TW593757B - Coating solution for forming transparent silica coating film and method for producing transparent silica coating film - Google Patents

Abstract

The invention provides a coating solution for forming transparent silica coating film which solution is stable and can readily form comparatively thick silica coating film on a substrate through single application of the coating solution without use of an organic solvent. The invention also provides a method for producing transparent silica coating film. The coating solution comprising an aqueous solution contains at least one silicon compound which is selected from the group consisting of silicon oxide, silicic acid, and a silicic acid hydrate and which has been modified whereby having silanol groups; a strong organic base; and a water-soluble polymer, wherein the silicon compound is dissolved in the aqueous solution in presence of the strong organic base.

Description

593757 5. Description of the invention (1) [Technical field to which the invention belongs] The present invention relates to a substrate for glass, ceramics, or the like on a substrate or a transparent silica coating film for forming a transparent silica coating film. The manufacturing method of the coating film, the night, and the transparent stone stone coating film is useful for forming a flattened film on a variety of substrates such as semiconductor elements and liquid crystal display elements. [Prior art] As a coating liquid for forming a silica-based coating film, it is known that a siloxane polymer obtained by superhydrolyzing and polycondensing alkoxy is dissolved in an organic solvent. [Problems to be Solved by the Invention] Hydroxyl (and cetyl alcohol; i ::: and control of hydrolysis that is not easy to achieve and control of the viscosity of the resulting liquid to maintain a certain s reaction. Furthermore, it is not easy to coat so that, as of now, the silica-based Coating film. There is also a problem entitled “Unable to manufacture stably with a high film thickness and must use organic materials.” The problems include: the price of alkoxysilane raw materials. Without using organic solvent, apply transparent silica coating film to form ^ 2 silica coating film and it is also very stable as a solution. Manufacturer of cloth solution and transparent silica coating film [Solution to Problem] Solution At least the above problems constitute at least one group of silicic acid and silicic acid hydrate.

C: \ 2D-O3DE \ 9M2 \ 91120716.ptci Page 5 has silanol-based silicon oxide, the first aspect of the invention is that it contains a compound selected from the following 593757 V. Description of the invention (2) A silicon compound, which has 樯It is recognized that Leng Meng, w — Qiang ^ 'and the water-soluble polymer's aqueous solution I > Valley fluid, and each of the above-mentioned silicon is affiliated with A ,, Liu Cong, Mo Shi, and Hua σ. Solution in the presence of the above organic test. / 合 ^ 'Combined liquid is characterized by the formation of transparent silica coating film for coating solution ^: 5 2nd, like, lies in the' like the first aspect of the transparent silica coating film formation according to rH article two, characteristics The above-mentioned organic strong test is selected from tetramethylammonium hydroxide (UMAH) and tetraethylammonium hydroxide compound. G ^ CTEAi〇 constitutes at least one group of the third aspect of the present invention is that if the town can use a coating solution, it is characterized by: strong bismuth silica coating film formation of butyl and trimethylamine composition test = Triethylamine and bismuth, which make the organic strong base and water mutually compatible, also contain a fourth aspect of the present invention, such as j / energy μ. The coating solution for forming a silicalite coating film is characterized in that any one of 7 is a product obtained by hydrolysis of silicon tetrachloride. The above-mentioned stone eve compound is the fifth aspect of the present invention, such as the coating solution for forming a 1- to 3 ° edge-silica coating film. Oxidation ... Arbitrarily placed in the room temperature at room temperature = the first compound is the sixth aspect of the present invention, such as 1 sq ... 1, and the product of the transmission. A coating solution for forming a silica coating film, which It is characterized in that any of the complaints are made of silicic acid or silicic acid η hydrate (Si02 · nH 〇) 82, the product of the above-mentioned silicon compound. The knife is heated in water and is seventh of the present invention. In one aspect, as in the coating solution for forming a No. 1 silica coating film as described in Nos. 1 to 6, any of the features is transparent, and the above water-soluble polymerization

