was 0.5 micron. In addition, 0.5 g / L of magnesium sulfate heptahydrate reagent was added to obtain a conditioning solution to be applied. [Specific Example 19] 1 liter of 0 · 1 mole / liter of calcium nitrate solution was added at 50 ° C to 200 ml of 1 mole / liter of zinc nitrate solution and 200 ml of 1 mole of paper: paper scale Applicable to Chinese National Standard (CNS) Eighty-four Secrets (210X297 public director): 35-one '~ 491912 Λ7 Γ; · B7 ί

------- - ' ... . J 五、發明説明（33) /升1 -磷酸氫鈉，以使之沉降。含有沉降物之溶液於 9 0。(：下保持1小時以使沉降物成熟’之後傾斜漂洗1 0 次。過濾並乾燥之後，由X -射線繞射分析發現該沉降物係爲磷鈣鋅礦（Z η 2 C a ( P〇4 ) 2 · 4 Η 2〇）。於1 公斤表7所列之水性高分子化合物之1 〇重量百分比水溶液中添加5 0 0克該磷鈣鋅礦，於球磨機中使用1 〇毫米直徑二氧化锆珠粒硏磨約1小時。硏磨之後’使用自來水將懸浮液中之磷鈣鋅礦密度調至5克/升。以前述雷射繞射/漫射粒徑分佈分析器測定，懸浮於該液體中之平均粒徑係爲1 · 6微米。另外，添加5克/升之碳酸鈉試劑以作爲鹼，得到欲施加之調理液。〔具體賓例2 0〕 1升Ο · 1莫耳/升硝酸鈣溶液於5 0 °C下添加 2 0 0毫升1莫耳/升之硝酸鋅溶液及2 0 0毫升1莫耳 /升1 -磷酸氫鈉，以使之沉降。含有沉降物之溶液於 9 0 °C下保持1小時以使沉降物成熟，之後傾斜漂洗1 〇次。過濾並乾燥之後，由X -射線繞射分析發現該沉降物係爲磷鈣鋅礦（Zn2Ca (Ρ〇4)2·4Η2〇）。於1 公斤該憐銘鋅礦中添加1 〇克表7所列之水性高分子化合物之1 0重量百分比水溶液，於球磨機中使用0 · 5毫米直徑二氧化锆珠粒硏磨約1小時。硏磨之後，使用自來水將懸浮液中之磷鈣鋅礦密度調至3 0克/升。以前述雷射繞射/漫射粒徑分佈分析器測定，懸浮於該液體中之平均本紙張尺度適用中國國家標準（CNS ) Α4規格（210 X297公釐） .36 - (請先閱讀背面之注意事項存填寫本頁) 一装· 订經濟部智慈財產局員工消费合作社印^ 491912 經濟部智慈財產苟員工消費合作社印說五、發明説明（34) ' 粒徑係爲0 . 3微米。另外，添加1 0克/升之磷酸三鈉試劑以作爲鹼及2克/升之聚氧化乙烯-壬酚醚以作爲界面活性劑，得到調理液。此情況下，在不脫脂之情況下使用試片，以同時進行淸潔及調理。〔對照例6〕 1 0 0毫升1莫耳/升之硫酸鋅溶液及1 0 0毫升1 莫耳/升1 -磷酸氫鈉溶液於5 0 °C下交替添加於1升〇 · 5莫耳/升硫酸亞鐵（Π )溶液中，以產生沉降物。含有沉降物之溶液於9 0 °C下保持1小時以使沉降物成熟’之後傾斜漂洗1 0次。過濾並乾燥之後，由X -射線繞射分析發現該沉降物係爲磷酸千枚巖（Ζ η 2 F e ( P 〇 4 ) 2 · 4 Η 2 Ο )，部分含有磷酸鐵。該磷酸千枚巖於硏錄中硏磨約2分鐘。硏磨後，以自來水稀釋，以5微米濾紙過濾，丟棄濾液。所得之沉降物於8 0。(：下乾燥1 小時而成爲粉末。於5 0 0克表2所列之水性高分子化合物之1 0重量百分比溶液中添加1 〇〇克該乾燥粉末，以自來水將該乾燥粉末調至密度1克/升而製備調理液。使用前述雷射繞射/漫射粒徑分佈分析器測定時，液體中之平均粒徑係爲6 · 5微米。、表8列出使用表7之調理液所形成之磷酸鹽層之特个生°表4列出對照例6之調理液所形成之磷酸鹽層特性。根據表8及4，本發明調理液使耐久性大幅改善。由對照例3及具體實例1 7之結果，明白顯示水性高分子化 (請先閱讀背面之注意事項再填寫本頁) ，裝· 訂 if 本紙張尺度適用中國國家標準（CNS ) A4規格（2Η)Χ297公釐） -37---------'.... J V. Description of the invention (33) / L 1-sodium hydrogen phosphate to make it settle. The solution containing the sediment was at 90. (: Hold it for 1 hour to allow the sediment to mature, and then rinse it 10 times. After filtering and drying, X-ray diffraction analysis revealed that the sedimentary system is a phosphorite (Z η 2 C a (P〇 4) 2 · 4 Η 2〇). Add 500 grams of the phosphoro-zincite to 1 kg of a 10 weight percent aqueous solution of the aqueous polymer compound listed in Table 7, and use a 10 millimeter diameter dioxide in a ball mill. The zirconium beads were honed for about 1 hour. After honing, the density of the phosphazite in the suspension was adjusted to 5 g / l using tap water. Determined by the aforementioned laser diffraction / diffuse particle size distribution analyzer, suspended in The average particle size in this liquid was 1.6 micrometers. In addition, 5 g / liter of sodium carbonate reagent was added as a base to obtain a conditioning solution to be applied. [Specific guest example 2 0] 1 liter 0 · 1 mole Add 200 ml of 1 mol / L of zinc nitrate solution and 200 ml of 1 mol / L of 1-sodium hydrogen phosphate at 50 ° C to settle. The solution was held at 90 ° C for 1 hour to allow the sediment to mature, and then rinsed with tilting 10 times. After filtering and drying, it was subjected to X-ray irradiation. Line diffraction analysis found that the sedimentary system was a phosphate calcium zinc ore (Zn2Ca (PO4) 2 · 4Η2〇). To 1 kg of the Pingming zinc ore was added 10 g of the aqueous polymer compounds listed in Table 7. A 10 weight percent aqueous solution was honed in a ball mill using 0.5 mm diameter zirconia beads for about 1 hour. After honing, the density of the phosphate calcium zinc ore in the suspension was adjusted to 30 g / liter using tap water. Measured by the aforementioned laser diffraction / diffuse particle size distribution analyzer, the average paper size suspended in the liquid applies the Chinese National Standard (CNS) A4 specification (210 X297 mm). 36-(Please read the back Note for depositing and filling in this page) Packing and ordering stamps of the employees' cooperatives of the Intellectual Property Office of the Ministry of Economic Affairs ^ 491912 Stamps of the employees' cooperatives of the Intellectual Property of the Ministry of Economic Affairs of the Ministry of Economic Affairs 5. Description of the invention (34) 'The particle size is 0.3 micron In addition, add 10 g / L of trisodium phosphate reagent as a base and 2 g / L of polyethylene oxide-nonyl ether as a surfactant to obtain a conditioning solution. In this case, without degreasing Use test strips for cleaning and conditioning at the same time. As in Example 6] 100 ml of 1 mole / liter of zinc sulfate solution and 100 ml of 1 mole / liter of 1-sodium hydrogen phosphate solution were alternately added to 1 liter of 0.5 mole / liter at 50 ° C. Ferrous sulfate (Π) solution to produce sediments. The solution containing sediments was held at 90 ° C for 1 hour to allow the sediments to mature, and then rinsed 10 times with tilting. After filtration and drying, X-rays were used. Diffraction analysis revealed that the sedimentary