TW200923035A - Method and use of nanoparticles to bind biocides in paints - Google Patents

Abstract

This invention relates to the use of a combination of selected substances in paint to prevent the settlement and growth of different biofouling organisms with a reduced negative effect on the ecosystems compared to present methods.

Description

200923035 IX. Description of invention: [Technical field to which the invention belongs] The method of combining various granules with biocide is said to be - === her loss ==== Clean the hull and reduce profit time. Similar to === efficiency is reduced and operating costs are increased. Other marine products have obvious _ ^ and iron sea surface equipment and factories also have marine sweat damage, mining, mechanical removal of the ship surface as a toxin and biological kill two two = introduction I especially, using water jet cleaning and using a brush = maple 1 However, most of the methods in the four methods are labor intensive and costly. The effective antifouling coating is “self-polishing copolymer, coating, this kind of coating base agent charm annihilation crane, _ is three base tin for chemical, ϋ r, the bio-killing of the material can gradually be Seawater hydrolysis, as described, for example, in British ιλα BA 1457590. These organotin copolymer coatings prevent the loss of perspiration by releasing organotin compounds during the polymerization process. The outermost coating of the ship in the water depletes the biocide and Removed from the surface of the hull. The organic f-based coating also contains copper oxide pigments, which are effective in preventing marine biofouling, while tributyltin protects clay and aquatic plants. It has been proven to contain organotin compounds especially Tributyltin coatings can cause negative environmental consequences, endangering marine life, leading to oyster deformation and conch change 200923035 I. It has been noted that organotin compounds degrade slowly, resulting in the accumulation of these compounds, in localized sediments. Many countries and International organizations therefore have restrictions and prohibitions on these applications and hope for stronger restrictions. In the face of the year 1 () month, the international J matter, anti-sweat system At the meeting, it was agreed to stop the sale and application of TBT anti-pollution. Article: 'The instrument is banned from January 1, 2003 and is completely banned on the hull on the 2nd day of the 2nd year. # Due to the recent restrictions in many countries With these toxic coatings, the shipowner had to switch to a less technically toxic, low-toxic copper oxide based coating; in normal fouling conditions, the life of the copper oxide coating rarely exceeds 2 years. The lifetime of the self-polishing dibutyltin coating is 5 years. The copper oxide coating is not satisfactory, it can not only meet the requirements of the ship and the ship's workmanship and owner, nor can it meet the requirements of environmental declination because Yes, the poison of the i brother. When the use of copper compounds reduces the concentration for ecological reasons, these lions need the lion's bio-killing barnacles and algae to be acceptable to ship owners and other types of marine industry owners. Recent advances in the field of self-polishing coatings include the use of zinc acrylate copolymers for ion exchange as a release mechanism. The potential environmental effects of antifouling toxic substances have prompted the development and use of A system for controlling fouling by surface modification, for example, by using a polymer having non-tacky or release characteristics containing hydrazine or fluorine, for example, a patent as described below, W〇_〇〇14166A1, υδ92ΐ 〇541〇>

JP53113014, US92847401, DE2752773, EP874032A2, and EP 885938A2. These coatings have been shown to be susceptible to brittleness, resulting in cracking and flaking. A new alternative technology was introduced as early as the 1990s. Although this technique is also referred to as self-polishing technology, the process for obtaining this technique no longer passes through the polymer solution; instead, it combines different water-sensitive and partially water-soluble binders, such as resins, alone. Used or mixed with acrylate as described in European Patent Ep 289 481, EP 526 441. Experience has shown that such coatings do not yet provide the same high and reliable performance as hydrolyzed 200923035 machine tin coatings. Recently, new polymers have been developed which are based on the same principle as organotin polymers, i.e., hydrolyze an insoluble polymer to provide a slightly water soluble product. Among them are self-polishing polymers such as those described in W08402915. Instead of incorporating an organic tin group into the polymer chain, the incorporation of an organic sulfonium group is described herein. Experiments have shown that these coatings have many properties associated with organotin copolymer technology. ^, and it was also found that the surface of these coatings may crack and peel off after a long time. This causes bleed out of the soluble components, resulting in a residual layer that is different from the original coating composition.

