Substrate with a self-cleaning coating
10 claims: 6 independent, 4 dependent
- 1基本的に透明な基材であって、該基材表面の少なくとも一部にコーティングが与えられており、前記コーティングのメソポーラス構造が光触媒性を示し、粒子の形態でメソポーラス構造中に取り込まれている少なくとも部分的に結晶化した酸化チタンを含む 基材を製造する方法であって 、 コーティングのメソポーラス構造を構成する物質の少なくとも1つの前駆体および少なくとも1種の有機構造化剤を含む液体組成物の調製;有機構造化剤の周囲での前駆体の沈殿および前駆体から誘導された分子の成長;直径0.5~100nmの酸化チタンの基本ナノ粒子または微結晶の液体組成物への添加;塗布すべき表面への組成物の塗布;および 有機構造化剤の除去を連続して含む方法であって、 酸化チタン微結晶が、その完全性をメソポーラス構造中で基本的に保ったまま前記構造に取り入れられており、それらの一部がその中で集合してナノ粒子になることが可能である方法。
- 2前記基材が、 基本的に透明で、平坦または曲線状の板ガラスタイプである、請求項1に記載の 方法 。
- 3前記コーティングが、二酸化ケイ素、亜当量酸化ケイ素、またはケイ素の酸炭化物、酸窒化物または酸炭窒化物から選択される、少なくとも部分的に酸化されているケイ素誘導体に基づく副層の介在とともに形成されている、請求項1また2のいずれかに記載の 方法 。
- 4前記副層が、少なくとも5nmの厚さを有する請求項3に記載の 方法 。
- 5前記副層が、10~200nmの厚さを有する請求項4に記載の 方法 。
- 6前記副層が、30~120nmの厚さを有する請求項5に記載の 方法 。
- 7前記コーティングがゾルゲル法により堆積されている、請求項1~6のいずれかに記載の 方法 。
- 8前記コーティングが30~800nmの厚さを有する、請求項1~7のいずれかに記載の 方法 。
- 9前記酸化チタンが0.5~100nmの直径を有するナノ粒子を含み、それら自体は直径0.5~10nmの基本粒子または微結晶のクラスターから形成されている、請求項1~8のいずれかに記載の 方法 。
- 10前記基材が、 ガラスまたは透明プラスティックに基づく基本的に透明な基材であって、反射防止機能性を有する薄層または複数の薄層が、基材表面とメソポーラス構造を有するコーティングとの間に挿入されている基材である 請求項1~9のいずれかに記載の方法 。
Independent claims10
45 paragraphs, as filed
The present invention relates to various materials found in buildings, vehicles, urban furniture, or household electrical equipment, ie, specifically, transparent substrates made of glass or polymers useful as flat glass, such as display screens. Suspended ceilings such as ceramic or glass-ceramic base materials that can be used in household electrical equipment, roof tiles, floor tiles, stones, cementic compositions and building materials such as metal surfaces, insulated glass wool or textile glass yarn that can be used as filter media, etc. , Quartz, and fibrous mineral materials for producing silica fibers and the like.
Recent studies have been conducted with the aim of improving the comfort of using these materials, especially making them easier to clean.
In particular, functional coatings with photocatalytic properties have been developed. These are TiOs that are crystallized, in particular, at least in part, especially in the Anatas form.<sub>2</sub>It is a coating containing, for example, has been described in the WO97 / 10185, WO97 / 10186, WO99 / 44954 and WO01 / 66271 patents. This type of semiconductor material, which is based on a metal oxide that is optionally doped (there are other oxides that can be photocatalytic, such as ZnO), undergoes a radical reaction that oxidizes the organic compound by the effect of radiation of suitable wavelengths. You can start. Therefore, this type of coating is very effective in decomposing organic stains when exposed to sufficient radiation for this purpose (generally ultraviolet and may be in the visible light range). Is. Furthermore, it has also been found that they exhibit some hydrophilicity, especially if the coating is based on titanium oxide and if exposed to the radiation for a sufficiently long period of time. Therefore, this coating is very effective in decomposing organic stains and removing mineral stains due to their hydrophilicity. However, its activity depends on exposure to radiation (of sufficient intensity) (long enough) of wavelengths for this purpose. Therefore, the behavior of this type of coating is strongly dependent on environmental conditions, especially solar and precipitation conditions, for outdoor exposure. Similarly, in the absence of suitable lighting, its nighttime activity tends to be lower than its daytime activity.