system was Phosphate Phosphate (Z η 2 F e (P 〇 4) 2 · 4 Η 2 〇), and partly contained iron phosphate. The Phosphate Phosphate was honed in the record for about 2 minutes. After honing, it was diluted with tap water, filtered through 5 micron filter paper, and the filtrate was discarded. The resulting sediment was at 80. (: Dry for 1 hour to become a powder. Add 1000 grams of the dry powder to 500 grams of the 10% by weight solution of the aqueous polymer compound listed in Table 2, and adjust the dry powder to a density of 1 with tap water. G / L to prepare a conditioning liquid. When measured with the laser diffraction / diffuse particle size distribution analyzer, the average particle size in the liquid was 6.5 microns. Table 8 lists the conditioning solutions used in Table 7. Specific characteristics of the formed phosphate layer Table 4 lists the characteristics of the phosphate layer formed by the conditioning solution of Comparative Example 6. According to Tables 8 and 4, the conditioning solution of the present invention greatly improves the durability. From Comparative Example 3 and specific The results of Example 17 clearly show the water-based polymerization (please read the precautions on the back before filling in this page), binding and ordering if the paper size is applicable to the Chinese National Standard (CNS) A4 size (2Χ) × 297 mm)- 37-

491912 A7 ______B7 五、發明説明（3δ) 合物之高性能。雖然對照例3較具體實例1 6差，但較對照例1之習用液體佳。然而，於對照例3中，二價或三價金屬之磷酸鹽的粉碎極爲困難，而且，於該液體製備1 〇日後，發現二價或三價金屬之磷酸鹽沉降。係因對照例3不含水性高分子化合物’故該二價或三價金屬之磷酸鹽粉末凝結。表9列出本發明申請專利範圍第4項之調理液的成分。於表9及及對照例7之加速成分係使用硫酸氫銨作爲觸媒而產製。雖然本發明對p Η未加以限制，但若聚合物或共聚物之ρ Η太低，則預先使用氫氧化鈉將聚合物或共聚物之Ρ Η調至中性爲佳，以防止磷酸鹽粉末再溶於液體中。耐久性試驗係於該調理液於室溫下保持1 0日之後進行。〔具體實例2 1〕 1 0 0毫升1莫耳/升之硫酸鋅溶液及1 0 0毫升1 莫耳/升1 -磷酸氫鈉溶液於5 0°C下交替添加於1升〇.5莫耳/升硫酸亞鐵（π )溶液中，以產生沉降物。含有沉降物之溶液於9 0 °C下保持1小時以使沉降物成熟，之後傾斜漂洗1 〇次。過濾並乾燥之後，由X -射線繞射分析發現該沉降物係爲磷酸千枚巖（Z η 2 F e ( Ρ Ο 4 ) a · 4 Η 2 Ο )，部分含有磷酸鐵。於1公斤該磷酸千枚巖中添加1克藉著預先稀釋表9所列之聚合物或共聚物所得之1 0重量百分比水溶液，於球磨機中使用本紙張尺度適用中國國家標準（CNS ) A4規格（210X 297公羡） „ 〇8 - (請先閱讀背面之注意事項再填寫本頁) 、1Τ 經濟部智惡財產局員工消費合作钍印製 /3491912 A7 B7 .修' 經濟部智慧財產^7’UH工消費合作社印災五、發明説明（36) 〇 · 5毫米直徑二氧化锆珠粒硏磨約1小時。硏磨之後，使用自來水將懸浮液中之磷酸千枚巖密度調至1 〇克/升而製備此具體實例所使用之調理液。以前述雷射繞射/漫射粒徑分佈分析器測定，懸浮於該液體中之平均粒徑係爲〇 · 5微米。另外，添加0 · 5克/升亞硝酸鈉試劑以作爲鹼，得到欲施加之調理液。〔具體實例2 2〕 1〇〇毫升1莫耳/升之硫酸鋅溶液及1 〇〇毫升1 莫耳/升1 -磷酸氫鈉溶液於5 0 °C下交替添加於1升 0 . 5莫耳/升硫酸亞鐵（Π )溶液中，以產生沉降物。含有沉降物之溶液於9 0 °C下保持1小時以使沉降物成熟，之後傾斜漂洗1 0次。過濾並乾燥之後，由X —射線繞射分析發現該0降物係爲磷酸千枚巖（Z η 2 F e ( P Ο 4 ) 2 · 4 Η 2 Ο )，部分含有磷酸鐵。於500克表 9所列之聚合物或共聚物之1 0重量百分比稀水溶液中添加1 0 0克該磷酸千枚巖，於球磨機中使用0 · 5毫米直徑二氧化锆珠粒硏磨約1小時。硏磨之後，使用自來水將懸浮液中之磷酸千枚巖密度調至1克/升而製備此具體實例所使用之調理液。以前述雷射繞射/漫射粒徑分佈分析器測定，懸浮於該液體中之平均粒徑係爲0 . 5微米。〔具體實例2 3〕 1 〇〇毫升1莫耳/升之硫酸鋅溶液及1 0 0毫升1 (請先閱讀背面之注意事項再填寫本頁) ，裝· 訂本紙張尺度適用中國國家標準（CNS〉A4規格（210X297公釐） 39 491912 經濟部智慧財產^7，肖工消費合作社印製 A7 … b ___ B7 ::… | 五、發明説明（37厂 ^〜莫耳/升1 -磷酸氫鈉溶液於5 0 °C下交替添加於1升 0 · 5莫耳/升硫酸亞鐵（π )溶液中，以產生沉降物。含有沉降物之溶液於9 〇 °c下保持1小時以使沉降物成熟’之後傾斜漂洗1 〇次。過濾並乾燥之後，由X -射線繞射分析發現該沉降物係爲磷酸千枚巖（Z η 2 F e ( P〇4) 2 · 4H2〇），部分含有磷酸鐵。於1公斤表9 所列之聚合物或共聚物之1 〇重量百分比水溶液中添加 2 5克該磷酸千枚巖，於球磨機中使用〇 · 5毫米直徑二氧化鉻珠粒硏磨約1小時。硏磨之後，使用自來水將懸浮液中之磷酸千枚巖密度調至0·5克/升而製備此具體實例所使用之調理液。以前述雷射繞射/漫射粒徑分佈分析器測定，懸浮於該液體中之平均粒徑係爲0 . 5微米。此外，添加0 . 5克/升之硫酸鎂7 —水合物試劑，得到所需之調理液。〔具體實例2 4〕 1升0 . 1莫耳/升硝酸鈣溶液於5 0 °C下添加 2 〇〇毫升1莫耳/升之硝酸鋅溶液及2 0 0毫升1莫耳 /升1 -磷酸氫鈉，以使之沉降。含有沉降物之溶液於 9 0。(：下保持1小時以使沉降物成熟’之後傾斜漂洗1 〇次。過濾並乾燥之後，由X -射線繞射分析發現該沉降物係爲磷鈣鋅礦（Zn2Ca (Ρ〇4)2·4Η2〇）。於1 公斤該磷鈣鋅礦中添加1 · 5克表9所列之聚合物或共聚物之10重量百分比水溶液’於球磨機中使用〇 · 5毫米 (請先閲讀背面之注意事項再填寫本頁) ，裝· 訂参本紙張尺度適用中國國家標準（CNS ) Α4規格（210 X297公廣） -40- 491912 A7 9〇V|i ^ B7 ；气:.___ 五、發明説明（38) (請先閱讀背面之注意事項再填寫本頁) 直徑二氧化锆珠粒硏磨約1小時。硏磨之後，使用自來水將懸浮液中之磷鈣鋅礦密度調至1 〇克/升。以前述雷射繞射/漫射粒徑分佈分析器測定，懸浮於該液體中之平均粒徑係爲0 · 6微米。另外，添加〇 · 5克/升之碳酸鈉試劑，得到所需之調理液。〔具體實例2 5〕 1升〇 · 1莫耳/升硝酸鈣溶液於5 0 °C下添加經濟部智慧財產苟3(工消费合作社印製 2 0 0毫升1莫耳/升之硝酸鋅溶液及2 0 0毫升1莫耳 /升1 -磷酸氫鈉，以使之沉降。含有沉降物之溶液於 9 0 °C下保持1小時以使沉降物成熟，之後傾斜漂洗1〇次。過濾並乾燥之後，由X -射線繞射分析發現該沉降物係爲磷錦鋅礦（Z η 2 C a ( P〇4 ) 2 · 4 Η 2〇）。於1 公斤該磷鈣鋅礦中添加2 0克表9所列之聚合物或共聚物之1 0重量百分比水溶液，於球磨機中使用0 · 5毫米直徑二氧化锆珠粒硏磨約1小時。硏磨之後，使用自來水將懸浮液中之磷鈣鋅礦密度調至5克/升。以前述雷射繞射 /漫射粒徑分佈分析器測定，懸浮於該液體中之平均粒徑係爲0 · 6微米。另外，添加1 0克/升之磷酸三鈉試劑以作爲驗，得到所需之調理液。〔具體實例2 6〕於1公斤表9所列之聚合物或共聚物之1 0重量百分比溶液中，添加1公斤Ζ η 3 ( Ρ〇4 ) 2 · 4 Η 2〇試劑，本紙張尺度適用中國國家標準（CNS ) Α4規格（210X297公釐） -41 - 491912 五、發明説明（_ 於球磨機中使用1 0毫米直徑二氧化錯珠粒硏磨約1小時。硏磨之後’使用自來水將液體中之z n 3 F e ( P〇4 ) 2 · 4 Η 2〇密度調至1克/升。以前述雷射繞射 /漫射粒徑分佈分析器測定，懸浮於所製備液體中之平均粒徑係爲1 · 2微米。另外，添加5克/升之偏矽酸鈉試劑以作爲鹼，添加2克/升之聚氧化乙烯一壬酌醚以作爲界面活性劑，得到欲施加之調理液。此情況下’在不脫脂下使用試片，同時進行淸潔及調理。〔具體實例2 7〕於1公斤Ζ η 3 ( p〇4 ) 2 _ 4 Η 2〇試劑中，添加 5〇克表9之聚合物或共聚物的1 0重量百分比水溶液’ 於球磨機中使用0 · 5毫米直徑二氧化锆珠粒硏磨約1小時。硏磨之後，使用自來水將液體中之Ζ η 3 ( Ρ〇4 ) 2 · 4 Η 2〇密度調至1克/升。調整之後，液體中之平均粒徑以前述雷射繞射/漫射粒徑分佈分析器測定，懸浮於該液體中之平均粒徑係爲0 · 5微米。〔對照例7〕 1 0 0毫升1莫耳/升之硫酸鋅溶液及1 〇 0毫升1 莫耳/升1 一磷酸氫鈉溶液於5 Ot：下交替添加於1升〇· 5莫耳/升硫酸亞鐵（u )溶液中，以產生沉降物。含有沉降物之溶液於9 〇 °C下保持1小時以使沉降物成熟’之後傾斜漂洗1 〇次。過丨慮並乾燥之後，由X -射線本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公董） mu' mi -III I * m. V —ϋ am ϋ^— (請先閱讀背面之注意事項再填寫本頁) 訂經濟部智惡財/i^7g (工消費合作社印製 -42 491912 A7 __ _ _B7^_^ _ 五、發明説明（4) 繞射分析發現該沉降物係爲碟酸千枚巖（Z n 2 F e ( P〇4) 2 · 4H2O)，部分含有碟酸鐵。該磷酸千枚巖於硏缽中硏磨約2分鐘。硏磨後，以自來水稀釋，以5微米濾紙過濾，丟棄濾液。所得之沉降物於8 0 °C下乾燥1 小時而成爲粉末。於1公斤乾燥之沉降粉末中添加1 0 0 克表2所列之聚合物或共聚物之1 0重量百分比溶液。以自來水將該磷酸千枚巖粒子調至密度1克/升而製備調理液。使用前述雷射繞射/漫射粒徑分佈分析器測定時，液體中之平均粒徑係爲6.5微米。表1 0列出使用具體實例之調理液所形成之磷酸鹽層之特性。