JP2009067625A - Surface treatment method for treating inorganic substrates, such as pottery surfaces, porcelain enamel surfaces, glass surfaces or the like of sanitary wares, general furnitures or the like - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To develop a coating and processing method of a fluorine-based compound by which the processing on site can be done and which solves the problem that the processing on site is unstable and can not be easily processed owing to the characteristics of the liquid coating agent because it has a very unique structure. <P>SOLUTION: The surface treatment method comprises raising the boiling point by adding glycol ethers to a fluorine-based compound that is produced using a silane coupling agent, and then coating it on the surfaces of inorganic substrates such as pottery surfaces, porcelain surfaces, glass surfaces or the like of sanitary wares, general furniture or the like only at one time towards one direction. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a surface treatment method by a coating method for inorganic substrates such as sanitary appliances using fluorine-based compounds, ceramic surfaces such as general furniture, enamel surfaces, and glass surfaces.

  Originally, coating agents such as fluorine compounds are coating agents made of a fluorine compound having a very special structure in a manufacturing method using a silane coupling agent. It is a great feature that it has excellent antifouling performance (see, for example, Patent Documents).

JP-A-7-216047

  However, coating materials such as fluorine-based compounds are mainly processed at the factory line because the raw materials are expensive and depend on construction conditions, and humidity, temperature, and construction conditions are required for on-site construction. It is unsuitable. Therefore, we developed a technology development to process and stabilize the coating agent made of a fluorine-based compound having a very special structure in the field construction.

  Conventional coatings mainly composed of fluororesin, fluororesin fine particles and fluorinated varnish are expensive materials, but they are soft, such as B to 4B, with pencil hardness and adhere to various base materials. Although it is easy and anyone can easily coat it, it was easy to remove by wiping with IPA (Isopropyl Alcohol) or thinner, etc. and the construction conditions were limited because it was also weak to wear.

  Fluorine compounds manufactured using the silane coupling agent developed by the inventor's technology, once combined with other elements, are highly safe chemicals that are resistant to heat and chemicals and solvents. A silane coupling agent is used for bonding with other elements.

  This silane coupling agent hydrolyzes by reacting with moisture in the air, and is considerably affected by storage stability, use conditions, purpose of use, etc., so on-site coating processing is unstable. It is difficult.

  In order to avoid this difficult problem as much as possible, the present inventor made a raw material for the silane coupling agent made of a fluorine-based compound, set the room temperature from 20 ° C. to 24 ° C. with an air conditioner, and coated the coating agent with 20 ml. After filling into a 100ml light-shielding bottle, it was degassed with nitrogen gas to minimize the damage caused by hydrolysis of the silane-based raw material in response to moisture in the air.

  In general, a silane coupling agent added to a fluorine-based compound is hydrolyzed on the alkoxy group side, becomes silanol, acts on an inorganic material, and exhibits its effect. Since an organic functional group side such as a sulfide group is also acted, an adhesion effect may be obtained.

  The alkoxysilyl group of the silane coupling agent becomes a silanol group when dissolved in water. This silanol group is unstable and undergoes a condensation reaction with the passage of time. As a result, a siloxane bond is generated and gels, so that it is difficult to store for a long time or always stock. In general, a silanol group is unstable in an aqueous solution, but stability is improved in a weakly acidic region. In addition, aminosilane is very stable in aqueous solution due to the interaction with amino groups.

  The coating agents made of fluorine compounds with a very special structure as described above are mainly used for coating processing in precision factories equipped with facilities under control conditions such as humidity, temperature, and construction environment. It was mainly used for water-repellent antifouling of microscopes, cameras, eyeglass lenses, liquid crystal screens, electronic devices and the like.

  The present inventor has made the coating agent made of a fluorine-based compound having a very special structure stable and fixed on a coating surface to be coated on inorganic materials such as general ceramics, porcelain tiles, glass, mirrors, cast enamels, and steel enamels. It is an object of the present invention to develop a coating method that enables reliable construction under any construction conditions in order to establish the stability of technical development.

  In addition, the coating agent made of a fluorine-based compound having a very special structure has a low adhesion to plastics, ABS, urethane resins, etc., so in that case, coat with a primer underneath. It is preferable.

  In order to solve this problem, the present inventor has developed a coating method and a base treatment method for the surface to be coated on which the coating agent is applied as a result of earnestly developing the technology.

