TWI303645B - Autodeposition compositions - Google Patents

Description

1303645 IX. Description of the Invention: Field of the Invention The present invention relates to an automatic sinking composition based on epoxy resin and acrylic resin, and a method of using the composition on a metal substrate to form an automatic coating. BACKGROUND OF THE INVENTION Automatic sedimentation technology has been in commercial use in the steel industry for about thirty years and has established a sound development foundation. For example, US Patent Nos. 3, 592, 699 (Stanbrucker et al.); 4, 108, 817 and 4, 178, 400 (both Roquele); 418〇6〇3 (Little Harwell); 4, 242 , 379 and 4, 243, 704 (both Hall et al); 4, 289, 826 (Little Harwell); and 5,342,694 (Amed) and 5,500, 460 (Amed et al.). The patents disclosed above are incorporated herein by reference. The automatic > berry composition is typically in liquid form, typically aqueous, solution, emulsion, or dispersion, forming a surface film on the surface of the immersed active metal with the attached resin or polymeric film, and allowing the metal object to remain in the bath For a long time. Even in the absence of active metals, the liquid remains stable for long periods of time and resists spontaneous precipitation or flocculation of any resin or polymer. "Active metal" is defined as a metal having a higher activity than hydrogen, i.e., a metal which can be dissolved at a substantial rate in an aqueous solution, emulsion or dispersion and which is accompanied by hydrogen. The composition and the method for forming a coating on a metal surface using the composition are referred to in the art and in the specification as "automatic sinking" or "self-precipitating" compositions, dispersions, emulsions, suspensions, water baths. , solution, process, square 1303645 method or similar terms. Automated dirty is often compared with electric foxes. Electroprecipitation can form an adhesive film similar to autoprecipitation. However, it is necessary to connect the metal to be coated with direct current for coating, and no external current is required in automatic sinking. Traditionally, the method of preparing an automatic coating has been carried out by emulsifying a mixture containing an epoxy resin, a crosslinking agent, and other additives added thereto. The emulsified mixture is further referred to as a solvent, and the automatic frequency composition of the water towel is dispersed in the water towel. The composition will automatically differentiate on the metal surface and form a glossy polymeric coating upon curing. However, the polymeric coating is sensitive to the surface of the substrate, so that it is easy to form coating defects such as trapping and edge withdrawal. Therefore, it is desirable to form on the metal surface, especially on the surface of zinc or mineral zinc metal, which is resistant to pinholes, stains or other surface defects. 'In addition, the automatic smear composition based on % oxy-resin will form a typical smooth surface layer when cured. However, not every end user needs light; surface. Therefore, it will make (4) add the thief to add the ship's silk paint _ ze or semi-gloss surface, of course, do not need this addition or increase the outline. [Detailed Description of the Invention] The epoxy resin used in the automatic slab composition is - the organic material of each phase two = two or more epoxy groups and the appropriate treatment agent anti-private book =, = = Object ° _ 脂 钱 钱 合物 与 工程 工程 工程 工程 工程 工程 工程 工程 工程 工程 工程 工程 工程 工程 工程 工程 工程 工程 工程 工程 工程 工程 工程1303645 The group bond is 丨, 2-epoxy group is substituted, and the condensate and the phenolic plaque are the female condensate of the sun. These condensate γ ΓΓ and their silk analogs are contained in the lacquer and the pot. I ^ two aromatic cores, triazabenzene, hydantoin, an epoxy group or an amine-based organic molecule 'and in each case with and/or an amine moiety removed. The hydrogen atoms are separated from the central steel by the hydroxides in the parent molecule. The rt is called "one or more", and (4) the oxidized monomer oligomer is too eutectic, and it is preferred to separate a methylene group. . The machine eight 7 (four) Wei with buckle _ on the rail test or "part of the mechanical knife, the village for the money machine Gu. Such as ."^sTa this invention of the epoxy difficult to include the diversification of the wealth of the _ _, the case of the second expectation; benzene two ^ good multi-class miscellaneous ^ double shot, double hope, phthalate and commercial feasible Sexuality, this invention is biased towards the use of two-year-old eight-fold eight sons. More carefully, the chemical structure of the following figure is the same as that of the knife containing the epoxy group: 1303645 A is equal to