<p> Therefore, it is an object of the present invention to further improve the functionality imparted by this type of "self-cleaning" or "delayed contamination" coating. The invention is described in detail in terms of improved efficiency, in various aspects, first with respect to radiation exposure conditions, second with respect to mechanical stress (wear resistance, etc.), and finally with respect to other functional combinations. The aim is to obtain a coating that can be "multipurpose". More specifically, an object of the present invention is antifouling, whether under normal irradiation conditions, at night or indoors, especially by the action of residual UV radiation from conventional luminaires, or by the action of UV radiation through flat glass. To obtain a coating that can exhibit activity. Products related to UV lamps, especially self-cleaning filters, are also the subject of the present invention.</p>
<p> The subject matter of the present invention is, firstly, basically transparent, especially based on glass or one or more polymers, or made of ceramic or glass ceramic, building materials (wall undercoat, concrete slab or block, architecture. For concrete, roof tiles, materials for ceramic compositions, terracotta, slate, stone types, or mineral insulating wool type glass or fibrous substrates based on glass reinforced yarn, even products containing quartz or silica. It is a base material which may be (good). This group is based on the fact that at least a portion of the surface of the substrate is coated and the mesoporous structure of the coating is photocatalytic and contains at least partly particularly anatas and / or rutile crystallized titanium oxide. It is a characteristic of the material.</p>
The term "mesoporous" means pores with a diameter of 2-50 nm. The mesoporous structures obtained by the methods described below are, in particular, the elements Si, W, Sb, Ti, Zr, Ta, V, B, Pb, Mg, Al, Mn, Co, Ni, Sn, Zn, In, Fe. Based on at least one compound of at least one of and Mo, it is covalently attached to O, S, N, C or other elements when appropriate. Titanium oxide, which is at least partially crystallized, is incorporated into the mesoporous structure, for example, in the form of fully identifiable particles. The entire mesoporous structure incorporating titanium oxide is basically strong, can adhere, and can exhibit excellent mechanical strength and wear resistance. Mesoporous structures can be composed exclusively of titanium compounds such as titanium or oxides, especially those crystallized in anatas or rutile forms. It is known that the titanium oxide thus incorporated exhibits a very high degree of photocatalytic activity. Thus, residual UV radiation after passing through one or two sheets of flat glass or residual UV radiation coming from indoor electrical lighting decomposes organic residues with respect to the substrate of the invention, which then become hydrophilic by radiation. Sufficient to be flushed onto or in a relatively uniform liquid film formed on the substrate. The coating of the present invention has both the functionality of photocatalytic decomposition of organic residues and the functionality of removing organic and inorganic residues (hydrophilic / lipophilic) by the effect of liquids such as condensed liquids. The high degree of performance provided by the present invention is probably due, at least in part, to the internal connection of the pore network, allowing contaminants to approach the titanium oxide particles well, as well as on the surface of these particles. It allows the photogenerated species to diffuse well into the coating.
In addition, such high durability of wear resistance and photocatalytic activity is excellent (see Examples below). Therefore, the present invention also allows for retention of pore size after wear, but one would otherwise expect wear to densify the surface layer and eventually lose antifouling properties.
Furthermore, the mesoporous properties of the substrate allow the concept of impregnation with functional agents such as deodorants, antibacterial agents or other such agents, following the formation of mesoporous structures.
It is advantageous that the substrate according to the invention is basically transparent and is of a flat or curved flat glass type, but in this type of application the accumulation of dirt that impedes visibility is the most troublesome and its transparency. This is because the cleaning operation is most necessary to guarantee the above. This is a large relief, eg, a flat glass with a pyramidal shape with a depth of a few millimeters, i.e. a flat glass that exhibits smaller surface bumps, such as that resulting from impressed glass or chemical etching with hydrofluoric acid. That is, it may be frosted glass or opaque glass.
Preferably, the coatings of the invention are sublayers based on silicon dioxide, subequivalent silicon oxide, or at least partially oxidized silicon derivatives selected from acid carbides, acid nitrides or carbonitrides of silicon. Formed with the intervention of. The sublayer has been found to be useful when the underlying surface is made of glass, but when alkali metal (sodium) ions emanating from the glass move into the coating of the invention, under certain conditions, the photocatalyst This is because it may impair sex. In fact, the sublayer forms an alkali metal barrier. The sublayer may be of the type described in Japanese Patent WO01 / 32578 described above. It is advantageous that it has a refractive index of 1.45 to 1.80, especially 1.50 to 1.75, for example 1.55 to 1.68. Such a relatively low index of refraction on a glass-type transparent substrate can prevent seemingly unattractive reflective effects.
