TW552297B - Structure having hydrophilic microporous antifouling layer and coating fluid for forming the same antifouling layer, and production of the structure - Google Patents

Abstract

The present invention provides a structure having microporous anti-fouling layer having new structure and coating fluid for forming the anti-fouling layer, and method for production of the structure. Said anti-fouling layer can reduce the rain streak foulings appearing on the surface of the structure such as a ceramic tile, especially the rain streak foulings caused by use of a silicone-based sealing agent. The micro-liquid grains having a silicon dioxide (silica) and siliceous substance for bonding are coated uniformly in the outer surface of the structure of the ceramic tiles according to the present invention, resultant substrate then is heat-treated at temperature of 300-700 DEG C to form siliceous binder. Thereby, the structure such as ceramic tile etc. having hydrophilic microporous anti-fouling layer can be obtained in the outer surface of the substrate. Said anti-fouling layer has a fine rough surface which can bond the micro-panicles of silicon dioxide and has many bent micropores communicating from the surface to the interior.

Description

552297 V. Description of the invention (1) [Detailed description of the invention] [Technical field to which the invention belongs] The present invention relates to structures such as micro, glass, ceramic tiles and the like having a novel structure on the outside. More specifically, the microporous antifouling having a novel structure on the outside, such as a broken brick with an antiflayer, functions as a coating liquid for forming an antifouling layer, and a structure for manufacturing the structure The function can well reduce the surface of the building's external wall tiles and the like, and the above self-cleaning due to the use of silicone-based sealants). Yu Yu (especially [prior art] Sometimes when the surface of a plate-like substrate such as a brick or a glass plate is formed, water diffuses on the surface of the membrane when it adheres to the surface of the substrate, and the film and the like also diffuse and flow on the surface of the membrane. In this way, ^ 丨 'is not conspicuous on the surface of the rainwater body, and it will not be conspicuous. As such a self-adhesive base film, a well-known catalytic titanium oxide (ATi〇1 is super hydrophilic in addition to the above-mentioned oxidation) In addition to the titanium film, there have also been disclosed 2 of them. Techniques for forming antifouling film on the surface of substrates such as bricks. Some are disclosed in porcelain: Publication Bulletin Brief Year No. 85. l = J = Please disclose The film is a coating consisting of 5 parts of acidic colloidal Dilysin II: ... cut, oxidized " or stone ^ cleavage, water or hydrophilic organic solvent 1 7-87 parts by weight (" parts by weight). The composition is formed by coating the surface with clay 8, glass, ceramics, etc., and heating at 30 to 2000 ° C to solidify the coating film. As a result, the coating film formed is hydrophilic It is not easy to be adhered by dirt. In addition, Japanese Patent Laid-Open Gazette No. 3 of 1998 0 6 4 6 disclosed the same

552297 V. The film of the description of the invention (2), this patent application describes coating a coating containing soluble potassium silicate and water-soluble stone sol on a steel plate and heating it at 150-250 ° C to form hydrophilicity. Method of coating film with excellent stain resistance. As described above, "in order to reduce the contamination of the surface of a substrate such as a tile, there have been proposals for forming an antifouling surface", but the proposals so far are as follows, which are not perfect. In other words, since the oxidation-based superhydrophilic film uses the photocatalytic action of titanium oxide, it has the disadvantage that it cannot exhibit antifouling properties in places not exposed to sunlight or at night. In addition, another question asked early, and one shouted, emulsified titanium-based super-hydrophilic skin :: then it can exhibit antifouling effect in the early stage] once the time = lower two, the effect of decomposing the pollution components will decrease, and the result will be * , Its: the stain effect is not significantly different from the tiles. ? Lu ί 2 I 特许 Publication Bulletin No. 1 58585 and 330646 of 998 5 The coated film is the same as the present invention, and also has currency and pollution resistance, but due to the presence of water + +-emulsified silicon, Has insufficient hydrophilic properties. Especially in the outer wall: during construction :: small, so when using the Shixi I-type sealant between its anti-fouling window frame and other places: = = J brick and the lower part of the material due to the silicone-based sealing material ~ Shan does not make a knife Prevent the pollution of rain scale caused by the leakage in the seal [problem to be solved by the invention]. In order to solve the above-mentioned problems, the present inventors have successfully developed a research into the substrate of the present invention, and as a result, a structure having a stained layer. Two microporous antifoulings having hydrophilic properties. Therefore, an object of the present invention is to provide a structure having a microporous antifouling layer on the surface, the problems described above, the outer body, and a coating for forming the antifouling layer.