, for the integer of 50. It is known in the art that this type of epoxy resin is a mixture of different 11 values and the same number of Weiji rides.至至至至至至至至至至至至至至至至至至至至至至至至至至至至至至至至至至至至至至至至至至至至至至至至至至至至至至至至至至至至至至至至至至至至至至至至至至至至至至至至至至至至至至至至至至2.1 is better. The chain epoxy resin is more useful as a resin component in the present invention. For example, the application number is 09/578,935, and the application is disclosed on May 25, 2, and is hereby incorporated by reference. a in the chain ring fat-filling towel, since (10), the ring = group on each of the (4) bonds can react with each epoxy resin molecule to form more polymer, so the fraction is larger than the starting ring. Oxygen resin. The specific reduction of the initial smear of this item is lower than the weight of the epoxy (75 to _, the frequency of the glycerin scale is often the initial % oxygen resin. The reason is not fully understood, but the pre-production Reacted = milk coffee compared with unreacted Wei turn, improved in quality and final automatic killing = material performance. If the epoxy resin contains more than one increased edge edge epoxy resin The strengthening effect is more obvious. The latex resin is cured with the diethylene triamine (wake), and the two-dimensional D hardness city is not more than 45 Wei Lin. The above epoxy group and a plurality of 1303645 energy bases which can increase the flexibility of the automatic smear coating, such as a long aliphatic chain (corresponding to a polymethylene group, and on a polymethylene group) 2 is better than 'better than 6 o'clock.), the polymethylene chain can be the backbone of the reinforced epoxy resin or its side chain; the chain of G-polymers (especially from diacids and ethylene glycol or a hetero chain of condensation of ethylene glycol oligomers; or a polyoxyalkylene bond (having (CH2)n-CHIH)-) m ' and n is 丨 to 3' m is 2 or more, R is Corresponding to the hydrogen or alkyl structure? "Chain." The better physical epoxy is intended to be derived from cardanol (extracted from cashew nuts) with an unsaturated hydrocarbon substituent. The molecular weight is about 350. Bifunctional epoxy. In the present invention, the average molecular weight can be increased by the elongation of the chain or up to 200% in terms of the average molecular weight of the resin or the epoxy resin composition. Therefore, the chain extender should contain at least two functional groups which can react with hydroxide, acid retardant and tickacid. In the embodiment of the present invention, it is also possible to use as a chain extender, such as (4) A, oxidizing and oxidizing, such as SYNFAC _ (manufactured by Milliken Chemical Co., Ltd.). In addition, dicarboxylic acids such as adipic acid are also suitable chain extenders. In the frequency of the present invention, the tree is condensed, such as Shuangshui A, and a combination of a broadening agent containing an increasing edge structure such as polymethylene, polyester, and polyoxygenated women. Such as poly-jujube such as polypropylene glycol, "polyol (transfer with hydroxide or / and the end of the polyphenol polyol), dimer fatty acids, long-chain two-touch (such as guanidine), long-chain diol (such as 1,12-nonanediol) and so on. The chain extender adjusts the degree of condensation (i.e., chain extension) required for the stoichiometric reaction product of the epoxy resin (the resin component in the automatic sink coating of the present invention). A 1303645 is generally said to be 'typically the amount of epoxy resin is kept in trace amounts and a large number of polymerizer reactions. For example, the epoxy group equivalent in the % oxygen resin is higher than the reactive nitrogen group equivalent in the chain extender. . The product so formed will contain unreacted epoxy groups (i.e., epoxy functionalization of the reaction product), and hydroxide, which may be present in the initial epoxy resin, or may be hardened to the chain extension. Formed between the Wei group of Wei. The reaction of the epoxy resin with the chain extender has its reaction time and temperature depending on the degree of condensation required and the desired degree of extension. In the context of the present invention, the reaction product = oxygen equivalent weight is greater than the surface or /; however, the starting epoxy resin reactant is only about 75 to about 罝. This state varies depending on the relative reactivity between the components and other factors, and optimization is determined by experiment. U can be added when it is desired to shorten the reaction time and/or the desired temperature, such as hydrogen, amine or other sequestration. The reaction can be carried out in a solvent which can simultaneously dissolve the epoxy resin and the solvent, such as an inert solvent aromatic hydrocarbon. It should also be understood that some of the starting materials in this invention may remain unreacted when the product has been used for autosinking. ,