  In the present invention, a glycol ether is added to a fluorine-based compound produced using a silane coupling agent in a surface treatment method applied to an inorganic base material such as sanitary ware, ceramic surfaces such as general furniture, and enamel surfaces, and glass surfaces. The boiling point was raised by addition, and then the coating was applied only once in one direction to the surface of an inorganic base material such as sanitary ware, ceramic surfaces such as general furniture, and enamel surfaces, and glass surfaces.

  Fluorine-based compounds are usually coated in precision factories equipped with equipment under control conditions such as silane coupling agents and humidity, temperature, and moisture. Coatings in industries such as lenses, microscope lenses, liquid crystal screens, electronic equipment, parts and precision equipment have been mainstream, but the present invention enables coating in a wide range of industries.

  This construction method is a dry construction method, and its main purpose is to provide a water-repellent antifouling coating for ceramics, porcelain tiles, glass, mirrors, cast enamels and steel plate enamels, and the substrate needs to completely remove moisture. By applying this processing, it becomes possible to provide wear resistance, durability and water-repellent antifouling effect over a long period of time, which is different from conventional fluorine-based coating agents.

  Therefore, in order to support the grounds for the wear resistance, durability, and water-repellent antifouling effect of the components comprising the fluorine-based compound, the present inventor, including water-repellent coating agents such as fluororesin coatings, industrial fluororesin coating agents A preliminary experiment was conducted using

  First, in order to prepare the material to be coated, a glass plate sample is prepared by the manufacturer: Central Glass Co., Ltd., prepared by cutting 50 sheets with a thickness of about 2mm and dimensions of 70mm x 120mm. Substrates made of halogenated hydrocarbons, hydrofluoroethers, hydrofluorocarbons, perfluoropolyethers, perfluoroalkanes, hydrofluoropolyethers, using nonflammable fluorine-based solvents, alone or in combination of two or more. The product is degreased and used, and completely wiped off with Kimwipe manufactured by Nippon Paper Crecia Co., Ltd.

  Next, in establishing the technical development of the present inventor, five raw materials of fluororesin manufacturers are selected as test comparison products, coating is performed under the same conditions, and after 24 hours, basic experiments on water repellency and durability are performed. went.

The coating agent used in this experiment was
No.1 Mixture of fluororesin, silicone and IPA (isopropyl alcohol)
No.2 Mixed solvent of fluororesin and halogenated hydrocarbon
No.3 Water repellent glass coating agent
No.4 Mixed solvent of fluoropolymer and hydrofluorocarbon
No.5 Polytetrafluoroethylene fluororesin (water soluble)
It is. Using the coating agents of No. 1 to No. 5 described above, the antifouling effect was compared with a component composed of a fluorine-based compound for which the applicant's construction method was constructed.

  For the water-repellent antifouling test, prepare glass from the manufacturer of Central Glass Co., Ltd. with a thickness of about 2 mm and dimensions of 70 mm x 120 mm, and apply the above coating agent to the glass for 24 hours. After leaving, after writing letters on the coated surface with oil-based magic, wiping with kitchen paper, and then wiping with IPA (isopropyl alcohol), 50 water-repellent antifouling effects were tested 50 times.

  The magic used was the product name: RiKota Marker water resistance (MADE IN CHIINA), the paper used for wiping was the product name: Erière (super absorbent kitchen towel manufacturer: Daio Paper Co., Ltd.), In the coating agents of No. 2 to No. 5, the surface film was completely removed in the first experiment, and the effect of playing magic was lost.

  With regard to the No. 1 coating agent, the antifouling test was repeatedly performed, and the traces of the magic wiped from the 10th time remained, and removal with kitchen paper alone was impossible.

  Then, after wiping and removing with IPA (isopropyl alcohol) and verifying the water repellent effect, the water repellent remained.

  On the other hand, the anti-fouling test with the component of the inventor's technically-developed fluorine-based compound was repeatedly performed, and the magic playing has deteriorated since the 20th time, but it does not require so much power and time to take It didn't take that much. Also, I felt that it would take some time if I did not put some effort from the 40th time, but the magic could be completely removed and the same result was obtained even 50 times.

  As a result of 50 comparative tests with this fluorine compound component and the No. 1 coating agent, processing of inorganic materials using the fluorine compound component and its coating method is water repellent and antifouling. The effect was obvious.