C: \ 2D-C0DE \ 9M2 \ 91120716.ptd 593757 5. Description of the invention (3) The system is selected from polyvinyl alcohol (PVA), polyethylene acetamide (PNVA), polyethylene amine (PNVF), polymer Dimethyacrylamide (PDMAA), Polyacrylamide (P / UM), Polypropylene Morpholine (pAM), Hydroxyethyl Cellulose (PEO, Hydroxypropyl Cellulose (HPC), and Carboxymethyl Base cellulose (CMC) constitutes a group of at least one polymer. 1 An eighth aspect of the present invention is a method for manufacturing a transparent silica coating film, f is characterized by having the following steps: Silanol-based = at least one stone earth compound, organic strong base, and water-soluble polymer aqueous coating solution composed of silicon, silicic acid, and silicic acid hydrate: ^, the above silicon compound is in the above organic strong Soluble in the presence of alkali, soluble in water-soluble transparent stone syrup coating film forming coating solution is applied to the treated film ii: step; and the coating film is burned as a transparent stone yoshi stone ^ ninth invention of the invention The method is as in the eighth aspect, characterized in that the organic strong base is selected from the group consisting of tetraammonium hydroxide (TM = above) (Fine) at least one kind of exhaustion formed by a group). And ... the fourth form of money (The tenth aspect of the Ming lies in the method of the eighth aspect. The organic strong test is at least one person selected from the group consisting of triethylamine, dibutylamine, and trimethylamine. You ^. The organic solvent made up of women. °, there is an organic test and the water is compatible with each other. The eleventh aspect of the i lies in the 8th to 1 ° aspect. In order to make a square-shaped product, use the water of tetra-gasified silicon in the ^ compound system μ:> aqueous solution of organic strong alkali = water% coating solution for use. Η 夕 石 涂膜 形

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The 2nd month of this month] 2 looks like 8th to 10th! 0 State in any _ over normal temperature, big 为 for ': use the particulate silicon oxide menstrual fluid for the above-mentioned silicon compounds; to: arbitrarily placed in the product 4 to make it soluble in organic strong alkali water / 1 transparent silicon Stone coating film forming coating solution. The thirteenth aspect of the present invention is the compound of any one of the eighth to eighth aspects (= is' as the above silicon compound is used by silicic acid or silicic acid n 2 ~ 10 2 (nH20) The product obtained by dispersing in water and heating to obtain #have: strong alkali aqueous solution to obtain a coating solution for forming a transparent silica coating film. 1

The 14th aspect of the present invention is the method according to any of the 8th to 13th aspects. The above-mentioned water-soluble polymer is selected from the group consisting of polyvinyl alcohol (PVA) and polyvinylacetamide (PNVA). ), Polyvinylpyridine (pnvf), Polydimethyridamine (PDMAA), Polyacrylamide (PAAM), Polyacrylamide Morpholine (PAM) Per Ethyl Cellulose (HEC), Hydroxypropyl Cellulose (HPC), and those who defect from cellulose. The fifteenth aspect of the present invention is the method of any one of the eighth to fourteenth aspects, which is characterized in that a transparent silica coating film having a thickness of ≧ 00 ηπ] or more is formed by one coating.

The transparent silica coating film provided by the present invention is very inexpensive, has good transparency and film quality and is of high quality, and can be easily manufactured by using ordinary coating methods. Therefore, it can be used to reduce manufacturing costs and can be widely used and use. The coating solution for forming a transparent silica coating film according to the present invention contains at least one kind of stone compound, a strong organic base, and a water-soluble compound selected from the group consisting of silicon oxide having silicon group, silicic acid, and silicic acid hydrate. Polymer in water

C: \ 2D-C0DE \ 91-12 \ 91120716.ptd Page 8 V. Description of the invention (5) The nature coating solution is to make the above-mentioned stone Xi-soluble in water-soluble Tu Xi, six sigma Here, in the presence of an alkali, the coating solution for forming a stone coating film of the present invention. In the silicic acid hydrate, the σ-based compound is composed of silicon oxide, silicic acid, and silicic acid-based compounds. When the so-called device is placed in the designated environment, di = disilicic acid and silicic acid hydrate are formed by at least ~ but eight of silicon elements. 3 It is a kind of silicon oxide and silicon with continuous meshes. Constructor of acid and son. In this way, when it is managed, it can be caused by the charge: 2, having a silanol group with a specified amount or more. Here, 'as an organic strong :,': two: in a state of an organic strong alkali solution. (TMA) and Hydroxide = February is used at least one species selected from the group consisting of tetramethylammonium hydroxide. Organic strong alkalis of the same degree can also make amines again! And for 3 machine tests, at least one compound selected from the group consisting of triethylamine and dibutyl can also be used. However, since ^ ^ k 4 is low, it is better to add an organic solvent such as C, which makes the organic strong base and water mutually compatible. Organic strong test is organic I, σ Meng & πA ^. ^, 4k /, can be the organic base of the cololysin compound, it is good to take the organic test solution is PHI 1 or higher organic test. It is known that silicon dioxide is soluble in water at 0.1 to 15% in official and western nH7 mu / shizhi / dish pH7 (r ILER, Kolloid-Chemie des Siliciumdioxids, Silikate, Cornell University Press Ithaca, New York (1955)), but its concentration is low, and of course there have been no reports of coating film formation. Furthermore, it has been reported that silicon compounds are decomposed in strong alkalis.