In the specific case of Jx month, the product obtained from the reaction of epoxy resin and chain extender is prepared before the emulsion is formed in water. That is, in the presence of a seeding agent, the reaction product solution in the organic solvent of the shirt type is emulsified with water to contain an organic solvent of the intermediate ship liquid. The organic solvent used in the emulsification step may be the same as the organic solvent in which the =oxy group is reacted with the chain extender. Other automatic precipitation components such as cross-linking agents, coalescents, flow control additives (leveling agents) ° dissolved or added directly to Weihua Bucai. Organic 1303645 Solvents can be removed from the emulsion by distillation or similar methods. The automatic precipitation composition of the present invention also contains a high-polymer substance which can be reacted with an epoxy resin to form a cross-linking when the automatic coating is applied, and the present invention can be used as an epoxy resin crosslinking agent. . In the treatment of the automatic sluice composition, if the elevated temperature is higher than 10 (TC, at least a part of each cross-linking agent will react with the epoxy tree ruthenium because it must be at a temperature higher than room temperature. The situation will be reacted, so the cross-linking agent is considered as a latent cross-linking agent or hardener during the treatment. In the present invention, the cross-linking agent is preferred to avoid auto-sinking at a temperature of 6 to rc. The gas composition forms a large number of cross-linking joints with the metal on the surface. However, if necessary, it is also possible to crosslink the latent Wei resin cross-linking with the anti-viral resin cross-linking agent to make the epoxy resin in the automatic hall. Before the formation of cross-linking. "Because it is an acidic liquid environment in the automatic precipitation bath, and the epoxy group in the epoxy resin will hydrolyze AA oxygen, or the county will contain oxygen before the red turn occurs, Therefore, the applicable epoxy resin crosslinking agent must be a substance that can react with hydroxide or unreacted epoxy groups. Suitable epoxy resin molecules must contain: (a) two similar fish gas oxygenates Or a thio group-reactive Wei group, such as a bribe or an amine , imine, thiol, oxy-oxygen, carboxylate, carboxylic anhydride, and (b) eight-person knives contain more than two protected isocyanate groups, and each-base-lang protection agent is tilted or formed in the molecular form The structure of the urinary net. Such a protected structure will not react with the hydroxide in the palace, w' 苒 至 是 是 是 是 是 超过 超过 超过 超过 超过 超过 超过 超过 超过 超过 超过 超过 超过 超过 超过 超过 超过 超过 超过 超过 超过 超过 超过 超过 超过 超过 超过 超过 超过 超过 超过5,500, 460 1 303 645 and 6, 096, 806, each of which is hereby incorporated by reference in its entirety in its entirety, in its entirety, U.S. Patent Nos. 5,5,0,460 and 6, 〇96,8,6 The molecule is a molecule that conforms to the following structure:

X spear X 77 is a single part, formed by removing the most ionizable hydrogen atoms from amines, alcohols, amines, and gases, or X and X, which combine to form urethane; R and R' are Any hydrocarbon or carbon hydrate derived divalent chlorocarbon or heterohydrocarbon _. The hydrocarbon or oxygen atom (4) is present in the form of a county, and any two hydrogen atoms are not bonded to the carbon atom on the filament. The divalent hydrocarbon or a group of hydrocarbon groups contains from 2 to about one stone atom and does not contain an unsaturated functional group other than the aromatic and silk. The versatile is an integer from 0 to 20, preferably from j to 15. Pure soil λ and inlet 』 from suitable aliphatic, cycloaliphatic, aromatic,

Aromatic monoethyl condensate, monoamine, and a single derivative are synthesized into a urinary sinter. : Two Relatively lower jumps can be effective silk protection. If you go to the _ name for a large number of reactions, the failure has read obstruction and / Wei Wei CA from 6-aminoacetic acid or 7 and the three slaves - bribes out of ' 12 1303645 isophorone diisocyanate (IPDI), The isocyanate protected with caprolactam is used as a crosslinking agent for an epoxy resin, such as the product of the VESTAG(R) N趴513(R) trademark of the company. If you use 4 cyanate type epoxy tree month cross-linking Qi! The base-protected isocyanate group to hydroxide ratio (NC0:0H) is typically about 〇· 〇5 to 1.2, and about 〇·1 to 〇·5 is more ambiguous. Other protective ships that can be used are hexamethylene diisocyanate (_). In the specific embodiment of the invention, the epoxy resin crosslinking agent and the epoxy resin are the same.