552297 V. Description of the invention (3) Dressing and method for manufacturing the structure. That is, since the titanium oxide-based superhydrophilic skin and film using a catalytic action are not formed in the porous porous antifouling layer of the present invention, there are no defects due to this. In addition, the antifouling layer of the present invention is the same as the coating films described in Japanese Patent Laid-Open Publication No. 1 58 585 and 330646, but also uses silicon dioxide, but the microstructure is the same as that described in these publications. There are differences in the coating film. Therefore, compared with the coating films described in these publications, it has a completely satisfactory function of preventing gluttonous materials caused by the elution of the silicone-based sealing material. Αα is not the same as the above: The problem solved by the present invention, that is, the object of the present invention, is to provide a structure having the aforementioned b ^ ^ ^ ^ ^ ^ antifouling layer on the outside of the substrate. u —Using the fine U-shaped porous f [solution to the problem] In order to solve the above problems, due to flutter, the micro-porous anti-m 'which is hydrophilic on the outside of the taxi is provided with a coating solution for forming a substrate and manufacturing the structure The body and the antifouling layer form the structure of the present invention on the outer layer of the substrate. The surface of the antifouling layer has protrusions: a hydrophilic fine porous antifouling surface, which has many from the surface inward; particulate The coating agent containing fine rough acidic adhesive to bind the fine silica pores and forming the above-mentioned antifouling layer with silicon. The coating agent contains: a substance with a mole number of SiO 2 and alkali. Evening and bonding silica. 18 3 ′ It is preferable to contain aluminum compound. In addition, the manufacturing method of the structure 3 ′ ’is a ceramic substrate sintered 89119042.ptd