表4列出使用對照例7調理液所形成之磷酸鹽層特性。根據表1 0及4，本發明調理液使原來爲習用技術缺點之耐久性大幅改善。比較對照例3及具體實例2 2及 2 7之結果，明白顯示該聚合物或共聚物之影響。雖然對照例3較具體實例2 1差，但具有較對照例1 之習用液體佳或相當之表面調理效果。然而，於對照例3 中’二價或三價金屬之磷酸鹽的粉碎極爲困難，而且，於該液體製備1 0日後，二價或三價金屬之磷酸鹽沉降。此因不含化合物或共聚物，故該二價或三價金屬之磷酸鹽再次凝結。本發明之優點如前文所述’本發明調理液改善鈦膠體調理液之耐久本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） (請先閲讀背面之注意事項再填寫本頁) £491912 A7 ______B7 V. Invention Description (3δ) The high performance of the compound. Although Comparative Example 3 is worse than Specific Example 16, it is better than the conventional liquid of Comparative Example 1. However, in Comparative Example 3, the crushing of the phosphate of the divalent or trivalent metal was extremely difficult, and after 10 days from the preparation of the liquid, the precipitation of the phosphate of the divalent or trivalent metal was found. Since Comparative Example 3 does not contain an aqueous polymer compound ', the phosphate powder of the divalent or trivalent metal coagulated. Table 9 shows the composition of the conditioning liquid in item 4 of the scope of the present invention. The acceleration components shown in Table 9 and Comparative Example 7 were produced using ammonium bisulfate as a catalyst. Although the present invention does not limit p Η, if the ρ Η of the polymer or copolymer is too low, it is better to adjust the P Η of the polymer or copolymer to neutral by using sodium hydroxide in advance to prevent phosphate powder Redissolved in liquid. The durability test was performed after the conditioning solution was kept at room temperature for 10 days. [Specific Example 2 1] 100 ml of 1 mol / liter of zinc sulfate solution and 100 ml of 1 mol / liter of 1-sodium hydrogen phosphate solution were alternately added to 1 liter of 0.5 mol at 50 ° C. Ear / liter of ferrous sulfate (π) solution to produce sediment. The sediment-containing solution was kept at 90 ° C for 1 hour to allow the sediment to mature, and then rinsed 10 times with tilting. After filtering and drying, X-ray diffraction analysis revealed that the sedimentary system was Phosphate Phosphite (Z η 2 F e (P 〇 4) a · 4 Η 2 〇), and partly contained iron phosphate. Add 1 g of 10 weight percent aqueous solution obtained by pre-diluting the polymer or copolymer listed in Table 9 to 1 kg of this phosphorous phyllite, and use it in a ball mill. This paper applies the Chinese National Standard (CNS) A4 specification. (210X 297 public envy) „〇8-(Please read the precautions on the back before filling out this page), 1T Consumer Cooperative Printing of Intellectual Property Office of the Ministry of Economic Affairs / 3491912 A7 B7 .Repair of Intellectual Property of the Ministry of Economics ^ 7 'UH Industrial and Consumer Cooperatives ’Disaster V. Description of the Invention (36) 0.5 mm diameter zirconia beads were honed for about one hour. After honing, the density of the Phosphate Phosphate in the suspension was adjusted to 1 using tap water. G / L to prepare the conditioning liquid used in this specific example. The average particle size suspended in the liquid was measured by the laser diffraction / diffuse particle size distribution analyzer described above. · 5 g / L of sodium nitrite reagent as a base to obtain a conditioning solution to be applied. [Specific Example 2 2] 100 ml of 1 mol / L of zinc sulfate solution and 100 ml of 1 mol / L of 1 -Alternative addition of sodium hydrogen phosphate solution at 50 ° C 1 liter of 0.5 mol / liter of ferrous sulfate (Π) solution to produce sediments. The solution containing the sediments was kept at 90 ° C for 1 hour to mature the sediments, and then rinsed with tilting 10 times. After filtration and drying, X-ray diffraction analysis revealed that the zero drop system was Phosphate Phosphite (Z η 2 F e (P 〇 4) 2 · 4 Η 2 〇), partly containing iron phosphate. 500 grams Add 100 grams of the Phosphite Phosphite to a 10% by weight dilute aqueous solution of the polymers or copolymers listed in Table 9, and use a 0.5 millimeter diameter zirconia beads in a ball mill for about 1 hour. After the grinding, the conditioning solution used in this specific example was prepared by adjusting the density of the phoenite phosphate in the suspension to 1 g / liter using tap water. It was measured by the aforementioned laser diffraction / diffuse particle size distribution analyzer and suspended in The average particle size in the liquid is 0.5 microns. [Specific Example 2 3] 1000 ml of 1 mol / L zinc sulfate solution and 100 ml 1 (Please read the precautions on the back before filling in this Pages), bound and bound paper sizes are in accordance with Chinese national standards (CNS> A4 specification (210X297 mm) 39 491912 Intellectual property of the Ministry of Economic Affairs ^ 7, printed by Xiaogong Consumer Cooperative A7… b ___ B7 ::… | V. Description of the Invention (37 Factory ^ ~ Moore / liter 1-Sodium hydrogen phosphate solution is alternately added at 50 ° C In 1 liter of 0.5 mol / L ferrous sulfate (π) solution to generate sediments. The solution containing the sediments was kept at 90 ° C for 1 