  Based on the results of the above preliminary experiment, in order to obtain further construction data on site, a ceramic construction wash ball, a coating method using a No. 1 coating agent and a component composed of a fluorine compound in the bathroom mirror, The water repellent effect, durability and antifouling performance were verified.

  Unlike the photocatalyst that reacts by absorbing ultraviolet rays, the No. 1 coating agent and the component composed of a fluorine-based compound do not have a self-cleaning function that decomposes dirt, so that dirt adheres. When the water-repellent effect is lost, it is necessary to wipe and clean the surface to be coated. Therefore, durability with respect to the water repellent effect and wear resistance is required.

  Therefore, for the verified contents, an experiment was conducted in which towels were wiped daily with a ceramic washbasin ball that specified the material to be coated and a bathroom mirror. For the bathroom mirror, we conducted an experiment using nylon bundles of cleaning tools sold at home centers.

In the case of ingredients consisting of No. 1 coating agent and fluorine compounds, after the ceramic washbasin and bathroom mirror are coated, the washbasin is wiped with a commercially available towel cloth every day.
As for the mirror, a neutral detergent was attached to a nylon bundle, and it was washed by scrubbing in a circle, and then showered to verify the water-repellent effect.

  As a result of the above verification, the No. 1 coating component has a water-repellent effect, but has a higher probability of attracting and adhering to dirt than a component made of a fluorine-based compound. It was clear that it was very expensive.

  In the present invention, since inorganic materials such as ceramics, porcelain tiles, glass, mirrors, cast enamels, steel plate enamels are baked and produced, there are innumerable pinholes on the surface that cannot be seen with the naked eye. In many cases, impurities are attached and mixed. In addition, the surface of the base material is uneven, and a construction surface for completely performing the surface treatment of the surface is assumed.

  For the base material to be coated, first, regarding the base treatment, the components are 70% silicic acid, 14% alumina, 3% calcium, 3% sodium, 2% magnetic iron, 2% potassium, other magnesium, titanium, manganese, etc. The Shirasu balloon made of a natural inorganic powder-like material is micro-micronized and processed as a paste, which is processed as a paste, so that the substrate surface is not damaged and the substrate surface is completely By enabling the surface treatment so as to bring about a good hydrophilic property, it is possible to further improve the adhesion effect between the fluorine-based compound and the substrate.

  Further, a complete steam degreasing process is performed using a steam machine in order to remove oil, impurities and the like adhering to and adhering to the pinholes formed after firing the substrate.

  Thereafter, the substrate is completely dried and wiped off, and degreasing treatment with a solvent is performed.

  What is used for this degreasing treatment is a non-flammable fluorine-based solvent comprising a liquid, a hydrofluoroether, a hydrofluorocarbon, a halogenated hydrocarbon, a perfluoropolyether having a boiling point in the range of 40 ° C to 98.4 ° C, Examples thereof include perfluoroalkane and hydrofluoropolyether. These nonflammable fluorine-based solvents can be used alone or in combination of two or more and degreased against the base material.

  This fluorine-based compound has a low boiling point temperature of 40 ° C. to 54 ° C. and high volatility. Therefore, in order to adjust the boiling point to 76 ° C. to 158.7 ° C. so as to be suitable for on-site construction, allyl glycol is used. (AG) Main glycol ether, ethylene glycol mono-n-butyl ether, ethylene glycol monohexyl ether, ethylene glycol mono-2-ethylhexyl ether, ethylene glycol monobutyl ether acetate, ethylene glycol monomethyl ether, ethylene glycol monoisopropyl ether , Ethylene glycol monoisobutyl ether, ethylene glycol monoallyl ether, ethylene glycol monophenyl ether, ethylene glycol monobenzyl ether, ethylene glycol dimethyl ether, diethylene glycol Monobutyl ether, diethylene glycol mono-2-ethylhexyl ether, diethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monohexyl ether, diethylene glycol mono-2-ethylhexyl ether, diethylene glycol monobenzyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether , Diethylene glycol di nbutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol mono n propyl ether, dipropylene glycol mono n butyl ether, dipropylene glycol dimethyl ether, triethylene glycol monobutyl ether -Tell, triethylene glycol monomethyl ether, tripropylene glycol monomethyl ether, tripropylene glycol mono nbutyl ether, triethylene glycol dimethyl ether, tetraethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol mono nbutyl ether, propylene glycol monoethyl ether, Propylene glycol monoethyl ether acetate, propylene glycol mono npropyl ether, propylene glycol monophenyl ether, propylene glycol monomethyl ether acetate, polyethylene glycol monomethyl ether, polyethylene glycol dimethyl ether, polyethylene glycol, polyethylene glycol methacrylate Luric acid ester, polyethylene glycol lauric acid sorbitan ester, polyethylene glycol lauryl ether, polyoxyethylene polyoxypropylene monobutyl ether, polyoxyethylene monomethyl ether, polypropylene glycol ethylene glycol ether, polyoxyethylene bisphenol A ether, polyoxypropylene bisphenol A ether , Polyoxyethylene trimethylol propane ether, polyoxyethylene pentaerythritol ether, polyoxypropylene trimethylol propane ether, polyethylene glycol methacrylate, polyoxyethylene methyl ether methacrylate phenyl glycol (PhG) based glycol ether, nonylphenol polyethylene Glycol ethers, for alone or in combination of two or more use. In that case, the addition content in the coating agent is more preferably in the range of 0.1 to 30% by mass.