The isocyanide-based epoxy resin of the knife domain 4 is described in detail in U.S. Patent No. 4,859. /曰Acrylic resin in this automatic immersion compound is obtained by the use of a benzoic acid monomer and can be combined with one or more non-propyl acrylate monomers in an automatic settling bath or in a catalytic Better stability is achieved when the age of the metal is formed on the surface of the hybrid metal. (10) The acid monomer includes acid, methacrylic acid, acrylate, methacrylate (particularly (10)), acrylonitrile, isobutylene salt, propylamine, methylamine and the like. Suitable non-acrylic monomers can be polymerized by (iv) olefinic acid and vinyl surface monomer.

Suitable propionate resins are easily available, especially for acrylic resins such as MAINCOTETL-5 and MAINCOTE AE-58 昏 昏 π 日 日 (white for Rohm and Haas products), AQUAMAC saturated steroids, containing ethylene The Weizhi, the (4), the unsaturated monomer, and the ethyl sulphate of Weizhong are obtained by polymerizing the heteropolymer of acetic acid. The preparation of acrylic resin has been known in the art as a prior art, and its preferred form of use is for hanging or dairy (containing intact granules in Lai Guan towel). 13 1303645 705 (Macquay products), RHOPLEX WL-9 Bu B85, 1822 (Rohm and Haas products), service 00^1^633 4621, eight 640 (Xinka products), -〇^1^0 78-6391 , 78-6408, 78-3936, 78-6334 (products of the National Starch Chemical Company) and 76 Resin 1018, 6033 (Unocal products). Among them, MAINC〇TE TL-5 acrylic resin is especially suitable. Other suitable acrylic resins may also form a stable automatic settling bath via a) in an automatic settling test, forming a surface on the surface of the active metal in the presence of a catalyst, c) providing an adherent film that is hygroscopic and not easily rinsed away, The suitability was determined in three tests.