593757

The fact that 1 A p _ j hair oxide dispersion is exempted (USP4576 92 1), but it is classified as a decree, and it is widely judged that the dispersion is not used as a coating liquid to form Report of coating film. Fengfa dissolves the number of particles of the silicon cloth solution, which is alkali degraded, and the amount of silicon is in the range, because the [chemical 1] cut of SiOH is the compound. The shape of the child ’s stone is changed to Shi Xishi to obtain ’silicon dioxide.

The concentration mechanism of organic strong bases in the south has not yet formed a large number of anions. The number of organic bonds in the burn bond of the present invention is shown in the following formula to 2.5. S is added by dissolving silicon with silanol groups to obtain transparency. Silica was clear, but it was inferred 'so it was dissolved. In particular, the Shi Ximu formed as described above. Then, such an aqueous solution having an alkali was formed at 5 wt% to form a transparent silica coating film. The bond angle Si-0-Si formed a silicon oxide bond system on water at 120 ° C to form a ceritol group. There are also iOH / nm2 0 compounds, which are used for coating film formation. The silanol group may be strong because of the unit weight of the alcohol group and the high concentration on the high density silanol group. A range of ~ 180 degrees shows a high response. People report that this -s i -O ^ s i s + H-0 ~ Η The present invention is a strong organic solvent to obtain a coating solution with a high concentration. According to the transparent description of the present invention, a strong organic base having a silanol group is soluble in water. A night alkali is added to a silicon compound having such a silanol group, and a stone shovel coating film for forming a transparent silica coating film having the silicon compound is added. The coating solution for formation is obtained by dissolving the f compound in tetramethylammonium hydroxide (TMAΗ) or the like as above, and the method for dissolving is not specifically

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V. Description of the invention (7) Don't be restricted. Ammonium ammonium (TMAί) needs to be heated after adding a gelatinous substance to dissolve it with a strong base. If you turn it on, you can get the 'fineness'. Soluble in TMAH. For example, it is also possible to dissolve the silicon by stirring and heat dissolving, or adding hydrogen to dissolve it, or by a series of solutions. It has a silanol group to the silicon oxide. As mentioned above, On the micro surface, higher organic strong alkali compounds will be formed into fine powders, and then arbitrarily placed, thereby dissolving the Shixi compound, adding water and adding tetramethylammonium oxide (TMAΗ), and then pressing the silicon compound to perform a sol-like step. Gas oxidation of four M ′ is based on heat to become soluble and to form a sol-like substance and oxidized stone as required. For example, the use of four-gas fossilized granular silica with silanol groups present at a large density at room temperature can be arbitrarily released in the gas. Where high concentration is used when oxalic acid or oxalic acid hydrate having lithophyl alcohol group is used, it is preferred to 'make it into a sol-like compound and dissolve it in a strong organic base such as TMAH. The dissolution of the following sol-like silicic acid hydrate is carried out through an extremely attention-grabbing process. That is, after adding an organic base such as TMAH, the dissolution rate is very small in a few days. Then, the dissolution rate gradually increases and is completely completed in a week Melt, and become a very stable transparent solution.

Then, a water-soluble polymer is added in order to increase the viscosity of the coating solution for forming a transparent silica coating film under the use of this transparent solution to improve its close adhesion to the substrate. Here, the water-soluble polymer is a water-soluble polymer having a polar group. By adding such a water-soluble polymer having a polar group, a thick film can be formed without cracks.