II 552297 V. Description of the invention (4) The surface is coated with liquid particles containing heat_quarrying and silicic acid for bonding at 300 ° -700 ° C, and then the mixture is obtained, thereby obtaining oxalic acid for bonding The structure that the substance becomes a silicic acid adhesive layer. The outer surface has the following hydrophilic microporous antifouling surface and many micro-rough surfaces that adhere to silica particles. In the invention I: Curved fine pores connected by parts. Microporous antifouling; the hydrophilicity of this structure formed on the outside of the substrate is not used and lacks long; the use of one-child, titanium oxide-based components described in the bulletin, and the same as the above-mentioned class I * Compared with the coating film of Fossil, there are eight people who can stand to prevent the seal due to the silicon S family, and π people are satisfied.卄 / The function of the rain scale pollution caused by the combined product In addition, the antifouling layer is rust, and the material can be observed (that is, the base, 'A eye looks smooth, because the body can directly play the original reed' / ) The original state, and as a result, the design of the base. , Shape, pattern, or decorative shape, etc., showing excellent [inventive embodiment] material and water 2: 2,; ... description, but the present invention is not limited to the structure of ^ = hole 1 ^ layer for specific patent applications determine. The structure of the present invention is from the outer surface of the substrate of the present invention and colloidal dioxide, and other dioxide; layered, medium, Zenglierennan 丨 private attack on some quilts is regarded as sticky and rough Observed from Dragon 89119042.ptd Page 8 552297 Five invention notes (5) Photomicrograph observed. Then, as shown in Fig. 1, on the surface of the microporous antifouling layer, SiO2 was observed on the surface of the microporous antifouling layer by β-sides, and the surface of the antifouling layer was rough. Although the roughness of this rough surface is very high, it can be measured with an atomic force microscope (hereinafter referred to as AMF). According to the results of "1, the average roughness should be 2-100 nm. It is best to measure the rough greenness of the surface. It is known that the method is roughly as follows: The force over-detection is applied to the small force between the sample and the probe (the atomic convergent 丨 from the ^ small shape of the Yagi wooden needle is formed in a small called a cantilever, " The front end of I, acting on the sample near the surface of the sample; ρ 成 is converted into a cantilever displacement and detected. The laser reflected light from the laser beam on Γ! Is incident on the photoelectricity through the mirror, and the electricity and electricity are detected. The device is divided into two or more, and the angle of the reflected light that changes with displacement (deflection) is taken as each detection 2, and the thickness is 0 "... the probe at the front end: degree = radius is 20 nm. Try The distance between the sample and the probe is a small force with a number of "two-curvature interatomic force of nN (nano Newton) or less. Next, the sample is scanned and adjusted by scanning in three dimensions using a piezoelectric element. .Generally, the accuracy is less than 0.111111. In the displacement of the arm, ^ MF is used to scan the fine shape on the surface of the sample position (X-axis, Y-axis): Set: = 'For the sample place, input the Z-axis feedback into the computer / 田 /, 5 Haizhi depicts the corresponding uneven surface of the sample surface (AMF observation image). The treatment of “Fu” and “A” can be obtained from this test; through such observation, 89119042.ptd $ 9 Description of the invention (6) Rough surface Degree =: The above-mentioned dioxide dioxide is micro-selected to break through the glass. It has the characteristics of a silicic acid y for adhesion at the mouth of t *. That is, "silicic acid in the atmosphere" is not present. Heat treatment: = Original characteristics of water glass :; In this way, in the present invention, it is the substance of the second chemical structure. Heat treatment will not be restored to the original; It is believed that, from this point of view, irreversible state) is a heavy function. Tiles can show excellent protection against rain scale pollution. That is, after a long period of less than 300 t, it can be stored in a private air for a long time, and the reserve-by-adhesion stone sulphuric acid material is not sufficient for large pollution; Nature, ... rain scale deliquescence will not be restored, and it will show better heat treatment than hydration, so the above speculation can be made. ^ The different functions of preventing rain scale pollution are due to vomiting. The appearance of the deficit layer is transparent. The naked eye looks smooth. Wonderful π: The original state of the material (that is, the outside of the substrate) is observed. As a result, = 1 takes full advantage of its original colors, patterns, or decorative shapes, and appears to be superior in design. For example, when the antifouling layer is formed on the window glass, it can prevent rain scale pollution and 'does not cause adverse effects on the vision, and when forming a T tile,' samely 'can prevent rain scale pollution while not Damage the decorative nature of the surface. When the cross section of the fine porous antifouling layer is viewed obliquely upward, as shown in FIG. 2, its thickness can be observed. That is, on the lower side of FIG. 2, there is a

552297

Plane area 'It is a cross section of a man monument. From this plane to the two types, the product: 瘪 morphological region $, it can be seen that in these two types of regions, the: side is equivalent to the cross-section of a fine porous antifouling layer ... The upper secondary product = region is a fine rough surface. /, The above figure 疋 & Figure 2 疋 The enlarged section of the electronic material B77 fouling layer with a magnification of 150,000 times can be used for more than 5 0 0 0 0 '= = the above-mentioned microporous observation. In addition, in this photograph, the thickness of the antifouling layer was observed from the photomicrograph. According to the observation result, the fineness is more than %%: anti :: 2 °, 0nm on the ground, preferably “is the door of the dark part 阽 _ ^ 々 口-there is a gap between the emulsified silicon particles, dark; The gap is formed from the surface to the pores, and the pore diameter of the micropores should preferably be 0.5 nm, and it is best to connect the two: Qu Yan. The new effect of the new Lai structure. In the layer of the present rabbit medicament, in addition to the dioxin and the oxalic acid adhesion, it is also preferable to contain a compound, the content of which is preferably 0.1 to 5 parts by weight. This is because the reduction in the amount of aluminum compound can be improved. If it contains a part by weight, its effect I will not be fully exerted, and if it exceeds 1, Lizard has decreased adhesion. Therefore, the microporous number used to form the present invention is within the above range: Fossil 5 is not particularly limited, '彳 is in a dioxygenation solution of ㈣ state = in milk = oxidized stone Xi Li alcohol g ® stem Kubu gas fossil # 私 或 角 声 者 oxidized stone compound, but from the viewpoint of ease of use, 'colloidal dioxin is preferred. The dioxin particles