Acrylic resins with poor suitability include RH〇PLEX 195〇, AC_64, TR

407, HA-8, HA-12, and B-60A (Rohm and Haas products), CMD_979〇 (Haitieke products) 'NACRYLIC 78-6354, 78-6207 (Xinka products), 76 resin 6510, Z6106, ST6004 and VC60012 (unocar products), and SACIRP_2i5A (Wittke Chemicals). The H item is issued by the Ethyl Ethylene and the sulphuric acid of the county, which is not strictly limited with respect to the entire molecular weight. Nonetheless, when the ratio of the acrylic resin to the oxygen curing agent is lower than 5:95, it can be observed that the coating surface has no effect on the coated surface containing only the Wei resin or even the other The ratio of epoxy resin and epoxy resin curing agent exceeds 60.40%, which will have a negative impact on the corrosion resistance of the autoprecipitated coated surface. The ratio of propylene eucalyptus to epoxy resin and epoxy resin is preferably between 10:90 and 50.50. Although it is known that the acrylic resin-based automatic slab coating surface 1303645 has poor anti-corrosion resistance compared with the epoxy resin-based automatic precipitation coating surface, it is found in the present invention that a suitable acrylic resin is added. The catalyst which does not affect the anti-corrosion property is automatically precipitated as an acid, an oxidizing agent, and/or a complex which accelerates the dissolution of the surface of the active metal in the presence of an autoprecipitating composition. The autoprecipitated catalyst can be obtained from molecules having the following functional groups: hydrofluoric acid and its salts, fluorofluoric acid and its salts, fluorotitanic acid and its salts, iron ions, acetic acid, phosphoric acid, sulfuric acid, nitric acid, and Hydrogen peroxide, peroxyacid, citric acid and its salts, tartaric acid and its salts. A suitable autoprecipitated catalyst is polymerized at a concentration sufficient to cause the redox potential of the autoprecipitating composition to be at least 100 millivolts above the standard hydrogen electrode. Automated cation catalysts can be selected in any of the above molecules depending on the desired target or result. The most suitable autoprecipitated catalyst contains the following three subcomponents: (C1) Each liter in the automatic settling bath contains a superior order of aggregation increments 4·4,0·8,1·0,1·2,1· 40 or 1·60 grams of fluoride ion. The following concentrations are shown in g/Ι. The addition of 5, 4·0, 3·6, 3·3 or 3 〇g/l fluoride ions in the superior order of aggregation is better. In the present invention, a fluoride which is soluble in an auto-settling bath in the form of an anion is tested to determine the optimum concentration, and is independent of the generation of ionization, binding, and complex ions. (C2) oxidant. In particular, it is preferred to contain hydrogen peroxide and ferric ion because it can effectively provide an oxidation potential in a liquid mixture which is automatically settled. Depending on the pin or other immersion metal and the autocluded liquid mixture, the oxidant containing hydrogen peroxide and trivalent 15 1303645 iron ions may provide at least an oxidation potential that is greater than that provided by the hydrogen plate, with an increasing order of 150, 175. , 200, 225 or 250 millivolts. The additional amount can provide an oxidizing potential of 550, 525, 500, 475 or 450 millivolts with an increasing superior order. (C3) A substance which can supply hydrogen ions in an automatic settling bath, and can effectively adjust the pH value to L 〇, 丨·4, 丨·6, 丨·8 or 2·〇 with an increasing superior order. With the increase of the content, it can be adjusted to 3·8, 3·6, 3·2, 3·0, 2. 8 or 2 6 with increasing superior order. The subcomponents (C1) to (C3) may not necessarily come from different substances. For example, hydrofluoric acid can provide both (C1) and (C3). Dissolving ferric ions in hydrogen The iron fluoride produced in the absence of acid provides both (C1) and (C2). Iron ions, hydrofluoric acid and hydrogen peroxide are very suitable as compositions for autoprecipitation catalysts. In the mixture in the reaction, the suitable concentration of iron ions is 〇·5, 〇·8 or 1.0 g/Ι, which is more suitable; the elongation is not greater than 2 95, 2.90, 2.85 with increasing superior order. , 2.80 or 2.75 g/Ι. The suitable concentration of ft is h 5〇, i 55, or 1·60 g/Ι, which is more suitable for concentrations of not more than 且, 7·〇, 5· 0, 4· 0 or 3· 0 g / 卜 and in the reaction of the automatic precipitation composition added to the emulsified air suitable concentration with an increasing order of paper is Q • coffee, Q · 丨 G, Q · H continent, 〇 · xian g / Ι, more suitable The concentration is not greater than and has an increasing superior order of 2·丨, 1·8, ^ 5, 1·〇〇, 〇·90, or 〇. 80 g/; l. The automatic setting composition of the present invention may also contain other additional ingredients. These additional ingredients include surfactants (emulsifiers or suspensions), fillers, antibiotics, 1303645 formulations, flow control or leveling agents, pigments and/or colorants. The concentration of the added components is selected according to the concentration of the corresponding component used in the epoxy-based autoclave-based compound, such as US Patent No. 5, Preparation, 6贱8〇6, and 09/578, Revealed in 935. The surfactant is a part of the suspension or emulsification of the automatic lining combination, and after the preparation of the autoprecipitate, it is not reacted with any active metal, and it is stored in the trap for 24 hours. Or separate. Both Yinshangzi surface agent and nonionic surfactant are suitable for use. Mixtures of different interface activities 2 are also suitable for use. The most suitable anionic surfactant in this project is the ether sulfate of the chemical formula of the following figure.