hour to allow the sediments to mature, and then rinsed by tilting 10 times. After filtration and drying, X-ray diffraction analysis revealed that the sedimentary system was Phosphate Phosphite (Z η 2 F e (P〇4) 2 · 4H2〇), and partially contained iron phosphate. To 1 kg of a 10 weight percent aqueous solution of the polymer or copolymer listed in Table 9 was added 25 g of the Phosphite Phosphate, and the ball mill was used for honing for about 1 hour using 0.5 mm diameter chromium dioxide beads. After honing, the density of the phyllite phosphate in the suspension was adjusted to 0.5 g / l using tap water to prepare the conditioning liquid used in this specific example. As measured by the aforementioned laser diffraction / diffuse particle size distribution analyzer, the average particle size suspended in the liquid was 0.5 micron. In addition, 0.5 g / L of magnesium sulfate 7-hydrate reagent was added to obtain the required conditioning solution. [Specific Example 2 4] 1 liter of 0.1 mol / L of calcium nitrate solution was added at 50 ° C 2000 ml of 1 mol / L of zinc nitrate solution and 200 ml of 1 mol / L of 1- Sodium hydrogen phosphate to settle. The solution containing the sediment was at 90. (: Hold it for 1 hour to allow the sediment to mature, and then rinse it 10 times. After filtration and drying, the sedimentation system was found to be a phosphite (Zn2Ca (PO)) by X-ray diffraction analysis. 4Η2〇). Add 1 · 5g of the 10% by weight aqueous solution of the polymer or copolymer listed in Table 9 to 1kg of this phosphate calcium zinc ore. Use 0.5mm in the ball mill (please read the precautions on the back first) (Fill in this page again). The paper size of the bound and bound reference papers is in accordance with the Chinese National Standard (CNS) A4 specification (210 X297). -40- 491912 A7 90V | i ^ B7; Gas: .___ V. Description of the invention ( 38) (Please read the precautions on the back before filling in this page) Honing the diameter of zirconia beads for about 1 hour. After honing, use tap water to adjust the density of the phosphate calcium zinc ore in the suspension to 10 g / l Measured by the aforementioned laser diffraction / diffuse particle size distribution analyzer, the average particle size suspended in the liquid was 0. 6 microns. In addition, 0.5 g / L of sodium carbonate reagent was added to obtain the required Conditioning solution. [Specific Example 2 5] 1 liter of 0.1 mol / L calcium nitrate solution at 50 ° C Add the intellectual property of the Ministry of Economic Affairs Gou 3 (industrial and consumer cooperatives printed 200 ml of 1 mol / L zinc nitrate solution and 200 ml of 1 mol / L 1-sodium hydrogen phosphate to settle. Contains sediment The solution was kept at 90 ° C for 1 hour to allow the sediment to mature, and then rinsed 10 times. After filtration and drying, X-ray diffraction analysis revealed that the sediment was a phosphorite zinc ore (Z η 2 C a (P〇4) 2 · 4 Η 2〇). To 1 kg of this phosphite-zincite, add 20 grams of a 10 weight percent aqueous solution of the polymer or copolymer listed in Table 9, and use 0 in a ball mill. · Honing of 5 mm diameter zirconia beads for about 1 hour. After honing, use tap water to adjust the density of the phosphazite in the suspension to 5 g / l. Use the aforementioned laser diffraction / diffuse particle size distribution The analyzer measured that the average particle size suspended in the liquid was 0.6 micron. In addition, 10 g / L of trisodium phosphate reagent was added as a test to obtain the required conditioning liquid. [Specific Example 2 6] To 1 kg of a 10 weight percent solution of the polymer or copolymer listed in Table 9, add 1 kg of Z η 3 (Ρ〇4 ) 2 · 4 Η 20 reagents, this paper size applies to Chinese National Standard (CNS) A4 specifications (210X297 mm) -41-491912 V. Description of the invention (_ 10 millimeter diameter dioxide beads in a ball mill 磨Grind for about 1 hour. After honing, adjust the density of zn 3 F e (P〇4) 2 · 4 Η 20 in the liquid to 1 g / l using tap water. Use the aforementioned laser diffraction / diffuse particle size distribution The analyzer determined that the average particle size suspended in the prepared liquid was 1.2 micrometers. In addition, 5 g / L of sodium metasilicate reagent was added as a base, and 2 g / L of poly (ethylene oxide) monoisopropyl ether was added as a surfactant to obtain a conditioning solution to be applied. In this case, the test piece is used without degreasing, and cleaning and conditioning are performed at the same time. [Specific Example 2 7] To 1 kg of Z η 3 (p〇4) 2 _ 4 Η 20 reagent, 50 grams of a 10 weight percent aqueous solution of the polymer or copolymer of Table 9 was added. 