Therefore, it is advantageous for this sublayer to contain Si, O, or to contain carbon and nitrogen. However, it may contain less material than silicon, such as metals such as Al, Zn or Zr. The sublayer can be deposited by sol-gel, thermal decomposition, especially CVD (Chemical Vapor Deposition). Using the latter technique, SiO is deposited directly on the ribbon of float glass in the case of a glass substrate.<sub>x</sub>C<sub>y</sub>Or SiO<sub>2</sub>The coating can be obtained very easily. However, it is also possible to deposit such coatings by vacuum technology, eg, sputtering with a Si (optionally doped) target or a silicon oxide target (eg, in an oxidizing and / or nitriding reactive atmosphere). It is possible.
The sublayer preferably has a thickness of at least 5 nm, particularly a thickness of 10 nm to 200 nm, for example 80 nm to 120 nm.
According to another advantageous feature of the substrate of the present invention, the coating having a mesoporous structure is deposited by the sol-gel method; its thickness is 30 to 800 nm; the titanium oxide incorporated into the mesoporous structure is It is optionally doped as described in patent applications WO97 / 10185 and WO97 / 10186, which are incorporated herein by reference, and contains nanoparticles with a diameter of 0.5-100 nm, especially 1-80 nm, which themselves. Is formed from clusters of basic particles or microcrystals with a diameter of 0.5 to 10 nm. The term "diameter" is used in a broad sense in this application. It is rather a measurement of the size of nanoparticles or microcrystals. The latter shape will approach a spherical shape, but otherwise it may have an elongated shape or a completely random shape in the form of rice grains.
Another object of the present invention is a method for producing the above-mentioned substrate, which is a liquid composition containing at least one precursor of a substance constituting the mesoporous structure of a coating and at least one organic structuring agent. Preparation; Precipitate precipitation and precursor-derived molecular growth around organic structuring agents; as defined above, of optionally doped titanium oxide nanoparticles or crystallites with a diameter of 0.5-100 nm. A method comprising the addition to a liquid composition; the application of the composition to a surface to be coated; and the removal of an organic structuring agent, wherein the basic titanium oxide particles or microcrystals have a mesoporous structure for their completeness. It is to provide a method that is incorporated into the structure while being basically preserved in it, and some of them can be aggregated in it to form a cluster. During the manufacture of such substrates, operating conditions (content, pH, temperature, etc.) eliminate the room for titanium oxide particles or microcrystals, especially the smallest of them, to assemble and / or grow with each other. Not done.
For the production of the substrate of the present invention, it is advantageous that the preparation of the liquid composition comprises the preparation of an oxide (particularly silica) precursor sol; aging of the sol; and mixing with a structuring agent. ..
Aging of the sol allows preliminary condensation of the oxide precursor, favoring the structuring of the condensed oxide coating on the surface of the substrate in large areas. Advantageous aging conditions include keeping the sol at a temperature of 40-60 ° C for 30 minutes-24 hours, with shorter aging times increasing the temperature.
In this case, it is advantageous that the oxide precursor is a hydrolyzable compound such as halide or alkoxide, and the structuring agent is preferably a quaternary ammonium type cationic surfactant such as cetyltrimethylammonium bromide. Alternatively, it is advantageous to choose from nonionic surfactants, including, for example, ethylene oxide or propylene oxide based diblock or triblock copolymers.
The subject of the present invention is also to apply the base material according to the present invention, particularly a base material which is basically transparent, to the production of "self-cleaning" flat glass which can simultaneously provide antifouling, anti-fog and anti-condensation behavior. This may be double glazing type building glazing or windshield, rear glazing, sunroof and side window type automotive windows. It may be a window for trains, planes and ships. It may be practical glass such as aquarium glass, store window glass and greenhouse glass, or flat glass used for interior fixtures, urban furniture or mirrors. It may be flat glass used in television, computer or telephone screen type display screens. This type of coating can also be applied to electronically controlled plate glass such as wire or layered heating windows, electrochromic glass, glass incorporated in liquid crystal films, electroluminescent glass or photovoltaic glass.