  In addition, when coating the surface to be coated with a spray gun, the volatility is very high, so spraying with a spray gun using a normal air compressor vaporizes the liquid fluorine compound. Therefore, it is difficult to coat the surface to be coated, and air and moisture are fused together at the tip of the spray nozzle, causing a condensation reaction through a chemical reaction. It will not bond to the coated surface.

In order to solve this problem, the present inventor solved this problem by adjusting the boiling point of the liquid solution of the fluorine-based compound and spraying it on the liquid solution of the fluorine-based compound by using a blow-type pressurized hot air gun.

  According to the present invention, as a result of conducting a verification experiment using the facilities of the Fukuoka Industrial Technology Center, the difference between the conventional method of performing normal degreasing and ground treatment and the method of performing the new method was confirmed. The resulting data is as follows.

Test method Contact angle meter (CA-DT) manufactured by Kyowa Interface Chemical Co., Ltd.
Test glass: (micro slide glass)
Fabric: stipulated in JIS L0803 (Cotton: No. 3)
Inspection contents: Contact angle and abrasion resistance test Test result Conventional method Contact angle after coating: 84.72
Abrasion resistance test 10,000 test results: contact angle is 55.4
New construction method Contact angle after coating: 100.5
Abrasion test 10,000 times test result: contact angle 91.6

  As a result of coating under the same conditions other than the base treatment, it was found that the new method gives better results in both contact angle and wear resistance than the conventional method.

  Here, the method according to the conventional method is the one subjected to the following processing.

  The coating method was applied to toilets, bathrooms, wash-basins, mirrors and glass that easily adheres to water, hot water, water, hot water, etc.

  First, the moisture and oil content of the irregularities and pinholes on the surface of the base material are cleaned and degreased while being rubbed with non-woven nylon using silicon-off, hydrocarbon, etc., and completely dried.

  A liquid solution of a fluorine-based compound is put in a cup on the surface to be coated, and then infiltrated with a soft brush, cotton, cloth, or non-woven fabric, and applied to the surface to be coated and left as it is. In this case, after confirming that there is no humidity problem or no moisture remaining, the coating is performed and left for 12 to 24 hours.

  After leaving for 12 hours to 24 hours, the coated surface to which the coating agent has been applied may be left as it is, but when uneven coating is noticeable, it is preferable to wipe it off using commercially available IPA (isopropyl alcohol).

  Moreover, the thing by a new construction method gives the process of each following process.

1. Polishing process To improve the adhesion between the surface of the base material and the fluorine compound, chemically synthesized fibers made of nylon and polyester made of fine particles, made of shirasu balloon, coated with ultrafine aluminum oxide particles Is used to perform polishing ground treatment.

2. Cleaning process After the treatment in 1 above is completed, the steam and other impurities mixed in the pinholes of the base material are steamed out, and the remaining impurities and oil that cannot be removed in the above 1 process are floated. Process.

3. Degreasing process After finishing washing in 2 above, the product is dried and hydrofluoroether, hydrofluorocarbon, halogenated hydrocarbon, perfluoropolyether, perfluoroalkane, hydrofluorocarbon having a boiling point in the range of 40 ° C to 98.4 ° C. A nonflammable fluorine-based solvent made of polyether is used alone or in combination of two or more, and degreased with respect to the base material.