C: \ 2D-mDE \ 9M2 \ 91120716.ptd Page Π 593757 V. Description of the invention (8) This is a water-soluble polymer with a polar group used in the present invention, and examples include polyvinyl alcohol (PVA), polyvinyl acetate Phenylamine (PNVA), Polyethylene Phenylamine (PNVF), Polydimethyacrylamine (PDMAA), Polyacrylamide (paam), Polypropylene Pyridoxoline (PAM), Hydroxyethyl Cellulose (HEC) , Hypromide, Vitamin C (HPC), Carboxymethyl Cellulose (CMC), etc. Soil is water having a polar group. ≫ Grain polymer ' The most suitable one can be appropriately selected from the above polymers, and it is preferable to select as stable a substance as possible. This is because a water-soluble polymer that decomposes or deteriorates due to alkali is not suitable in terms of stability of the coating solution. For example, and saponification and neutralization of denaturation, the complete soap is qualitatively good, this type is soluble, and it is added when it is soluble in water.

In the case of using PVA (in the case of the present invention, polyvinyl acetate saponified poly (vinyl acetate) saponified), the use of generally used PVA '86 will cause acetic acid to escape and ammonia or water-soluble amines will cause p The problem that tritium is reduced and the Shixi compounds are deposited. In this case, adding organic strong alkali is not a problem, but it is better to use chemical PVA. When a completely saponified pvA is used, a coating liquid that is good and can withstand long-term storage can be obtained.

The addition amount of the water-soluble polymer having a polar group varies from polymer to polymer 1 but generally ranges from 0.1 wt% to 5 wt%. In addition, the 4 compound is added before the coating, that is, for example, before or after the silicon compound is dissolved in the organic solution, or by the water-soluble polymerization of the transparent group of the present invention with the dissolved F to form a When a coating material for forming a shiyuishi coating film is used in practice, 'this polymer is a film having a flexible film thickness and toughness. The solution works with a film-forming aid, and,

593757 V. Description of the invention (9) When the addition amount of the compound changes, it can be used to achieve free control of the film thickness which is difficult in the conventional coating method. It is further possible to form a film thickness of 100 nm or more with a single coating. Shi Xishi coating. The coating solution for forming a transparent silica coating film of the present invention thus prepared can be used directly as a coating solution, which contains 5 wt% or more of a silicon compound, and because the stone compound having a stone compound can be formed as an oligomer A transparent silica coating film with sufficient thickness. In order to form a transparent silica coating film by using the coating solution for forming a transparent sparite coating film of the present invention, this coating solution is prepared by a dip coating method, a spin coating method, a spray coating method, a stencil printing method, a roll coating method, and a setae The conventional coating method such as brush coating method is applied on the substrate, and then the satin firing is performed at a temperature of 40 ~ 80 0 ° C (preferably 450 ~ 700 ° C) to form the coating film. Especially for coating on large substrates, it is best to use a low-speed spin coating method. In this way, a uniform coating film can be formed on a large substrate larger than 15 inches, and a uniform transparent silica coating film of 100 to 50 Onm can be formed by firing. Therefore, the transparent coating solution for forming a water-soluble poly-character having a polar group according to the present invention has a practical film thickness and functions as a film. In addition, "make this water-soluble poly-eight" excellent in storage stability. When the amount of freely controlled film thickness is changed, a 500 nm film can be borrowed. ’Once applied, a thicker gel film can be formed by sol-gel method with a film thickness of 1 00 ~ ^^, which can significantly increase the film thickness. This-research results are reported in practice C: \ 2D-CODE \ 91-12 \ 91120716.ptd page 13

593757 V. Description of the invention (ίο) Important. Due to the repeated application of ^^ '~ = in the manufacturing process, it can reduce the cost of efficiency for the purpose of manufacturing the second thickness. Jia Ke took a lot of work, but greatly reduced. On the other hand, the object of the coating of the present invention is not particularly limited. ^ J forming the coating solution plate, glass substrate, ceramic substrate: if including semiconductor-based silicic acid Glass, quartz broken glass, etc. If the surface of the glass is coated with silica, the transparent silica stone coating film formed by using the transparent silica coating film of the present invention is tough and transparent due to the role of the film assistant under the polar c liquid. It is: the soluble polymer has good adhesion, and there is no pinhole or micro-cracking, so :; the compactness of the object. The coating solution of the present invention is a coating-good product. Stone coating film, low shrinkage, you do n’t have to worry about cracks. It ’s easy to form thicker silicon. Flattening film or protective film grows in semiconductors: θ θ, which is especially suitable for the formation. Furthermore, on conventional substrates such as liquid-day display elements, the conventional silica-based coating solution is mainly obtained by dissolving a prepolymer obtained by hydrolysis in an organic solvent. The change over time of j: j is a practical problem. 'However, the transparent stone of the present invention; = the coating solution for forming is a complete aqueous coating solution without using an organic solvent, and the sol viscosity does not change with time, and furthermore, it makes ^ and ^ moxibustion to a limit 'It is also safe to form a transparent silica coating film during the manufacturing process = advantages. And Li Maqi [Embodiments of the Invention] Next, the present invention will be described in detail using examples and comparative examples.