When the substrate of the present invention is applied to plate glass (based on glass or transparent plastic), one or more thin layers other than the above-mentioned sublayers based on at least partially oxidized silicon derivatives are applied to the surface of the substrate. It may be inserted between the coating and the coating having a mesoporous structure. These are, in particular, antistatic functions, thermal functions (heating by applying current leads, low emissivity function, sun blocking function, etc.) or optical functions (reducing light reflection and / or reflection) such as stacking of antireflection layers. It may be a layer having (by making the color of the base material lighter). Patent applications WO 97/10186 (described above) and WO 02/02472 are incorporated herein by reference with respect to such functional layers applied to flat glass in a known manner, preferably in laminated form.
The substrate according to the present invention may be made of any building material that can be used in the production of indoor or outdoor partition walls, wall exterior materials, roofing materials and flooring materials, apart from its use as flat glass. Good (metal, wood, stone, cement, concrete, terracotta, ceramic, wall undercoat, etc.).
If instead based on mineral insulating wool or based on textiles based on glass tempered fibers, the substrate can act as a filter medium or can be used for suspended ceilings that are not easy to clean.
The subject of the present invention is<u style="single">According to claim 1.</u>Woven base material, non-woven base material (needle punch mat, felt, wool, etc.), woven base material, mesh base material, molten silica fiber with a diameter of 1 to 20 μm, cleaning glass fiber (90%) Blocks or alumina of fired fibers (known as "hard silica") based on silica)<u style="single">Bim</u>Light fiber, deodorant filter, filter for decontamination of industrial waste, antibacterial filter, filter for decontamination and purification of domestic air, passengers of transportation means (automobiles, trains, planes, ships, etc.) It is also applied to manufacture filters for purifying compartments, filters for purifying cigarette smoke, and filters for purifying household electrical equipment (refrigerators, etc.).
The present invention will be described by non-limiting examples.
<u style="single">Example 1</u> On the glass, which is still in the form of a ribbon of float glass, a sublayer based on the acid carbide of silicon, called SiOC for convenience (without determining the actual oxygen and carbon content in the coating), was deposited, but the glass It is a transparent silica-soda-lime glass with a thickness of 4 mm, such as the one sold by Saint-Gobain Glass France under the name Planilux. This sublayer is a Si precursor, especially SiH diluted in nitrogen.<sub>4</sub>Utilizing an ethylene mixture, deposited by CVD using nozzles placed sideways on the ribbon of the float glass on the flat glass production line in the float chamber when the glass is still at a temperature of about 550-600 ° C. I let you. The resulting coating was about 50 nm thick and had a refractive index of about 1.55. A sample having a size of 10 cm × 10 cm was cut out from the float glass provided with the SiOC alkali metal barrier sublayer thus obtained. These samples were cleaned, rinsed, dried and UV / ozone treated for 45 minutes.
A coating having a mesoporous structure was formed on the sublayer. First, 22.3 ml of tetraethoxysilane, 22.1 ml of absolute ethanol and 9 ml of HCl are mixed with desalinated water (pH 1.25) until the solution is clear, then the flask is placed in a 60 ° C water bath for 1 hour. As a result, a liquid treatment composition was obtained.
Second, a solution of cetyltrimethylammonium bromide (CTAB) on the one hand, and a solution of the polyoxyethylene / polyoxypropylene block copolymer sold by BASF under the registered trademark Pluronic PE6800 (molecular weight 8000), on the other hand. It was added to the sol obtained as described above at a ratio such that the CTAB / Si molar ratio was 0.1 and the PE6800 / Si ratio was 0.01. It was obtained by mixing 0.686 g CTAB, 20 ml ethanol and 10 ml sol; and 3.78 g PE6800, 50 ml ethanol and 25 ml sol.
TiO crystallized as anatas and about 50 nm in size<sub>2</sub>The nanoparticles were added in various ratios to one of the two liquid compositions thus obtained just prior to deposition on the sample. Sedimentation was performed by spin coating with a starting amount of 3 ml per sample (other equivalent deposition techniques include immersion coating, spraying, laminar flow coating, roll coating, flow coating, etc.).
The sample was then subjected to the following annealing treatment: 30 minutes 100 ° C, hold for 2 hours; 15 minutes 150 ° C, hold for 2 hours; 15 minutes 175 ° C, hold for 2 hours; 10 minutes 200 ° C, no holding; 3 hours 20 minutes 300 ° C, 1 hour hold; and Hold at 50 ° C for 2 hours and 30 minutes for 1 hour. The pores of the coating thus formed are 2-3 nm in size when the cationic surfactant CTAB is used as the structuring agent and 4-5 nm in size when the copolymer PE6800 is used as the structuring agent. It was.