One way to solve this problem is to modify the decane-based polymer with different comonomers as described in EP0646630, EP1016681 and EP1127902. Another method is to add fibers to enhance and enhance the strength of the cohesiveness throughout the coating, particularly the residual layer formed, as described by w〇〇〇771〇2. A third method is to develop a coating in which a mixture of an organic cerium copolymer and a resin is used to reduce residual layer lamination as described in EPG 8G2243. The use of low molecular weight plasticizers, more specifically, is the use of chlorinated paraffins, as described in Ep 775,733. Barnacles and algae are economic and technical issues along the west coast of Sweden and along the North Atlantic coast. The mature barnacle is a “faceted crustacean” characterized by a fresh-sized _ shape and a surrounding layer. The animal = body surface _ mechanical strength is very high and it is therefore difficult to mechanically remove the pot from the surface. The animal undergoes different stages of development, that is, the last minute segment of the free-moving ί ^ is called the secret segment. The instar larvae are screened for the attachment surface by the help of a neural dog. - a "glue" = protruding soil ί glans secreted by the gland _ get the animal attached to the solid S two things undergo metamorphosis into adult and fixed animals. One of the first organisms that stained in the old copper coating with (10) degrees of copper is the same, algae is relatively insensitive to copper, and the amount of steel exudation is high. Therefore, the copper-containing marine anti-sweat 7 200923035 is made, producing a more specific mites to "lion,. This axis inhibits the movement of spores or inhibits photosynthesis. The two methods lead to the reduction of algae pollution. Antifouling coatings assisted by biocides should be sexual, ie only for fouling organisms. _ Do not harm other materials. Mechanical coatings: Coatings should also be designed to achieve controlled release of active substances. An effective method is to form a bond with a molecule of A. Since the size and low (4) of the macromolecule are difficult to record, it is determined that the κ is dependent on the rate of ruthenium from the polished surface. ^ External 'In order to prevent the accumulation in water and sinking matter, and thus the marine environment, it is another important aspect of Lin Jian's target age. (4) Several compounds have been shown to have anti-sweat activity. Some of the agents known to have pharmacological effects. It has been reported that a pharmacological compound selected from the group consisting of blood = ί 多 ΐϊ ΐΐ , , , , 阻碍 阻碍 促进 = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = "* ^ Yue Shi propylene apomorphine * coffee * ⑴- desert hidden Pavilion 'has inhibitory properties. Another pharmacological physiology that has been specifically inhibited by barnacles is the agonist Mito (4), R): 4 (t = 3 worms, a ff) base hh_ flavor saliva. The low concentration of the agent can prevent the attachment of the station $ from 1 η Μ to 10 η Μ. Mittor is a new type of α =, which contains a 4-substituted Miqua ring, and has a g-adrenergic receptor (or adrenergic receptor 1) inhibitor mechanism for the 2_adrenergic receptor, and In the regulation of high blood pressure (high blood pressure) ms anesthetic, to (8), dextromethorphan ^; = animal water particles are silk-sized metals and semiconductors difficult, recently in the field of nanometer 200923035 degrees material is widely