4). Boiling point adjustment process After the above 3 work is completed, after wiping with a dry cloth and drying, the raw material itself made of a fluorine-based compound is diluted with a very volatile solvent. It is unsuitable. In order to solve this problem, glycol ethers were added in the range of 0.1% to 30% in order to adjust the boiling point to 76 ° C to 158.7 ° C so that construction at the site can be done easily. It was solved by using.

5). Application process About coating method of this fluorine-based compound, antifouling and water repellent effect may be significantly impaired if it is applied in a circle or overlaid on the left and right several times. Apply only once to flow smoothly in one direction. What is used by hand coating is preferably soft cloth, cotton, non-woven fabric, Kim towel or the like. When coating is performed by the spray method, the coating agent having the boiling point adjusted as described in 4 above is used. At this time, the spray gun used was coated with a blow-type hot-air supply gun to solve the cause of the condensation reaction caused by the chemical reaction caused by the fusion of the liquid air and moisture.

6). Infrared irradiation process After coating, it is preferable to irradiate for 30 minutes to 60 minutes with an irradiator using a handy type 1 kw IRT near infrared lamp in order to further enhance the binding reaction with the substrate.

7). Finishing process
After drying for 24 hours, if there is uneven coating, it can be finished without damaging the surface material by wiping with IPA (isopropyl alcohol).

  Specifically, first of all, using a synthetic glass fiber made of nylon and polyester, coated with ultrafine particles of aluminum oxide, using a shirasu balloon made of ultra-micron natural mineral powder, Polish to remove scales, scales and impurities attached to the surface.

  After that, apply steam to the irregularities and pinholes, so that dirt, oil, etc. are floated and washed with steam, and then wiped dry, and the boiling point is in the range of 40 to 98.4 ° C. The base material is degreased using a non-flammable fluorine-based solvent composed of hydrofluoroether, hydrofluorocarbon, halogenated hydrocarbon, perfluoropolyether, perfluoroalkane and hydrofluoropolyether.

  A liquid solution of a fluorine-based compound is put in a cup on the surface to be coated, and then infiltrated with a soft brush, cotton, cloth, or non-woven fabric, and applied to the surface to be coated and left as it is. In this case, after application, the bonding of the coated surface and the coating agent is accelerated by irradiating the coated surface substrate with an irradiation machine using a handy type 1 kw IRT near infrared lamp for 30 minutes.

  After confirming that the surface to be coated is free of humidity and humidity, perform coating and leave it for 12 hours.

  After leaving it to stand for 12 hours, the surface to be coated with the coating agent can be left as it is, but if the coating is uneven, wipe it off using commercially available IPA (isopropyl alcohol).

  The coating film of the fluorine compound developed by the inventor has a resin content in the coating liquid composition of about 0.1 to 2.0% by mass, and the antifouling layer of the coating film to be formed depends on the processing conditions. And a film having a thickness of 0.1 nm to 10 nm or less.

For the performance test after coating, we requested the Fukuoka Prefectural Industrial Technology Center for contact angle and 30000 wear resistance tests. The results of the verification data were as follows.
Test method Contact angle meter (CA-DT) manufactured by Kyowa Interface Chemical Co., Ltd.
Test glass: (micro slide glass)
Fabric: stipulated in JIS L0803 (Cotton: No. 3)
Inspection contents: Contact angle and abrasion resistance test Test result Contact angle after coating: 101.4
Abrasion resistance test 30000 times test result: contact angle is 95.1

  From the above results, assuming that the wipes were wiped 10 times every day, the result was 6% less than the initial water-repellent effect of the coating process in just a few years of 8 years and 2 months. Moreover, even after wiping with IPA (isopropyl alcohol) after verification, the water-repellent effect was maintained without peeling.

Claims (1)

  Glycol ethers are added to fluorine-based compounds produced using silane coupling agents to raise the boiling point, and then the surface of inorganic substrates such as sanitary ware, ceramic surfaces such as general furniture, enamel surfaces, and glass surfaces. A surface treatment method applied to an inorganic base material such as a sanitary ware, a ceramic surface such as general furniture, an enamel surface, and a glass surface, wherein the surface is applied only once in one direction.