SIMS analysis of coatings with mesoporous structures proved that the Ti / Si atomic ratios were in exact agreement with those of the original liquid composition. SIMS analysis also confirmed that the nanoparticles were evenly distributed in the three dimensions of the coating.
The table below shows the various properties of the coating during formation and after 500 cycles of Opel wear testing. In the latter case, the value shown is in parentheses. The Opel test (Building Standard EN1096-2, January 2001) showed a 9.4 cm long coated surface (this part is called a track) with a diameter of 14 mm, a thickness of 10 mm and a density of 0.52 g / cm.<sup>2</sup>Felt 400g / cm<sup>2</sup>Is applied, and then translational motion (50 reciprocating motions over the entire length of the track per minute) is combined with 6 revolutions / minute (1 cycle = 1 reciprocating motion) to give the felt. ..
The coating thickness e (nm) was measured from the SIMS profile and SEM micrographs.
TiO<sub>2</sub>(μg / cm<sup>2</sup>) Was measured from X-ray fluorescence emission.
Photocatalytic activity was measured by the following method: 1. The test is about 15 cm<sup>2</sup>Performed on the coating of; 2. Weigh the sample, the thickness of the base material, and the light transmittance T<sub>L</sub>And haze H<sub>d</sub>(Both%) were measured; 3. Palmitic acid solution (8 g of acid per 1 L of chloroform) was sprayed 3-4 times in a row at a glass / spray distance of 20 cm and deposited on a vertical substrate; 4. Samples were weighed after palmitic acid deposition to determine the thickness (nanometers) of deposited palmitic acid; 5. Light transmittance T after deposition<sub>L</sub>And haze H<sub>d</sub>Was measured; 6. Approximately 50W / m<sup>2</sup>Changes in haze were measured as a function of UVA irradiation time of intensity; 7. Graphed the time when haze decreased by 50%: t this time<sub>1/2 disappeared</sub>Call; and 8. The photocatalytic activity of the coating was evaluated as the palmitic acid disappearance rate v (nm / h) defined by the following method. v (nm / h) = palmitic acid thickness (nm) / (2 × t<sub>1/2 disappeared</sub>(h)).
TiO in coating<sub>2</sub>The values of photocatalytic activity divided by the amount of are also shown in the table below. Finally, the optical properties, i.e. light reflection R<sub>L</sub>And haze H<sub>d</sub>Indicates (%).
The exam number is defined as follows: 1 and 2: CTAB is used as the structuring agent, Ti / Si ratios are 0.1 and 0.25, respectively; 3 ~ 7: PE6800 is used as a structuring agent, and Ti / Si ratios are 0.1, 0.25, 0.5, 1 and 2, respectively.
<tables num="1"><img file="JP4739677B2_D0001.tif" /></tables>
The thickness of the layer is the incorporated TiO<sub>2</sub>It fluctuated from 200 to 500 nm depending on the amount of nanoparticles. After 500 Opel cycles, only the thickest (450 and 500 nm) coatings experienced compression to less than half the original thickness. However, the photoactivity of these coatings was tested.
The coating is a cationic surfactant and the lowest TiO<sub>2</sub>Concentration (2.2 μg / cm<sup>2</sup>) From 43nm / h for structured coatings, copolymers and best TiO<sub>2</sub>Concentration (66 μg / cm<sup>2</sup>) Shows photoactivity that fluctuates up to 684 nm / h in the case of a structured coating. v / TiO<sub>2</sub>The ratio is always equal to at least 9.
After 500 Opel cycles, partial or full functional retention was observed, with the best TiO<sub>2</sub>The optical properties are not impaired except in the case of the thickest layer with density (Ti / Si = 1 and 2). For other layers, R<sub>L</sub>And H<sub>d</sub>Values remain below 11.4 and 1.2%, respectively.
Tests 3-7, low output (1.5W / m) from conventional lighting lamps<sup>2</sup>) UVA irradiation (as test 3'~ 7') was repeated. Recorded v (nm / h) and v / TiO<sub>2</sub>The value is for the N test: 3': 0 and 0; 4': 0 and 0; 5': 13 and 0.75; 6': 19 and 0.57; and 7': 28 and 0.42.