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593757 V. Description of the invention

This is limited, and it goes without saying. (Example 1) 1.0 g of particulate silica having a particle size of 5 to 50 · was added to a 0 wt% concentration of hydroxide and 5 ml of a tetramethylammonium aqueous solution, and slowly stirred with an electromagnetic stirrer. The particulate silica was slowly dissolved and completely dissolved after 2 hours to obtain a colorless and transparent solution. To this was added 5 ml of distilled water, and after stirring, 10 ml of a 1% human aqueous solution was added, and the mixture was fully stirred. The obtained transparent solution with weak viscosity was used as the coating solution of this example. The solution was applied by dip coating and fired at a temperature of soda glass for 1 hour. As a result, a transparent silica coating film was formed. A transparent conductive tin oxide film was formed on the transparent silica coating film thus formed to perform alkali resistance. Evaluation of impermeability. This transparent conductive tin oxide film is formed by the following method: the coating liquid for forming a transparent conductive tin oxide film is used to apply this coating by dip coating method at a temperature of 5 50 ° C In the method of satin firing, the sheet resistance value was measured to be 600 Ω · cm, which is the same value as that in the case of using a commercially available silica-coated substrate. Thus, it was confirmed that alkali dissolution of the glass substrate The fact that the adverse effect was not found. (Example 2) Mix 7000 g of oxalic acid η hydrate with 500 m 1 of steamed hall water and stir at 95 ° C for 5 hours. A sol-like substance Sol was added to this substance 1 5wt% aqueous solution of tetramethylammonium hydroxide Shu 〇ml stirred be 3〇 minutes

ΙΙΜΙIHH C: \ 2D-CODE \ 9 Bu 12 \ 91120716.ptd ~ ^ \ c " " ~ " 593757

And this mixture was left to stand at normal temperature. After that, about 3 days "now melted", but the dissolution rate gradually increased from the 5th day, that is, two, days: two 'completely dissolved to obtain a transparent solution. _ This solution is added 10wt%: water> valley 5ml of solution was stirred thoroughly, and a point-like solution was obtained. This solution was used as the coating solution of this example. Snn coated the rH cloth solution on the nanoglass by dip coating, dried, and then: / Burning for 1 hour 'As a result, a transparent silica coating film with a film thickness of 35 Å was formed. 2 On the transparent stone spar coating film thus formed', a transparent v electrical tin oxide film was formed in the same manner as in Example i, and As a result of measuring its sheet resistance value, it was 59 ω • cm, and no adverse effect caused by alkali dissolution of the glass substrate was found. (Example 3) a 7 g of tetrachlorosilane was stirred by an electromagnetic stirrer. Add 200 ml of pure water slowly. This hydrolysis reaction is exothermic and intensely produces white chloride. After the resulting reaction mixture is cooled to room temperature, 1 N ammonium hydroxide is added under cooling. Until the pH reaches 7.0. Filter out the precipitated genus / cereal Then, it was washed three times with steamed crane water. The precipitate thus obtained was added with a 15 wt% tetramethylammonium hydroxide aqueous solution 10 m 1 and left at room temperature. The sol-like substance was slowly dissolved, and it took 5 days. It will completely dissolve in time. To the formed transparent solution is added 1.0 wtG / GpVA, and it is fully stirred as a coating solution. This coating solution is coated on soda glass by dip coating, and dried at 50 ° Calcined at 30 ° C for 30 minutes. As a result, a film thickness of 32nm was formed.