studied. Applications. These applications include · silk domain with potential = technology #: particles with a size of 30 nM have 5_sub-surface; ^ such as two particles have 20% of atoms on their surface, a ^ size of 10 ηΜ = sub-surface on the surface, this is the same as the taste of a nano-form of a given mass. This is the year. On July 29th, the British brother used anti-fouling and anti-fouling in the coating. Other applications compete for m, but (d) is to change the structure of the coating surface, for example to make it 4, smoother to reduce the 纟n / / application and impact on the ocean structure, in 2003 12 = in = ^, 尔 f newspaper published, UK) or chronology? More http://innovation. im-boot. org/ffl〇dules .php?name=NeJsi ^artlele&sld=129) 'But it is not the concept of the nano-special combination of biocide in the public. The present invention relates to a kind of facial towel nanoparticles. With biocide, the method, application and application 'from the ability to specifically and effectively prevent adhesion, such as ^ touch. People's Wei Wei Wei light on the silk surface and nano-Si Shijiao has a strong simplicity, this performance caused People's __ and try ^ 200923035 to get from their marriage, the interaction, the purpose of the report 'is to provide a kind of coating _ nanoparticle and biology [implementation] In order to make your (four) commissioned inspection - step by step The structure, features and objects of the invention are set forth in the following detailed description with reference to the accompanying drawings. Published studies have shown that nanoparticles such as copper oxide (oxide) and oxygen (diameters of 33 and 35 nm, respectively) can be used to maintain controlled release, such as antifouling, and fine particles are due to their large specific surface area. (the ratio of particle surface area to volume). (5) and granules The specific surface areas were 29 and 21 m2/g, respectively. Supported CuO and ZnO nanoparticles with mitomidazole and other antifouling agents such as chlorothalonil, seaweed, Irgaro, Diur〇n and When the fungus is mixed in the dimethyl group, it can be observed that there is a significant difference between the two sides. Most of the rice can be adsorbed even at low particle concentrations, especially when using Zn〇 nanoparticles. Design - a coating system that includes low levels of mitoxanthin and nanoparticles that limit the diffusion of antiperspirant through the coating film. The susceptibility of the mitox bite is highly advantageous compared to the other antifouling agents listed above. The antifouling agents listed above show a common feature in which nitrogen is present in all compounds in the form of secondary or tertiary amines, T groups, or heterocycles. However, studies have shown that the miso portion of the Mito taste bite has an optimum geometry suitable for adsorption to the particle surface. In order to study the importance of large surface area, we studied minometidine with various 200923035 granules (10), (5), A-cut, TiG2), and Shixi Knee! And the interaction of a micron size face-). When the particles replace the nanoparticles, the adsorption of the Mituto surface can be accumulated. When the surface is adsorbed on the surface of the particles, the large adsorption surface needs to produce a "" antifouling method. The biocide 1 required for the anti-sweat method has low ecological and economic advantages. S3, the influence of the environment, appropriate control of the release of the anti-fouling substance in