552297 V. Description of the invention (8) = Contamination = 6 " 9% by weight, preferably 85-98% by weight. Below 50nm, preferably 10-30nm. : Adhesive for stone material. The dioxide township == layer test 2 0.1-30 wt%, preferably wt%. In the 7th and 7th days, fii hair: the coating liquid used to form a fine porous antifouling layer is divided by :: the situation where the sex decreases with the use of water glass :: usefulness ::: ΐ: Specifically, these compounds can be used alone, or two or more kinds can be used to form the matrix of the fine porous antifouling layer of the present invention: oxidized oxide, oxalic acid, and water-soluble ΪΓ :: particles and adhesion After being treated with silicic acid substance, it can exist in a stable state in 300 /, soil-exfoliation] ",, treatment

Devices (such as concrete bricks, etc.), glass, aluminum concrete, and silicon II: Examples thereof may include the walls of ceramic J (: stone II, etc.) I chambers, such as Tao Jing, a special synthetic secondary purpose that is stable at high temperatures; Body; bathtub, unit bath plate, mirror, lens, window slope: etc. All glass faucet accessories, architectural glaze, or unglazed. The glass-on-library product can be made of df t, which has a glass layer on its outer surface. In this way, due to the existence of the glassy soil layer, the adhesion between the U-shaped porous antifouling layer and the outside of the substrate can be improved.

552297 V. Description of the invention (9) Result 'The fine porous antifouling layer is difficult to peel from the substrate. The enamel brick refers to the enamel layer, the Mingzhu refers to the enamel layer as the coating layer of the f glass layer of the metal, and the glass itself refers to the glass itself. Soil surface Next, a method for producing the fine structure of the present invention on the outer surface of the substrate will be described. The antifouling layer is uniformly coated with fine liquid particles containing a silicic acid substance for silica on a substrate such as ceramics, and then fired at 300-70 (Tc (preferably *. 7⑽C)). The silicic acid for bonding becomes a silicic adhesive that does not exhibit deliquescent (ie, irreversible) properties even when hydrated, and thus forms a fine roughened surface having silicon dioxide particles adhered to the substrate. Surface and has a curved fine pores, hydrophilic microporous antifouling layer that communicates with the surface of the frozen evening surface. The right second hair will say that t / 'The coating solution applied on the outer surface of the substrate such as ceramics should contain a colloidal state. Stone dioxide and 〇. &Quot; ο weight. The stone acidic material for bonding is preferably the following composition: 60-99% by weight 〇 · 1-30% by weight 〇 · 01-10% by weight 85-98 The molar ratio of 1% to 1% by weight and 0.1 to 5% by weight is preferably 18-93. It is preferable to reduce the adhesiveness, and if it is less than the silicic acid substance for colloidal silicon dioxide adhesion The composition is particularly preferably the following composition. The composition of the silicic acid substance for colloidal silica adhesion in this coating liquid is 3 丨〇2 / Alkali 40-80. This is because if it is greater than 93 552297 V. Description of the invention (10) 1 8 ', the antifouling performance will be reduced = used to form the microporous antifouling of the present invention 2 is particularly limited and can be various coatings Application method: Combine coating with hand curtain coating, dip coating, spray coating or thin coating, etc. σ is used to coat the fine liquid particles of H_nm with brush coating, especially using thin coating. The coating liquid is applied on the outside of the substrate. Therefore, in the present invention, the liquid is thin and thin, and specifically, a thin film coating method can be used; The liquid particles in the middle of the mouth are washed and dried, and the device that generates powder mist or ultrasonic waves is used: ": These devices are used first when they are impacted. For example, the method of screening to a predetermined method includes, for example, Japanese Patent Laid-Open Publication 2 °° 0: 1: 9. The upper HI liquid particles in the reverse direction of the flow path and the disk gravity pass through in order to drop ^, and the liquid particles in a predetermined particle size range reach the target. = Surface method, and this method is preferred. The heat treatment after the application of the fine liquid particles on the surface of the substrate is 300-700. ^ It is important to make the silicic acid for adhesion even if it passes through the thermal mass. Through the deterioration, the silicon particles formed on the substrate are adhered to the outer surface of the base. Hydrophilic microporous anti-corrosive micropores with micro-chains on the outer surface of the substrate are formed with Deng's connected pores. The heating temperature is limited to the above range because: 心 0 ^ 用 石 夕 酸It is difficult to completely change the quality of the substance even if it is hydrated. 89119042.ptd Page 14 552297 V. Description of the invention (11) :: it agent: The nature of the silicic acid substance for adhesion is still difficult to fully ° C ^ ^ ^ ^ ^ Contributing power of the baffled layer b. If the glass content in the antifouling layer exceeds 70 〇 U, the moisture absorption and antifouling performance of the antifouling sound will decrease. ♦ The double I layer is provided with the metaphor of the fine porous antifouling layer of the present invention on the outer surface of f ί. In this implementation, it is necessary to make ceramic tiles. The manufacturing method is as follows. This was applied to a glazed tile having the following composition for forming fine liquid particles. From 97.8% by weight 2.0% by weight 0.2% by weight 55 Colloidal silica water glass (equivalent to anhydrous base material) Moore number of oxide S i 02 / alkali is higher than that of glazed sintered bricks used The size is 45 x 95 x 6min. The application of the above coating liquid on the concrete brick is performed by the following method: the above coating liquid is sprayed from the nozzle to the opposite impact plate to generate fine liquid particles (that is, 'powder' Fog), according to the descending flow path, the ascending flow path and the descending flow path opposite to gravity: pass the tiles moving through the conveying belt under the last descending flow path. The bricks coated with the obtained fine liquid particles were heat-treated in a conveying continuous firing furnace. The time required to pass through the firing furnace is 15 minutes. During this period, the maximum temperature is 600 ° C. The structure of the fine porous antifouling layer formed on the outer surface of the tile obtained after firing is shown in the electron micrographs in Fig. I and Fig. 2. Fig. 1 is a surface structure of a fine porous antifouling layer, and Fig. 2 is a sectional structure thereof.