C. \ 2D-C0DE \ 9l-12 \ 91120716.ptd page 16 W757 Description of the invention (13) Transparent silica coating film. Ming i ΐ: On the formed transparent silica coating film, a lunar m tin oxide film was formed in the same manner as in Example 1 and the sheet-shaped electric m value was measured to be 57 ° Ω cm. No glass substrate was found. , Xuan Zang (Embodiment 4) caused by the adverse effects. Add 20 g of granulated stone syrup with a particle size of 5 to 50 nm, and add 20% hydrogen hydroxide = 1 gml of tetraethylammonium hydroxide aqueous solution, and use an electromagnetic feeder to slowly drop it. : Pull: Silica slowly dissolves. It completely dissolved in hours, and a colorless and transparent solution was obtained. j Add 10ml of steamed storage water and stir, then add 1 (wt%) of m water and stir well. The obtained transparent > valley liquid having weak viscosity was used as the coating solution of this example. This coating solution was coated on soda glass by dip coating, and after drying, it was calcined at 500 ° C for one hour. As a result, a transparent silica coating film with a film thickness of 29 mm was formed. On the transparent silica coating film thus formed, a transparent V-electricity tin oxide film was formed on the transparent silica coating film thus formed, and the sheet resistance value was measured to be 67 Ω · cm. No inspection of the glass substrate was found. Adverse effects caused by dissolution. (Continuous Example 5) '2.0 g of particulate silica having a particle size of 5 to 50 nm was added to 3.0 wt% of trimethylamine 3.0 ml and 1.0 ml of acetone, and slowly stirred with an electromagnetic stirrer. The oxidized oxidized solution was slowly dissolved, and completely dissolved after about 1 hour to obtain a colorless and transparent solution. To this was added 5 ml of distilled water, and after stirring, 10% of "eight water" was added.

593757 V. Description of the invention (14) The solution 1 m 1 is fully stirred. The obtained transparent solution having weak viscosity was used as the coating solution of this example. This coating solution was applied on soda glass by dip coating, and after drying, it was calcined at a temperature of 500 ° C for 1 hour. As a result, a transparent crushed stone coating film was formed. On the transparent silica coating film thus formed, a transparent conductive tin oxide film was formed in the same manner as in Example 1, and the sheet resistance value was measured to be 7 3 Ω · cm 'No alkali dissolution place of the glass substrate was found. Adverse effects. (Comparative example) That is, 5 g of fine-grained silica with a particle diameter of 5 to 50 nm was added to 5 ml of trimethylamine at a concentration of 0 wt%, and the mixture was slowly stirred with an electromagnetic stirrer. Although a part of it melted, no further change was found after being left for 5 days. The solution part is filtered, and m is added to this as in Example 丨 as a coating. This is also the same as in Example 1 +, and the sample is mainly clothed on soda glass, but the toughness and transparency can not be obtained. membrane. Beibei [Effect of the invention] According to the above results, you can hear; 々r Η ^ ^ " According to the present invention, the following effects can be achieved ... · that is, in the presence of silanol-based silicon oxide or power failure, 卞 · Co., Ltd. of Isha-Kojima acid hydrate is used as the material, and the transparent stone stone coating film provided by the factory without having to worry about cracks, and the shrinkage rate is low, and the film is suitable for use as a flat film. Therefore, the present invention Suitable for use in glass, ceramics, etc. -When a chemical or protective film is formed on a semiconductor substrate and the transparent silica of the present invention is applied, the coating solution for soil film formation is a complete water

Page 18 593757 V. Description of the invention (15) The soluble coating solution can safely form an unrestricted transparent silica coating film in the manufacturing process because it does not need to use an organic solvent. Moreover, the price of the coating solution of the present invention is much lower than the price of the conventional coating solution using an alkoxysilane.

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Claims (1)