the coating film ί ° mitox molecular combination with the fresh-sized metal oxide f ^ This is enough to control the leakage of the coating into the water compound. Since the compound size giant is combined with the nanosized gold derivative and the rice is used alone, the recording property is very good. Its size ship, Mito's - metal emulsion particles are stable in the SPC coating film and will not leak into the water. Therefore, the Handu of the coated antifouling particles is consistent in the "lifetime, period. The shape of the if H particles and the Shiqi gum nanoparticles provide a large amount of the Mitoxite bite | the rice material can be bonded thereto Therefore, Mittomi bites the witch and the ί 个 录 录 是 是 录 录 ι ι ι ι ι ι ι ι ι ι ι ι ι ι ι ι ι ι ι ι ι ι ι ι ι ι ι ι ι ι ι ι ι ι ι ι The total surface area is sufficient to adsorb all the mitomibine bites without wasting the organism* Β ίί露 水中When the water layer of the surface layer of the mitomio is detached from the metal oxide, desorption. In contrast, ΐ ΐ 匕ΐ 匕ΐ 匕ΐ 匕ΐ 匕ΐ 匕ΐ 匕ΐ 匕ΐ 匕ΐ 匕ΐ 匕ΐ 匕ΐ 匕ΐ 匕ΐ 匕ΐ 匕ΐ 匕ΐ 匕ΐ 匕ΐ 匕ΐ 匕ΐ 匕ΐ 匕ΐ 匕ΐ 匕ΐ 匕ΐ 匕ΐ 匕ΐ 匕ΐ 匕ΐ 匕ΐ 匕ΐ 匕ΐ 匕ΐ 匕ΐ 匕ΐ 匕ΐ 匕ΐ 匕ΐ 匕ΐ 匕ΐ 匕ΐ 匕ΐ 匕ΐ 匕ΐ 匕ΐ 匕ΐ The binding site of the killer. Therefore, when metal nanoparticles are used, the amount of the oxide can be used, thereby reducing the influence of the metal oxide on the environment. The toxic substances used in the current hull coatings are generally according to the present invention. Mito 11 200923035 Imididine is relatively harmless. In fact, medetomidine according to the present invention is harmless to a pharmaceutical preparation approved for internal use. The mitox bite can also be biodegraded, so the substance is in vivo. Less accumulation. Other imidazole-containing biocides ^ For example, the antifungal agent miconazole is used. The imidazoline-containing compound spiroimidazoline & such as "Catemine3,, (S18616 {(S)- snail [(1-Evil) -2-Amino-3-indene oxime ? ene)-4,29-(89-chloro-19,29,39,49-tetrahydronaphthalene)]., 戍Example 1 Various nanoparticles and bio-extinction Materials and Methods for Killer Interactions A total concentration of 5 mM biocide was added to 50 ml of o-diphenyl solvent. The relevant concentrations of nanoparticles were then added according to the protocol (Sigraa, Stockholm, Sweden) -Aldrich Sweden Ltd., after each addition: The concentration of the non-adsorbed mitote-flavored bite was measured using standard HPLC-UV techniques (〇H〇n Pharma, Helsinki, Finland). According to the literature, Mitomi® UV Maximum absorption at 220 nm. UV-spectroscopy prior to HPLC analysis (Australia The GBC 920 UV/Vis Spectrophotometer from Victoria Scientific Instruments Ltd. analyzes the UV maximum absorption to determine the given value of the literature. The sample analysis is performed using an HPLC-UV system that includes a Merck-Hitachi L-6200 pump ( Merck_Hitachi, Darmstadt, Germany), a C18 column with a pre-screening program (0.5 μm) produced by Supelco Discovery® (Sigma-Aldrich Sweden Ltd., Stockholm, Sweden) (25 cm>< 4. 6 mm, 5 m) and a Spectra-Physics 100 UV spectrometer operating at 220 nm (Spectra-Physics, Jrvine ca, USA). The mobile phase was Milli-Q water: acetonitrile (〇. Tri I acetic acid TFA v/v (mobile phase A): 0.1% trifluoroacetic acid TFAv/v (mobile phase B)), flow gradient was 2 minutes 6% mobile phase B 15 minutes 60% mobile phase B ' 3 minutes 100% mobile phase b, equilibrated for 3 minutes, 2 minutes later returned to the starting value, flow rate is l 〇 ml / min. Using UV detector (22〇nm) 200923035