0 was used in a ball mill. Honing of 5 mm diameter zirconia beads for about 1 hour. After honing, the density of Z η 3 (PO 4) 2 · 4 Η 20 in the liquid was adjusted to 1 g / liter using tap water. After the adjustment, the average particle diameter in the liquid was measured by the aforementioned laser diffraction / diffuse particle size distribution analyzer, and the average particle diameter suspended in the liquid was 0.5 μm. [Comparative Example 7] 100 ml of 1 mole / liter of zinc sulfate solution and 100 ml of 1 mole / liter of 1 sodium hydrogen phosphate solution were added alternately to 1 liter of 0.5 mole / liter. Liter of ferrous sulfate (u) solution to produce sediment. The solution containing the sediment was kept at 90 ° C for 1 hour to allow the sediment to mature ', and then rinsed with tilting 10 times. After consideration and drying, the paper size of the X-ray is applicable to the Chinese National Standard (CNS) A4 specification (210X297). Mu 'mi -III I * m. V —ϋ am ϋ ^ — (Please read the Please fill in this page for the matters needing attention.) Order the Ministry of Economic Affairs' wisdom and bad fortune / i ^ 7g (printed by the Industrial and Consumer Cooperatives-42 491912 A7 __ _ _B7 ^ _ ^ _ V. Explanation of the invention (4) The diffraction analysis found that the sedimentary system was Dianite phyllite (Z n 2 F e (P〇4) 2 · 4H2O), partly contains iron citrate. The phoenite phosphate is honed in a mortar for about 2 minutes. After honing, it is diluted with tap water. Filter through 5 micron filter paper and discard the filtrate. The obtained sediment is dried at 80 ° C for 1 hour to become a powder. To 1 kg of dried sediment powder is added 100 g of the polymer or copolymer listed in Table 2. A 10 weight percent solution. The conditioning solution was prepared by adjusting the phoenite phosphate particles to a density of 1 g / liter with tap water. The average particle diameter in the liquid was measured using the laser diffraction / diffuse particle size distribution analyzer described above. It is 6.5 microns. Table 10 lists the characteristics of the phosphate layer formed using the conditioning solution of the specific example. Table 4 lists The characteristics of the phosphate layer formed by using the conditioning solution of Comparative Example 7. According to Tables 10 and 4, the conditioning solution of the present invention greatly improves the durability that was originally a disadvantage of conventional techniques. Compare Comparative Example 3 and Specific Examples 2 2 and 2 7 As a result, the effect of the polymer or copolymer is clearly shown. Although Comparative Example 3 is inferior to Specific Example 21, it has a better or equivalent surface conditioning effect than the conventional liquid of Comparative Example 1. However, in Comparative Example 3 ' It is extremely difficult to pulverize the phosphate of a trivalent or trivalent metal, and after 10 days from the preparation of the liquid, the phosphate of the divalent or trivalent metal is settled. Since the compound or copolymer is not contained, the divalent or trivalent The phosphate of the metal coagulates again. The advantages of the present invention are as described above. The conditioning liquid of the present invention improves the durability of the titanium colloid conditioning liquid. The paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm). (Please read the back (Notes to fill out this page)

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<RW s) LO嗽 mi 露《溪國氍齩氍 ijs 艇1M虼 (αϊιι 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） - 49 - 491912 A7B7 五、發明說明（47 ) 經濟部智慧財產局員工消費合作社印製 ffllfe^isa氍態务孽fcffi^9 嗽 ^Γ) r—H ◎ ◎ ◎ ◎ ◎ ◎ 卜 ι-I CO CN t 1 r- τ—1 r- CN| Csl l i—i Csl l ^—< cn l ro Csl l CO i τ—H m l Csl cn ◎ T—i CS i r—i CO ON 寸 λ i ◎ ◎ ◎ ◎ ◎ ◎ 卜 τ—Η oo i—1 Csl Csl v〇 \ I VsO i-1 un CnI Csl l r-H CO l τ—H m l CN C<1 l τ—H CN i ，< cn ? CNI CS ◎ r-1—< CN i τ—H cn σ\ CO j—i ◎ ◎ ◎ ◎ ◎ ◎ oo τ—Η o\ τ—1 CO CO 卜 i -H 卜 i VO CO CO l τ—i l i-i cn l CN| Cs| l τ—H CnI l y—i cn l cs CO 〇\ ◎ y—i C<1 i r—H un 〇> CN| H ◎ ◎ ◎ ◎ ◎ ◎ r < OO r—H CO CO 卜 r-H VO \ 1 寸 Csl C<1 l τ—H CN l i—H m l csl C<l l < < Csl i r—H CO l CN ON ◎ 1—( CO i \ < CTN 具體實例編 r-H t—H ◎ ◎ ◎ ◎ ◎ ◎ 卜 1~1 OO τ—i cn Oi r- t—1 Λ-i υη cs CS i y—i Csl l r-H cn l CNl CO l C<I r—H CO i CNl ON ◎ 卜 l—H CSI ? i s; SPC ο GA < 1 a N MP SPC o w GA < • r-H 1 a N MP SPC o m GA < • t-H 1 a N MP SPC SPC SPC SPC SPC 外觀 C. W.(g/m2) C . S · ( // m) P比例（％ ) 外觀 C. W.(g/m2) C . S . ( // m) P比例（％) 製備後即時測量製備後1 0日裝--------訂---------(請先閱讀背面之注意事項再填寫本頁) 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -50- 491912 A7B7 五、發明說明（48 ) 經濟部智慧財產局員工消費合作社印製具體實例編號 Zn2Ca(P〇4)2. 2H2O CO 0 巴豆酸〇 Na3P〇4 · I2H2O Ο 聚氧乙烯-壬酚醚 (E011) 2.0 〇 120 〇\ Zn2Ca(P〇4)2. 2H2 0 MD 順丁烯二酸 1000 Na2〇〇3 m 〇〇 Ζϋ3(Ρ〇4)2 · 4Η2〇 0 麵缑氍K] 堪齡 m 1 1 2000 MgS〇4 · 7H2〇 m 〇 • 1 Zn2Fe(P〇〇2· 4Η2〇 0 經羧基置換之聚乙烯醇 1 1 500 1 1 Zn2Fe(P〇4)2. 