Therefore, the substrate having the coating of the present invention has photoactivity even under low power UVA irradiation in terms of palmitic acid decomposition.
<u style="single">Example 2</u> Needle-punched silica fiber felt, sold by Saint-Gobain Quartz under the name "Needle-punched Quartzel mat" (fiber diameter 7-16 μm), has a diameter of 47 mm, a thickness of 8 mm and a density of 1000 g / m.<sup>2</sup>The disc was dipped in the composition of Test No. 6 and further impregnated, and then subjected to the above heat treatment. The mass increase of the disc thus obtained was 10%.
These discs were tested for their ability to decompose methanol at a volume concentration of 350 ppm in gaseous nitrogen under UV illumination (190-350 nm) by filtration at a flow velocity of 62.5 ml / mm.
Light power 48mW / cm<sup>2</sup>So, the efficiency, that is, the ratio of decomposed methanol was 100%. 25.6mW / cm<sup>2</sup>At the output of, it is about 96%, 8.22 mW / cm<sup>2</sup>Even under low power lighting, it was even about 58%.
Accordingly, the present invention makes available substrates that can provide the optical clarity quality required for flat glass applications and permanent self-cleaning functionality under outdoor atmospheric weather and corrosive conditions. Very advanced photocatalytic functionality can also be used at night or indoors by benefiting from low intensity radiation, such as those produced by conventional lighting or sunlight through glass, and for wastewater and air pollution decontamination applications. And allows filtration.
1 sheet
Sheet 1
Every citation, both ways
| Document | Relation | Office |
|---|---|---|
| WO01032558A1 | Cites | World Intellectual Property Organization (WIPO) |
| JP10231146A | Cites | Japan |
| JP11262669A | Cites | Japan |
| JP2001254072A | Cites | Japan |
| JP2004536014A | Cites | Japan |
| JP2002533233A | Cites | Japan |
| JP05503499A | Cites | Japan |
| E. Stathatos et al. ,Nanocrystallite titanium dioxide films made by the sol-gel method using reverse micelles,J. Sol-Gel Sci. Technol. ,NL,Kluwer Academic Publishers,1997年 6月,Vol. 10, No. 1,pp. 83-89 | Non-patent | – |
| F. G. Gao et al. ,Photocurrent generated on a carotenoid-sensitized TiO2 nanocrystalline mesoporous electrode,J. Photochem. Photobio. A,スイス,Elsevier Science S. A. ,2000年 1月 3日,Vol. 130, No. 1,pp. 49-56 | Non-patent | – |
27 members in 16 offices
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| KR20040103962A | Republic of Korea | A | |
| EP1497234A1 | European Patent Office (EPO) | A1 | |
| MXPA04010162A | Mexico | A | |
| MXPA04010162A | Mexico | A | |
| BR0309276A | Brazil | A | |
| FR2838734B1 | France | B1 | |
| PL372454A1 | Poland | A1 | |
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| US7510763B2 | United States of America | B2 | |
| KR100973747B1 | Republic of Korea | B1 | |
| EP1497234B1 | European Patent Office (EPO) | B1 | |
| AT486825T | Austria | T | |
| ATE486825T1 | Austria | T1 | |
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Numbers
- Publication
- 4739677
- Application
- 583962
Titles2
- Japanese
- セルフクリーニングコーティングを有する基材を製造する方法
- English
- How to make a substrate with a self-cleaning coating
Classification
- CPC, 29
- B01J21/063
- C03C17/00
- B01J37/0018
- B01J37/036
- C03C17/006
- C03C17/256
- C03C17/3417
- C03C17/3423
- C03C17/3435
- C03C17/3441
- C03C25/42
- C03C25/52
- C03C2217/212
- C03C2217/425
- C03C2217/477
- C03C2217/71
- C03C2218/113
- C04B41/5041
- C04B41/52
- C04B2111/2061
- Y10T428/315
- Y10T428/2438
- Y10T428/24364
- Y10T428/31
- Y10T428/249957
- B01J35/39
- B01J35/45
- C03C17/34
- C04B41/50
- IPC, 17
- C03C17 34
- A61L9 00
- A61L9 01
- B01J32 00
- B01J35 02
- B01J37 02
- B32B9 00
- B01J21 06
- B01J35 45
- B01J37 00
- B01J37 03
- C03C17 00
- C03C17 25
- C03C25 42
- C03C25 52
- C04B41 50
- C04B41 52