Monitor peak separation. Manual injection is called micro-literation, and I use ^ «^t^(3.20^.1999) (^IMilfordMA ^ w company).叼waters results when CuO and ZnO nanoparticles are mixed with mitoxantine and other antifouling agents such as Baiqing, bacteriostatic, SeaNine, Irgarol, Diuron and carbendazim dimethyl strepone 2A) and 2B)], a significant system of interaction was observed. Most of the mitox is lightly adsorbed even at the side grain concentration, especially when Zn0 nanoparticles are used. This makes it possible to design a package of low-content mites and nano-scales to reduce the anti-fouling surface of the ship. Silk ♦ (iv) Adsorption is highly advantageous compared to other antifouling agents listed above φ. The antifouling agents listed above exhibit a common feature; nitrogen appears in all compounds in the form of secondary or tertiary amines, nitriles or heterocycles. However, studies have shown that the sodium saliva portion of mitomib has an optimal geometry suitable for adsorption to the surface of the particles. It should be noted that although medetomidine showed the best adsorption, in the present study, some other compounds, especially SeaNine, Diun), also showed adsorptivity. Example 2 Study Materials and Methods for Interaction of Nanoparticles and Biocides of Various Sizes Different nanoparticles purchased from Sigma (Sigma-Aldrich Sweden Ltd., Stockholm, Sweden) (211〇, (;11〇,人1203) , 1^0, 1102, SiO 2 ) 'has not been further purified. To a large beaker containing 5 〇 ml of mitoxantidine (Orion Pharma, Helsinki, Finland), 5 〇 ml of o- 13 200923035-toluene was added. Nanoparticles were added, and after each addition, the number of free mitoximines was detected using the Fast ic-(10) detection technique (as in Example 1 above). Results In order to study the importance of the surface area, we studied mitox p meters. Bite interaction with various metal oxide nanoparticles (Zn0, Cu〇, Α12〇3, %〇, Ή〇2), nano-silica (SiO 2 ) and a micron-sized particle Cu〇 (5 μπ〇 ( See Figures 3 and 4). When microparticles are used instead of nanoparticles, the adsorption of medetomidine is rather subtle. The importance of 'large adsorption surface area' when these knots are adsorbed on the surface of the particles. 3 Release rate of biocide on particles Materials and Methods The coatings selected for these studies were self-polishing coatings with xylene as solvent and self-polishing Lefant marine coatings from Lotrec Ltd. (Sweden 1^11 (11 〇)' Add 1〇1111 containing 1〇§ nanoparticles to (1 liter of coating) ((::11〇 and ZnO) (sigma-Aldrich Sweden Ltd., Stockholm, Sweden), surface adsorption Mittomi bite (〇ri〇n, Helsinki, Finland) Pharma) or SeaNine (Rliome & Haas, Philadelphia, PA, USA), stir well for 5 minutes to mix. Prepare 3 samples and apply with a paint applicator to break the coating thickness evenly in this experiment. It is 2 〇〇 micron. The application surface is HM0 cm and placed in artificial seawater for 8 weeks. Results The mitox glutinous rice bite-nanoparticle interaction (Mito taste bite-Ql〇 and mitox flavor a (fixed ~ ZnO) For the release rate study (Figure 5). After 8 weeks, the release of the mitoxantidine-nanoparticle modified coating in the mitoxantidine-nanoparticle modified coating was reduced by 20 compared to the mitomididine coating as an additive. %. Figure 6 shows The result of the interaction of SeaNine-nanoparticles showed a similar release amount similar to that of mitomidazole-nanoparticles. Example 4 Preparation of an antifouling coating using a combination of nanoparticles and biocide to select a mitoxantidine modified coating As an example of a typical coating, it includes the main solvent, diphenylbenzene (self-polishing Lefant marine coating from Reeding, Lotrec Co., Ltd.), in order to prepare a coating containing both nanoparticles and biocide, first The two components are mixed in a solvent which strongly adsorbs the biocide, such as diphenylbenzene. Typically, in W xylene, 10 grams of nanoparticles are mixed with up to 10% excess of unadsorbed medetomidine (using a simple magnetic stirrer), and after complete adsorption (usually mixed for a few minutes) the solution is slowly added. In the paint, the scissor is fully irritated, and the slashing machine is in the sputum.) Until the winning time iff 5-1G minutes, the winning coffee depends on the mixing rate. The nanoparticles were purchased from Sigma (Sigma_Aldrich, Newt, Stockholm, Sweden), and the money was not further purified. Mitto ♦ was fixed from 〇ri〇n Pharma of Lanchelinki. _Although the solid paste of Hefei County Hege has been carried out, it is feasible to make different types of melamines, modifications, and examples, and this modification is also within the spirit and scope of the present invention. ^ , Creation; can be made with various ships and purposes, so this application is filed by the company. Methyl {local thioamide)' c) 15 200923035 (4, 5-dioxa-2-n-octyl-3(2H)-isothiazolone) by Philadelphia, Pennsylvania