4Η2〇 v〇〇聚乙烯醇 1__ 1 1 叫 Na20 · Si02 · 5H2〇 wo 〇 1 成分 (g/L) 成分單體單體 (w t % ) (ppm) 成分 (g/L) 成分 (g/L) 溫度（°c ) 金屬磷酸鹽粒子稍 Κ] -Μ 氍鬆 Κ]胡單體之共聚物總量界面活性劑時間（秒铝Φ 爷蛔鹼鹽本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐）裝--------訂---------(請先閱讀背面之注意事項再填寫本頁) -51 - 491912 A7B7 五、發明說明（49) 經濟部智慧財產局員工消費合作社印製 1、鋸^15齲氍璲 frsMilw00嗽〇 ο<ι ◎ ◎ ◎ ◎ ◎ ◎ 寸 i—i CN CnI y—\ i 1 un CO All t—i CO i l—H cn l Csl Csl ? < 1 CN l r-H cn l CNl cn LO r-H CN) r-H cn o\ 1—1 ◎ ◎ ◎ ◎ ◎ ◎ OO ΐ < 1 < 寸 CNl 〇\ \ < 卜 CN| CsJ l t—H CO i r-H m i CSI C<l l t—H CN i H cn l CSI Csl On ◎ r- H CSJ l CN| 〇〇 T—Η ◎ ◎ ◎ ◎ ◎ ◎ 卜 ί 1 < OO y....... i CO csl OO r—H T—< OO C<l Csl l cs ? i 1 cn csl CO l H Csl i r—1 cn l CN) cn On ◎ r—H CS i \ 1 CO a\ 卜 ◎ ◎ ◎ ◎ ◎ ◎ νο τ—1 卜 τ—H CNl CN 卜 r-H vn i I VO Csl Csl i t—1 Csl ? r™H CO l CN C<1 ? T'·"' < CO ? T—( cn l CN CJN 卜 r—H Csl i r-H 賴 K 靡 4 \ 1 ◎ ◎ ◎ ◎ ◎ ◎ 卜 1—Η 00 1 \ 寸 CNl 卜 y—i i—H r- CN Csl l t—H Csl l l—H cn l C<l CN l t—H Csl i y—i m l Csl 〇\ ◎ v〇 τ·Η CS l i—H U ο m < ο < 1 5=1 Ν pLn CJ PLh 00 o ω < o < -1—( 1 N Ph U CL, CO o pq < ϋ < 1 a N dn U Ph OO u (¾ CO U Oh 00 U Oh 00 U 00 騷户^s cs a bfl u /^S OO u 萃 J_J J-Λ CL, 顧产^、 CM a u s 00 u 摩 J_J -1A PL, m ,. m Μ m 〇 t—H Si 裝--------訂---------(請先閱讀背面之注意事項再填寫本頁) 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -52- 491912 A7B7 五、發明說明（50 ) 經濟部智慧財產局員工消費合作社印製 6撇具體實例編號 Ζη3(Ρ〇〇2· 4H2〇〇甲基丙烯酸苯乙烯磺酸 • \〇 CN Zn3(P〇4)2 4H2O CN Ο 順丁烯二酸 100 N a 2 0 · S i 0 2 • 5H2〇 υη Ο 裝s Κ) _ 二贓螽Η 〇 120 CN Zn2Ca(P〇4)2 • 2H2〇 VO Ο u C2H5 s 順丁烯二酸乙烯基磺酸〇 NasP〇4 · I2H2O Ο 1 Zn2Ca(P〇4)2 • 2H2〇〇 0.6 K u C3H7OH s 順丁烯二酸 1500 Na2 C 0 3 0.5 1 S CO CN Zn2Fe(P〇4)2 • 4H2〇〇 Ο • ' 丙烯酸 100 2000 MgS〇4 · 7H2〇 Ο I 1 CNl CN Zri2Fe(P〇4)2. 4H2O 0.5 ' • 順丁烯二酸乙酸乙烯基 500 • I 1 g Zn2Fe(P〇4)2 • 4H2〇〇 Ο C2H4OH 100 • 1 1 — NaN〇2 νη Ο 1 s 成分 (g/L) ώ (w t %) 成分 (w t %) 成分 (w t % ) a 成分’ (g/L) 成分 (g/L) (°C ) 金屬磷酸鹽粒子式1之單體 α , β -不飽和單體共聚單體共聚物鹼鹽界面活性劑溫度時間裝--------訂---------(請先閱讀背面之注意事項再填寫本頁) 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -53- 491912 A7 B7 五、發明說明（51 ) 經濟部智慧財產局員工消費合作社印製 fflftNi a 氍態壬gfcMW ο τ« 加J m m n Nn 卜 CO ◎ ◎ ◎ ◎ ◎ ◎ r—Η v〇 CN On i—1 VO r ' Ή v〇 OJ CSI i r—H i r—H CN l r·—H CN l t—H CN i r—H CO i CN o 〇> ◎ υη τ—1 CM 1 CN ◎ ◎ ◎ ◎ ◎ ◎ 卜 ι 4 ι H 寸 CN r- t—H v〇 t—H r- CN CO l CN i H CO i CNl ΐ τ—H CNl i τ—1 CO CN cn σ\ ◎ οο ι—Η CNl l ι—Η s: un CN ◎ ◎ ◎ ◎ ◎ ◎ r- r_H ON t 崎寸 CN OO 1—H t i υη CO CN] i r-H CN t CO CN i t i CNJ i r-H cn t CO i—i σ> ◎ ι—Η CN i CO 寸 Οί ◎ ◎ ◎ ◎ ◎ ◎ τ Η r'—H CO CN υη y—i CNl All r—H <N i cn ? Ol CO ? i—H CN i cn i CN CN ◎ 1~1 CN l i—i CO ON CO CN ◎ ◎ ◎ ◎ ◎ ◎ r- ι 1 i oo r-H m CN OO VO 1—< 寸 CN CN l t—H CO l cn i cs l r-H CO ? τ—H CO CN ON ◎ \〇 τ—Η C<l ? τ—H V〇 ON CN CNI ◎ ◎ ◎ ◎ ◎ ◎ r- t-H OO t—H cn CSJ oo r-H t^· r—H vn csi CS l t-H CM i ι—H cn i CN CM i OI i—H cn i Csi On ◎ ι—Η OJ l f < 1—H CN ◎ ◎ ◎ ◎ ◎ ◎ 寸 r-H 1—H CN CN 卜 υη i—H cs All CN ι—H CO i CN i τ—H l cn 卜〇\ ◎ VO τ—Η CNl i t-H ON 1 Ϊ CJ CLh cn ο Ρϋ < Ο < Ν Ρη o cn o m < o < -ϊ-Η ：z; S=! N d. 〇 Ph OO ϋ ω < o I < < 5=1 N Oh o Ph C/D 〇 Ph ΏΠ U Ρη C/D 〇 PM oo u CM c/^ 願 ^—s cs a — u /--N a 、^〆 OO u 沴、^/ 屡 ΛΛ CLh 顧 /^、 CS S DD ◦ a cn u 、^〆 λλ pu 鹚展 _盤ffiW M S m _ ο ®ί Η -----------裝--------訂 --------(請先閱讀背面之注意事項再填寫本頁) 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -54-< RW s) LO Mi Mi Lu "Xi Guo 氍齩氍 ijs boat 1M 虼 (αϊιι) This paper size applies to China National Standard (CNS) A4 (210 X 297 mm)-49-491912 A7B7 V. Description of the invention ( 47) Printed by the Consumers' Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, ffllfe ^ isa, state of affairs, fcffi ^ 9, ^^) r—H ◎ ◎ ◎ ◎ ◎ ◎ BU-I CO CN t 1 r- τ—1 r- CN | Csl li—i Csl l ^ — < cn l ro Csl l CO i τ—H ml Csl cn ◎ T—i CS ir—i CO ON inch λ i ◎ ◎ ◎ ◎ ◎ ◎ τ—Η oo i —1 Csl Csl v〇 \ I VsO i-1 un CnI Csl l rH CO l τ—H ml CN C < 1 l τ—H CN i, < cn? CNI CS ◎ r-1— < CN i τ —H cn σ \ CO j—i ◎ ◎ ◎ ◎ ◎ ◎ oo τ—Η o \ τ—1 CO CO bu i -H bu i VO CO CO l τ—il ii cn l CN | Cs | l τ—H CnI ly-i cn l cs CO 〇 \ ◎ y-i C < 1 ir-H un 〇 > CN | H ◎ ◎ ◎ ◎ ◎ ◎ r < OO r-H CO CO HrH VO \ 1 inch Csl C < 1 l τ—H CN li—H ml csl C < ll < < Csl ir—H CO l CN ON ◎ 1— (CO i \ < CTN specific Example editor rH t—H ◎ ◎ ◎ ◎ ◎ ◎ bu 1 ~ 1 OO τ—i cn Oi r- t—1 Λ-i υη cs CS iy—i Csl l rH cn l CNl CO l C < I r-H CO i CNl ON ◎ ll—H CSI? Is; SPC ο GA < 1 a N MP SPC ow GA < • rH 1 a N MP SPC om GA < • tH 1 a N MP SPC SPC SPC SPC SPC Appearance CW (g / m2) C. S · (// m) P ratio (%) Appearance CW (g / m2) C. S. (// m) P ratio (%) Measurement immediately after preparation 10 days after preparation Loading -------- Order --------- (Please read the precautions on the back before filling this page) This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) ) -50- 491912 A7B7 V. Description of the invention (48) Printed by the Consumer Property Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, the specific example number is Zn2Ca (P〇4) 2.2H2O CO 0 Crotonic acid〇Na3P〇4 Nonyl ether (E011) 2.0 〇120 〇 \ Zn2Ca (P〇4) 2.2 2H2 0 MD Maleic acid 1000 Na2 〇3 m 〇〇ZOϋ3 (Ρ〇4) 2 · 4Η2〇0 缑氍 K ] Can age m 1 1 2000 MgS〇4 · 7H2〇m 〇 • 1 Zn2Fe (P〇〇2 · 4Η2〇 0 Polyvinyl alcohol substituted by carboxyl group 1 1 500 1 1 Zn2Fe (P〇4) 2. 