593757 Six, apply for the scope of profit 92ίΠ7 The coating solution for the formation of alkali stone coating film is 5 wt% or more of κ cold liquid of organic strong fork, and at least one silicon compound selected from the group consisting of silanol-containing oxidation and silicon hydrazone hydrate, tetramethylammonium ( TMAH), tetraethylammonium hydroxide (TEAH), triethylamine, and dimethylamine-at least one organic strong base, and ， ^^ ~ 5)?% Selected from polyvinyl alcohol (PVA), Polyvinylacetamide hydroxyethyl pd /, 4-vinylformamide (PNVF), polydimethylpropionamine (PDMAA), polypropylene acetamide (pAAM), polypropylene fluorene (==), Cellulose (HPC) and methyl bis (hydrazone) constitute a group of at least one water-soluble polyfluorene ^ ^ liquid, //, characterized in that the above silicon compound is a water-soluble coating solution that dissolves in the upper two and lower cores By. Knowing the existence of 2 :: Please apply for the transparent silica coating film formation of item i of the patent scope: wherein the organic strong base is at least one compound selected from the group consisting of triethylamine 'and methylamine, and contains An organic solvent that makes the two solvents compatible with water. , Strong alkali into 3 uses;:! The transparent stone evening stone coating film of any one of items 1 to 2 of the patent scope is open, cloth; f, among which ... the compound is a product obtained by four gas decomposition. / ,, $ Passing water into 4: "transparent stone stone coating of any one of the items 1 to 2 of the scope of interest, the coating solution for liquid coating, wherein the above silicon compound is: arbitrarily shaped in normal temperature atmosphere The product obtained by leaving 1, 1, 1 、 The silicon warp is used for 5: t:: 干 Liganwei any one of items 1 to 2 of the transparent silica coating film π coating for use> Valley fluid, its towel, the above-mentioned Shixi compounds Department of Shi Xiac or Shi Xi page 21c: \ Total file \ 9I \ 91120716 \ 91120716 (replace 593757 Case No. 91120716 6. Scope of patent application The product obtained by dispersing the compound (S i 〇2 · nH2 0) in water and heating it. 6 · A method for manufacturing a transparent stone siberite coating film, which is characterized by having the following steps: selecting an aqueous solution containing 5 wt% or more of an aqueous solution containing strong organic compounds, selected from silicon oxide and silicic acid having silanol groups And silicic acid hydrate, at least one chopping compound selected from the group consisting of at least one selected from the group consisting of tetra f · (TMAΗ) hydroxide, tetraethylammonium hydroxide (TEAΗ), triethylamine, dibutylamine, and trimethylamine f organic strong base, and 0.1 wt% to 5 wt% selected from the group consisting of polyvinyl alcohol (PM), polyethylene acetamide (PNVA), polyethylene formamide (PNVF), polypropylene diamine (PDMAA), Polyacrylamide (PAAM), polypropylene-: (Imo ^ & ^ ^ ^ (HPC) ^ ^ cloth / combined / night, and the above-mentioned water-soluble compound A PHI 1 or more water-soluble coating solution Luo Luo f above organic In the presence of a strong alkali, dissolve in a solution and apply it on the object to be treated; form a transparent silica coating film with a coating thickness of 400 to 800. 0: fire it as a step for the penetration coating; and apply this coating film on 7 As described in & 2-The step of coating transparent transparent stone. 7 · As in the 6th in the scope of patent application, the above organic strong base is selected and transparent The manufacturing method of the silica coating film comprises a group of at least one organic solvent which is compatible with monoethylamine, dibutylamine, and trimethylamine. The substance 'also contains the organic strong base and water 8 · For example, the sixth method of the scope of patent application, in which the transparent silica coating film as the above-mentioned item of Shi Xihua ^ is manufactured to be soluble in organic strong test θ system using the coating solution for hydrolysis of silicon tetrachloride production &Quot; " formation of transparent silica coating film from aqueous solution 9 · The manufacturer of transparent silica coating film such as the scope of application for patent ^ f ^ A326 \ Total file \ 91 \ 91120716 \ 9112〇7 丨 6 (Replace Ptc 593757 Mlt 9112Q71R ^ Please apply the patent scope method, ', Chinese, as the product of the above-mentioned Shi Xi compounds placed in any gas, you can use particulate silica to pass through the organic coating for the formation of transparent Shi Xi stone coating film. Water solution instead !. .For example, the method for manufacturing a transparent stone spar stone coating film of item 6 or 7 of the scope of patent application, as the above silicon compound, use silicic acid or silicic acid η hydrate (S1 2 ηΗ20) dispersed in water and be heated. The obtained product is a transparent silica coating film forming coating solution I 0 obtained by dissolving in a strong organic solution in an aqueous solution. 11. A method for manufacturing a transparent silica coating film according to claims 6 to 7 of the scope of patent application, wherein Those who form a transparent stone stone coating film with a thickness of 100 nm or more in one coating. % VI Λ said correction m \\ A326 \ Total file \ 91 \ 91120716 \ 91120716 (replace) -l.ptc Page 23