552297 V. Description of the invention (12) From these electron micrographs, it can be confirmed that in the structure of the fine porous antifouling layer formed on the structure of the present invention, the micro-roughness having the protrusions of silica particles on the outer surface of the substrate The surface has a plurality of curved fine holes communicating from the surface to the inside. The electron micrograph of FIG. 2 is a magnification of 15,000 times, but the microporosity formed on the surface of the tile of the example can also be confirmed from the electron micrograph of 50,000 times. The above structure of the antifouling layer. In addition, it was confirmed with the naked eye that the fine porous antifouling layer was transparent. The specific measurement results of the structure of the fine porous antifouling layer are as follows. Pore diameter ... 1 2-4 2nm thickness ... 1 20nm average surface roughness ... 2 5 nm An evaluation test was performed on the thus prepared fine porous antifouling layer. [Evaluation test of antifouling performance] An evaluation test of antifouling performance used in the present invention was performed by placing 12 pieces of 45 X 95 X 6mm ceramic tiles on a 5-off board and applying a silicone-based sealing material to the joint. The reason for this is that, in the cement-based joints of the yoke f, the inventors have basically no ketone-based sealing material as the joints, and they are plated on the rainwater. At the same time, it is also shown that the present invention has an excellent function of preventing elution by the silicone-based sealing material. The anti-fouling performance of 25 tiles is as specific as that in the joints, and it is drenched in dirt and finely produced. Separator is applied on the flexible side and exposed on the outside. It was originally used for stone studies. Therefore, the use of silicon can promote the appearance of dirt on the antifouling layer of ceramic tiles.> Can be completed 89119042.ptd page 16 552297