4 2 0 v 0 〇 Polyvinyl alcohol 1__ 1 1 is called Na20 · Si02 · 5H2 〇wo 〇1 Component (g / L) Component monomer Monomer (wt%) (ppm) Ingredient (g / L) Ingredient (g / L) Temperature (° c) Metal phosphate particles slightly K] -Μ 氍松 Κ] Hu monomer copolymer total surfactant Time (second aluminum 蛔蛔 alkali salt size of this paper applies to China National Standard (CNS) A4 specifications (210 X 297 mm)) -------- Order --------- (Please first Read the notes on the back and fill in this page) -51-491912 A7B7 V. Description of the invention (49) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 1. Saw ^ 15 caries frsMilw00 〇 ο ◎ ◎ ◎ ◎ ◎ ◎ inch i—i CN CnI y— \ i 1 un CO All t—i CO il—H cn l Csl Csl? &Lt; 1 CN l rH cn l CNl cn LO rH CN) rH cn o \ 1—1 ◎ ◎ ◎ ◎ ◎ ◎ OO ΐ < 1 < inch CNl 〇 \ \ < bu CN | CsJ lt—H CO i rH mi CSI C < llt—H CN i H cn l CSI Csl On ◎ r- H CSJ l CN | 〇〇T—Η ◎ ◎ ◎ ◎ ◎ ί 1 < OO y ....... i CO csl OO r—HT— < OO C < l Csl l cs? I 1 cn csl CO l H Csl ir—1 cn l CN ) cn On ◎ r—H CS i \ 1 CO a \ Bu ◎ ◎ ◎ ◎ ◎ ◎ νο τ—1 bu τ—H CNl CN bu rH vn i I VO Csl Csl it—1 Csl? r ™ H CO l CN C < 1? T '· "' < CO? T— (cn l CN CJN Bu r—H Csl i rH Lai K W 4 \ 1 ◎ ◎ ◎ ◎ ◎ ◎ Bu 1—Η 00 1 \ inch CNl Bu y—ii—H r- CN Csl lt—H Csl ll—H cn l C < l CN lt—H Csl iy—iml Csl 〇 \ ◎ v〇τ · Η CS li-HU ο m < ο < 1 5 = 1 Ν pLn CJ PLh 00 o ω < o < -1— (1 N Ph U CL, CO o pq < ϋ < 1 a N dn U Ph OO u (¾ CO U Oh 00 U Oh 00 U 00 Sao ^ s cs a bfl u / ^ S OO u Extraction J_J J-Λ CL, Gu Chan ^, CM aus 00 u J_J -1A PL, m,. M Μ m 〇t—H Si equipment-- ------ Order --------- (Please read the precautions on the back before filling this page) This paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm) -52 -491912 A7B7 V. Description of Invention (50) Economy Printed by the Intellectual Property Bureau of the Ministry of Intellectual Property, Consumer Cooperatives, 6 Specific Example Numbers Zη3 (PO2 · 4H2OO, Methacrylic Acid, Styrene Sulfonic Acid · \ 〇CN Zn3 (P〇4) 2 4H2O CN 〇 Maleic acid 100 N a 2 0 · S i 0 2 • 5H2〇υη 〇 Loading s K) _ two concubines 〇120 CN Zn2Ca (P〇4) 2 • 2H2〇VO 〇 u C2H5 s maleic acid vinyl sulfonate Acid 〇NasP〇4 · I2H2O 〇 1 Zn2Ca (P〇4) 2 • 2H2〇〇0.6 K u C3H7OH s maleic acid 1500 Na2 C 0 3 0.5 1 S CO CN Zn2Fe (P〇4) 2 • 4H2. 〇〇 • 'Acrylic 100 2000 MgS〇4 · 7H2〇〇 I 1 CNl CN Zri2Fe (P〇4) 2. 4H2O 0.5' • Maleic acid vinyl acetate 500 • I 1 g Zn2Fe (P〇4) 2 • 4H2〇〇〇 C2H4OH 100 • 1 1 — NaN〇2 νη Ο 1 s Ingredients (g / L) Free (wt%) Ingredients (wt%) Ingredients (wt%) a Ingredient '(g / L) Ingredient (g / L) (° C) Metal phosphate particle Formula 1 monomer α, β-unsaturated monomer comonomer copolymer alkali salt surfactant temperature time loading -------- Order ---- ----- (Please read the precautions on the back before filling this page) This paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm) -53- 491912 A7 B7 V. Description of the invention (51) Printed by the Consumers 'Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs fflftNi a 氍 statefgcMW ο τ «plus J mmn Nn NCO ◎ ◎ ◎ ◎ ◎ ◎ r—Η v〇CN On i—1 VO r' Ή v〇OJ CSI ir —H ir—H CN lr · —H CN lt—H CN ir—H CO i CN o 〇 > ◎ υη τ—1 CM 1 CN ◎ ◎ ◎ ◎ ◎ ◎ ι 4 ι H inch CN r- t— H v〇t—H r- CN CO l CN i H CO i CNl ΐ τ—H CNl i τ—1 CO CN cn σ \ ◎ οο ι—Η CNl l ι—Η s: un CN ◎ ◎ ◎ ◎ ◎ ◎ r- r_H ON t 崎 inch CN OO 1—H ti υη CO CN] i rH CN t CO CN iti CNJ i rH cn t CO i—i σ > ◎ ι—Η CN i CO 寸〇ί ◎ ◎ ◎ ◎ ◎ ◎ τ Η r'—H CO CN υη y—i CNl All r—H < N i cn? Ol CO? I—H CN i cn i CN CN ◎ 1 ~ 1 CN li—i CO ON CO CN ◎ ◎ ◎ ◎ ◎ ◎ r- ι 1 i oo rH m CN OO VO 1— < inch CN CN lt—H CO l cn i cs l rH CO? τ—H CO CN ON ◎ \ 〇τ—Η C < l? τ—HV〇ON CN CNI ◎ ◎ ◎ ◎ ◎ ◎ r- tH OO t—H cn CSJ oo rH t ^ · R—H vn csi CS l tH CM i ι—H cn i CN CM i OI i—H cn i Csi On ◎ ι—Η OJ lf < 1-H CN ◎ ◎ ◎ ◎ ◎ ◎ inch rH 1-H CN CN 卜 υη i—H cs All CN ι—H CO i CN i τ—H l cn 卜〇 \ ◎ VO τ—Η CNl i tH ON 1 Ϊ CJ CLh cn ο Ρϋ < Ο < Ν Ρη o cn om < o < -ϊ-Η: z; S =! N d. 〇Ph OO ϋ ω < o I < < 5 = 1 N Oh o Ph C / D 〇Ph ΏΠ U Ρη C / D 〇PM oo u CM c / ^ Wish ^ —s cs a — u /-N a, ^ 〆OO u 沴, ^ / repeatedly ΛΛ CLh Gu / ^, CS S DD ◦ a cn u, ^ 〆λλ pu 鹚展 _ 盘 ffiW MS m _ ο ®ί Η ----------- Install -------- Order -------- (Please read the notes on the back before filling (This page) This paper is sized for China National Standard (CNS) A4 (210 X 297 mm) -54-

Claims

491912491912

六、申請專利範Application for patent

A8 B8 C8 D8 圍第8 8 1 1 2 3 3 3號專利申請案中文申請專利範圍修正本 (請先閲讀背面之注意事項再填寫本頁) 民國9 0年1 1月修正 1 . 一種供於金屬表面上形成磷酸鹽層之預處理使用之調理液，其特徵爲其含有一或多於一種二價或三價金屬之磷酸鹽粒子，且含有一或多於一種加速成分，選自單醣、多醣及其衍生物，其中該磷酸鹽粒子含有直徑小於5微米之粒子，總濃度係爲0 · 00 1〜3 0克/升，而該二價或三價金屬係爲一種或多於一種選自Zn，Fe ，Mn，Ni , Co, C a及A 1之金屬，該加速成分之總濃度係爲百萬分之χ 〜2 0 0〇份數。 2 · —種供於金屬表面上形成磷酸鹽層之預處理使用之調理液，其特徵爲其含有一或多於一種二價或三價金屬之磷酸鹽粒子，且含有一或多於一種加速成分，選自原磷酸鹽、多磷酸鹽及有機膦酸化合物，經濟部智慧財產局員工消費合作社印製其中該磷酸鹽粒子含有直徑小於5微米之粒子，總濃度係爲0 · 0 0 1〜3 0克/升，而該二價或三價金屬係爲一種或多於一種選自Zn，Fe.，Mn，Ni ，Co , C a及A 1之金屬，該加速成分之總濃度係爲百萬分之1 〜2〇〇〇份數。 3 · —種供於金屬表面上形成磷酸鹽層之預處理使用之調理液，其特徵爲其含有一或多於一種二價或三價金屬本紙張尺度適用中國國家梂準（CNS ) A4規格（210X297公嫠）經濟部智慧財產局員工消費合作社印製 491912 A8 B8 C8 D8 #、申請專利範圍之鱗酸鹽粒子’且含有一或多於一種水溶性高聚物化合物的加速成分，選自乙酸乙烯基之聚合物、其衍生物、及乙酸乙烯基與其他單體之共聚物， ’ 其中該磷酸鹽粒子含有直徑小於5微米之粒子，總濃度係爲0·001〜30克/升，而該二價或三價金屬係爲一種或多於一種選自Z.n ，Fe ，Mn ，Ni ，Co ， C a及A 1之金屬，該加速成分之總濃度係爲百萬分之i 〜2〇0〇份數。 4·一種供於金屬表面上形成磷酸鹽層之預處理使用之調理液，其特徵爲其含有一或多於一種二價或三價金屬之磷酸鹽粒子，且含有一或多於一種加速成分，選自藉著聚合下述單體i )及低於5 0重量百分比之下述單體 i i)所得之聚合物或共聚物，單體i )下式)所示之單體或選自α—、/3 -不飽和· 碳酸單體，單體i i)可與該單體i)共聚之單體， R1 H2C = C-C〇OR2 .................. (1) 1 ( R 1 : Η或C Η 3，R 2 : Η或具有Cl〜5之烷基或具有C 1〜5之羥烷基），其中該磷酸鹽粒子含有直徑小於5微米之粒子，總濃度係爲0 , 0 0 1〜3 0克/升，而該二價或三價金屬係爲一種或多於一種選自Zn，Fe ，Mn，Ni ，Co，本紙張尺度適用中國國家揉準（CNS ) A4規格（210X297公釐） -2 - (請先閲讀背面之注意事項再填寫本頁) 裝. ▼線 491912 A8 B8 C8 D8 々、申請專利範圍 C a及A 1之金屬，該加速成分之總濃度係爲百萬分之1 〜2〇〇0份數。 