Produced by Rohm and Haas Company], d) Irgarol (2-indolethio-4-tert-butylamino-6-cyclopropylamino-s-triterpene), e) Diuron (3-(3, 4-dichlorobenzene) Base)-1,1-dicarbazide), by DuPont Agricultural Producrts, Germany

Wilmington produces; f) and p-carbazone (N-(dioxadifluoromethylthio)-oxime', Ν'-dimethyl-N-p-nonylbenzene extender). The second A, Β diagram shows the relationship between the adsorption rate of the antifouling agent (mitolimidine, chlorothalonil, bacteriostatic, SeaNine, Irgarol, Diuron, and bismuth bacteriostatic) and the surface area (m2) of the nanoparticles. The nanoparticles in FIG. 2A) are ZnO nanoparticles in o-diphenylbenzene. The nanoparticles in FIG. 2B) are CuO nanoparticles in o-diphenylbenzene. The third graph shows the adsorption rate of the mitox bite and the Zn〇 in the o-diphenylbenzene (<53 nm),

Ti02 (<40 nm), CuO (33 nm), A1203 (<43 nm), SiO 2 (l 〇 nm),

Graph of MgO (12nm) nanoparticles and CuO (5μπ〇 surface area (m2). The fourth graph shows the adsorption rate of medetomidine and the surface area of Ζη〇 and CuO nanoparticles in o-xylene, acetonitrile and butanol ( The relationship between m2) and the time of The relationship between the week. The sixth figure is ZnO and CuO nanoparticles - mitoxantidine modified marine coating or Zn 〇 and CuO nanoparticles - SeaNine, SeaNine, Mito taste bite modified marine coating in Mitomi Diagram of the release amount of pyridine and SeaNine (ng) versus time (week) [Main component symbol description]

Claims (1)

200923035 X. The scope of application for patents: 1 The method of preventing 海洋 ί ί ί ί ί ί ί ί ί ί ί ί ί ί , series _ including one and two norms, one of which is used to prevent π from the marine fouling biological matrix. The method of the stomach, wherein the compound containing the shot is Mito, and the method described in the item 3 is for preventing the marine substrate from contaminating the biological matrix f i. ZnO, TO? method, wherein the metal nanoparticle is selected from Cu0, 1, 203, a group consisting of SiO 2 and MgO. ==:= Use = Marine fouling biomatrix: + method wherein the metal nanoparticles are CuO. The m-Fan γ3 term described for preventing the marine substrate from being contaminated by the marine method, wherein the metal nanoparticles are as such. A method for preventing fouling of a biological substrate by the ocean' wherein the protective coating further comprises a neighboring diamide. 7 A method for preventing the marine substrate from degrading the biological matrix by the ocean', wherein the protective coating further includes an ocean coating, which is used to prevent the marine fouling of the biological substrate as described in Item 1. The marine staining method, the shot, containing the Mi (4) compound is a mitox miso, and the metal 'Nanqi granules'. The metal, the nanoparticles are selected from the group consisting of (5), Zn〇, Ti02, A1203, SiO2 and MgO. 9. A method for preventing marine fouling caused by a marine fouling biological substrate as described in claim 8 wherein the metal nanoparticles are (10). 200923035 1 0 · As for the method of claim 4 (4), the method of preventing damage to the sea body caused by the fouling of the biological matrix, wherein the metal nanoparticles are touched. 1 1 · - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - . 12==: The product described in Item 11 of the scope is a marine fouling product caused by a marine fouling biological substrate, wherein the compound containing the material is tolidine. '13 · A product as described in Item 11 which prevents the marine fouling caused by the fouling of the biological substrate, wherein the metal nanoparticles are selected from the group consisting of CuO ΖηΟ, Τι02, A1203, SiO2 and %〇. 14 · For the product mentioned in item i 3 of the patent scope for preventing marine pollution caused by marine fouling biological matrix, wherein the metal nano-grain is (10). 15· As claimed in the patent scope! The product described in the item for preventing fouling of the material caused by the marine fouling of the biological substrate, the towel, the fresh metal particles are twisted. 16 · The patent scope is as described in the work item; Defaced creature A matrix-introduced, fouled product, wherein the protective coating further comprises o-xylene. 17 A product for preventing marine fouling caused by marine fouling biological matrices, as described in the application of the scope of the patent scope, in which protective marine coatings are applied. 18 1 8 ·=Applicable to the product described in Item 11 for preventing marine fouling caused by marine fouling bio-based α. Among them, the compound containing the microphone is the Mito taste bite and the metal nano A particle, the metal nanoparticle being selected from the group consisting of CuO, ZnO, Ti2, A1203, SiO2, and MgO. 200923035 19 2 0 • A product for preventing marine fouling caused by marine fouling bio-based as described in claim 18, wherein the metal nanoparticles are (10). A product for preventing marine fouling by marine fouling organisms according to item 18 of the patent scope, wherein the metal nanoparticles are Zn0. 19