In this test r 'The effect of rainwater on the surface of the brick that is exposed to ultraviolet rays' is also under the following conditions to avoid placing the sample in the sunlight, only the rainwater can be placed under the eaves, and Enclose it around. T ® on the M? The same evaluation test was carried out for the vehicle ('Comparative Example 1') without the above-mentioned fine porous antifouling layer and the hydrophilic coating 2) having the prior art in order to perform the comparison. Case

,,,,,,,. The results are shown in Table 1. From the test results, it can be seen that the tiles with the anti-fouling layer of Tianxi hole of the present invention are dry under the conditions of good sunlight and large amount of ultraviolet radiation, and under the conditions of insufficient sunlight and small amount of ultraviolet radiation =, good The function of preventing rain stains due to the leachables of the silicone-based sealing material, the ceramic tiles without the fine porous antifouling layer, and the porcelain tablet with the hydrophilic coating of the prior art are effective in both cases. Not good. It ^ performance difference is not small, but big. In addition, in order to compare the structure of the tiles with the fine porous antifouling layer of the present invention, the electron microscope was used to observe the tiles formed with the hydrophilicity layer of the prior art. The photographs are shown in FIG. 3. As can be seen from the photograph in FIG. 3, the surface of the coating layer formed by the current method has no fine rough surface with silicon dioxide particle protrusions, and there is no structure with many curved pores communicating from the surface to the inside. The specific manufacturing method of the tile used in this test to form a hydrophilic coating film containing a dioxide of the prior art is referred to Example 5 described in Japanese Patent Publication No. 1 998 330 646 , As follows °. Dissolve soluble potassium silicate and aqueous silica sol into Si〇2 / K2〇

552297 V. Description of the invention (14) A colloidal transparent liquid having a molar ratio of 5.5, and 17.9 parts by weight of calcined ground acid test metal salt was added to the solid component at a weight of 1,000, and then added, It was cold-cooled to room temperature to form an inorganic adhesive composition having a solid content of 30%. To 100 parts by weight of the side composition, green inorganic pigment 67, 7 parts by weight, and 18 parts by weight of water and 22 parts by weight of water were mixed and dispersed in a ball mill to form a S 2 ΐ film-forming solution. Then, this forming solution was applied to a ceramic tile similar to the example to prepare a comparative ceramic tile. Table 1 Post-pollution function without UV blocking

iComparative example 1 (ordinary tile) Comparative example 2 (Japanese Patent Publication No. 330646 of 1998) Example ◎: No rain scale pollution 〇: Basically no rain scale pollution △: Rain scale pollution

X: Rain scale pollution is serious [Effect of the invention] Sexual point = The towel of the present invention, because a hydrophilic ^ fine porous antifouling layer having the above structure is formed on the outer surface of the substrate, so there is no catalytic oxidation-induced superhydrophilicity The lack of antifouling function at night, such as a film, and the lack of more spears over time, the catalytic effect decreases, and the antifouling

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552297 V. Description of the invention (15) The problem that the function is also reduced accordingly. In addition, compared with the coating film using silicon dioxide described in the aforementioned prior patent publication, the antifouling layer of the present invention has a completely satisfactory function of preventing the scale pollution caused by the leachable of the silicone-based sealing material. . According to this, the structure having the fine porous antifouling layer of the present invention on the outer surface of the substrate has a prominent effect. #

89119042.ptd Page 19 552297 Brief description of the drawings Fig. 1 is an electron micrograph of the surface of a fine porous antifouling layer formed on the outer surface of a tile obtained from an example. Fig. 2 is an electron micrograph of a cross section of a fine porous antifouling layer formed on the outer surface of a tile obtained in an example. Fig. 3 is an electron micrograph of a cross section of a hydrophilic coating film containing a dioxide dioxide formed on the outside of a squat in the prior art. _

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Claims (1)