5 .如申請專利範圍第1〜4項中任一項之供於金屬表面上形成磷酸鹽層之預處理使用之調理液，其中該調理液另外含有鹼金屬鹽及/或銨鹽及/或其化合物。 6 .如申請專利範圍第5項之供於金屬表面上形成磷酸鹽層之預處理使用之調理液，其中該鹼金屬鹽或錢鹽係爲一或多於一種選自原磷酸鹽、偏磷酸鹽、原矽酸鹽、偏矽酸鹽、碳酸鹽、碳酸氫鹽、硝酸鹽、亞硝酸鹽、硫酸鹽、硼酸鹽及有機酸鹽之鹽，而其總濃度係0 · 5〜2 0 克/升。 (請先閲讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 -3 - 本紙張尺度逋用中國國家橾準（CNS ) A4規格（210X297公釐）A8 B8 C8 D8 No. 8 8 1 1 2 3 3 3 Chinese Patent Application Amendment (please read the precautions on the back before filling this page) Republic of China 1 January 1 Amendment 1. One for Conditioning liquid used for pretreatment for forming a phosphate layer on a metal surface, which is characterized in that it contains one or more phosphate particles of a divalent or trivalent metal and contains one or more acceleration components, selected from monosaccharide , Polysaccharides and derivatives thereof, wherein the phosphate particles contain particles smaller than 5 microns in diameter, the total concentration is 0. 00 1 to 30 g / l, and the divalent or trivalent metal is one or more than one The total concentration of the acceleration component is a metal selected from the group consisting of Zn, Fe, Mn, Ni, Co, Ca, and A1, which is χ to 2000 parts per million. 2-A conditioning fluid for pretreatment of forming a phosphate layer on a metal surface, characterized in that it contains one or more phosphate particles of one or more divalent or trivalent metals and one or more accelerations Ingredients selected from orthophosphate, polyphosphate, and organic phosphonic acid compounds, printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, where the phosphate particles contain particles less than 5 microns in diameter, and the total concentration is 0 · 0 0 1 ~ 30 g / l, and the divalent or trivalent metal is one or more than one metal selected from the group consisting of Zn, Fe., Mn, Ni, Co, C a and A 1, and the total concentration of the acceleration component is 1 to 2000 parts per million. 3 — — A conditioning solution for pretreatment of phosphate layers on metal surfaces, characterized in that it contains one or more divalent or trivalent metals This paper is sized for China National Standards (CNS) A4 (210X297 public money) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 491912 A8 B8 C8 D8 #, the patent application scope of the phosphonium salt particles, and contains one or more than one water-soluble polymer compound acceleration component, selected from Polymers of vinyl acetate, their derivatives, and copolymers of vinyl acetate and other monomers, where the phosphate particles contain particles less than 5 microns in diameter, with a total concentration of 0.001 to 30 g / L, The divalent or trivalent metal is one or more than one metal selected from Zn, Fe, Mn, Ni, Co, Ca, and A1, and the total concentration of the acceleration component is i ~ 2 parts per million. 〇〇〇parts. 4. A conditioning liquid for pretreatment for forming a phosphate layer on a metal surface, characterized in that it contains one or more phosphate particles of a divalent or trivalent metal and one or more acceleration components Is selected from a polymer or copolymer obtained by polymerizing the following monomer i) and the following monomer ii) below 50% by weight, the monomer i) is a monomer represented by the following formula) or is selected from α —, / 3-unsaturated · carbonic acid monomer, monomer ii) monomer that can be copolymerized with this monomer i), R1 H2C = CC〇OR2 ...... .. (1) 1 (R 1: Η or C Η 3, R 2: Η or an alkyl group having Cl ~ 5 or a hydroxyalkyl group having C 1 ~ 5), wherein the phosphate particles contain a diameter less than 5 microns The total concentration of the particles is 0, 0 0 1 to 30 g / l, and the divalent or trivalent metal is one or more than one selected from Zn, Fe, Mn, Ni, Co. This paper size is applicable China National Standard (CNS) A4 (210X297 mm) -2-(Please read the precautions on the back before filling out this page). ▼ Line 491912 A8 B8 C8 D8 々, patent application scopes C a and A 1 Metal that Quick thirds of the total concentration of 1 part per million for the Department of ~2〇〇0 copies. 5. The conditioning liquid for pretreatment for forming a phosphate layer on a metal surface according to any of claims 1 to 4 of the scope of the patent application, wherein the conditioning liquid additionally contains an alkali metal salt and / or an ammonium salt and / or Its compounds. 6. The conditioning liquid for pretreatment for forming a phosphate layer on a metal surface as claimed in item 5 of the scope of patent application, wherein the alkali metal salt or money salt is one or more than one selected from orthophosphate and metaphosphate Salts, orthosilicates, metasilicates, carbonates, bicarbonates, nitrates, nitrites, sulfates, borates, and organic acid salts, and their total concentration is 0 · 5 ~ 2 0 g /Rise. (Please read the precautions on the back before filling this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs -3-This paper size is in accordance with China National Standard (CNS) A4 (210X297 mm)