Six, the scope of patent application 1 · A kind of in the body 'its special =, with a small amount of adhesive will be ^ 2 · If you apply for a microporous anti-microscope can be in the shape of particles 3 · If you apply for a micro-porous anti-1000 rim below 4 For example, if the thickness of the water-based fine soil layer is applied 5. If the water-based fine concavities and convexities are averaged 6. If the water-based fine soil layer is applied> The deficient layer also contains 7. The water-based fine soil layer 2 and 8 · If the outside of the substrate is applied Bu θ 丨 j; \ i upper,-J · levy · upper β has -¾¾ ¾ micro arsenic 'f-hole antifouling layer structure ^ 疋 face 疋 has a sudden poison-custom ^ micro fine rough particles- ί 2 Facing the internally connected curved pores and bonding with oxalic acid-silicone particles. Dioxide was observed on the cross-section of the Shishucheng fine porous antifouling layer with 7 ί:;:! 1 item which is hydrophilic on the outer surface of the substrate: ΐ: Range 1 item has hydrophilicity on the outer surface of the substrate. The structure of the structure, wherein the pore diameter of the above-mentioned fine pores is f :, and the structure surrounding the first, second or third item is on the outer surface of the substrate: the structure of the pore antifouling layer has a diameter of 20 to 50 nm. /, Τ on m, and Tian Xi hole prevention Patent area 1, 2 or 3 The porous antifouling layer has a roughness of 2-100 mm. "In the above-mentioned 彳 放 细 面面 的 # 围 ί 1 之" or item 3 of the structure with a piercing pore prevention layer on the outer surface of the substrate 髀 πaluminum compound. "In the above-mentioned fine porous prevention patent scope, the first Item 2, 2 or 3-The structure of the porous antifouling layer, which has a content of fluorene silica on the outer surface of the substrate of 50 to 99. Among them, the above-mentioned fine porous anti-patent patent range is 2 or 32%. 〇 Item has pro-_ 89119042 • Ptd 552297 6. Scope of patent application Water-based fine porous antifouling layer is transparent. The structure of θ ', in which the above-mentioned microporous anti-corrosion structure is a structure in which the surface of one layer is a microporous anti-fouling layer with protrusions on the surface, and the anti-fouling communicates from the surface to the inside = the fine roughness of silica particles Surface, with a lot of silicon oxide particles bonded, love the fine pores and the second with a silicic acid adhesive, its thickness is 2-50m, the sign is ... the above-mentioned fine porous antifouling layer is transparent 1 〇 · — This kind of structure, 1 The surface of the fouling layer is a raised, anti-fouling layer with a fine porosity on the surface. The anti-fouling layer is mostly from the surface to the inside. 2 J 2 = fine chain surface of oxide particles, with a small amount of silicon dioxide. The particles are adhered, 苴 = curved micropores, and the unevenness is revealed with a silicic acid adhesive :: t The above-mentioned fine porous antifouling layer is permeable to dirt Λ-Λ Λ body, and there is a microporous defense on the outside Foul sound = The surface of the two-component mixture with protrusions on the surface of the dioxide to form a border, the above-mentioned microporous antifouling layer is transparent, and also contains V, its characteristics, and the structure, and its outer surface has microporosity Of :: Compound. Protruding crane crane micro 4 2 The surface of the anti-oxidant chants the surface ^ surface, and the particles of silicon dioxide are adhered to each other, and the micro-pores are mixed with stone acid acid C, one of which is the content of stone dioxide. It was 50-99 mass%. The antifouling layer is a kind of microporous antifouling layer that is water-soluble and fine.-1 4 · A finely wicked antifouling ear on the outer surface of the substrate, which is hydrophilic and / or hydrophilic Shi Xi and adhesive Shi Xi acid material and V η number liquid, the ear number ratio is 18-93. And Sl (V-base Mo layer, page 22, 89119082.ptd 552297) 6. The method for manufacturing a patent-applied structure is characterized in that the antifouling layer has a fine rough surface that adheres silicon dioxide particles and has a number of The above-mentioned manufacturing method involves applying a coating solution containing silicon dioxide and a silicic acid-containing substance to a curved fine hole that communicates with the surface toward the inside, and then applies the temperature to 300 °-700 ° C. Heat treatment, so that the silicic material for bonding becomes silicic adhesive. 5. A method for manufacturing a structure having a fine porous antifouling layer having a hydrophilic property on the outer surface of the substrate, such as item 14 of the patent application, wherein The above application _ liquid is powder mist. _ 89119042.ptd Page 23