Μ+ · c^so2-CKCH2'CH2 〇)p R where: Μ is a monovalent cation or a higher number of cations, and ammonium is more preferred. Expected ‘, 纳纳 is eight is%> day < silly order is B, 3, 4 best. R" is a burnt-based Weisi, and the filament # is preferred. And δ = 30 sub- and contains 15 to 2G carbon atoms. Suitable agents such as D on the side _1 (sintered double-seeking salt) , Μμ (4) with E~12 ^ K-12 ^ RhidapexTM CO-128, -143 ^ EP_1〇〇^ on X \ 17 1303645 -120 and -227, DisponsilTM AES-13 and AerosolTMOT (succinic acid succinate). One of the most suitable anionic emulsifiers is Rh〇dapexTM C0-436, which is indicated in its supplier's report as a salt containing 58% of pyrithione. In the present invention, both water and organic solvents can be used. The carrier or vehicle of the autoprecipitating composition, however, the autoprecipitating composition is more free in volatile solvents. Epoxy resins, acrylic resins, epoxy resin curing agents and other compositions can be dissolved in a solvent and emulsified in water. The solvent can be removed by vacuum distillation after emulsification to form an acrylic resin, an epoxy resin, an epoxy resin curing agent, and a substance suspended in a liquid medium as a whole particle. Although many solvents are used in the present invention. Does not reduce the technical benefits of the final automatic precipitation composition, It will remain in the autoprecipitated composition. These residual solvents will be removed by warming in the final solidification stage of the autoprecipitation. A suitable solvent is a mixture containing (i) an aromatic sum of 6 to 1 carbon atoms ( 11) ig having 3 to 8 carbon atoms. A suitable concentration is 10 wt% of the weight of the anhydrous component combination. Suitable solvents such as toluene and methyl isobutyl ketone (mibk). In the present invention, automatic precipitation Preferably, the composition contains a coalescent component, the component contains a monoacid and a glycol material, and the diol has more than one terminal hydroxyl group. The single scale of ethylene glycol is easy to obtain and can effectively inhibit foam formation. , but by many areas > dyeable control method _ use. propylene glycol monoether has been invented to stabilize the emulsion of the product of the invention more than ethylene glycol single bond, especially with methyl, tert-butyl, n-butyl The base and propylene glycol are better. 1303645 Single vinegar is not ideal for the product's resistance, but it can also be effective at low concentrations' so when economic reasons and / or must meet the strict solvent release standard For corrosion resistance requirements, the monoester is Good choice, 2,2,4_trimethyl-3-pentanol monoisobutyrate (filming aid) is preferred. Pigment, wire filling or miscellaneous toner _ and other automatic liquid The selection method of the mixture is the same as 'the requirement of bribe is fresh. The suitable dyes are carbon black, 敝 New 'Lin, 喧, Xuan 敝, ship yellow or benzidine yellow pigment, etc.. If the acrylic resin is suspended The liquid and epoxy resin suspensions are ready to be drunk before the preparation of the autodeposition composition. The reaction of the (10) acid resin with the cyclopentate is more advantageous. In the process of regulating the process, the addition of the surfactant is refined. j (while adding a better effect) will contact (four) g scales. These added ingredients will be carved or combined in the acrylic tree, so that the acrylic resin suspension will be more elegant. This is the temperament of the lion's automatic sluice. That is to say, the automatic sedimentation mixture of the _discrimination_enoic acid resin can be maintained in a stable state even if it reacts with the active metal to form a coating over a long period of time. It is more advantageous if the surfactant used in this treatment is the same as the surfactant added when preparing the epoxy resin suspension. Of course, the amount of the interface 9 (four) 力 is based on the selected acrylic finger surface and the efficacy of the surfactant. The typical dose weight is from about G. 2% to about 1 G% (depending on the acrylic resin composition). Similarly, the same curing agent or the same type of curing agent as in the preparation of the epoxy resin suspension is suitable, and the curing profile is also based on the selected acid resin, curing agent strength and the required automatic coating. The nature of the cloth is determined by a typical dosage of about 0.5% to about 1% by weight of the curing agent (according to the composition of the acrylic resin composition. - Generally speaking, in the air before the first with the epoxy tree. Before the reaction, the surfactant and curing agent are preferably mixed with the acrylic acid solution for Q. 丨 hours to 10 hours. The automatic sluice composition does not add catalytic catalysis before use and for several weeks of storage. Automatically precipitating the stability of the composition and affecting the storage. The coating step of the present invention comprises: (&) contacting the substrate having the active metal surface with the aforementioned automatic smear composition and catalyst for a sufficient time to A wet coating film composed of (4) acid resin female and epoxy resin, and (b) removing the coated metal autoprecipitating composition. (4) washing the coated metal The surface 'washes the absorbed but not fine components from the parts that have adhered in the bath. (4) The coated metal is heated to form a cured coating. When the # wet adhesive coating is heated, the visible epoxy And the epoxy tree sizing agent will form a thermosetting polymer, and different acrylic resins can sometimes be added to form a thermosetting polymer. ' " . , before adding the automatic precipitation composition, the reaction The metal surface needs to remove the oil 5 first, and the degreasing technology made by washing with water can also be used for the present day. The washing of the suicide is treated with running water, but generally speaking, the immersion is not more than (10) seconds in the room. 20 1303645 It is better not to exceed 20 to 60 seconds in temperature. The final method can be used to make gold; I surface is in contact with autoclave. If it is not (immersion), sprayed, etc., it is better to immerse. The contact time between the &Mingzhong/S' metal and the automatic H composition is preferably 〇5 to 1〇 minutes, and the frequency thickness (four) meaning "displayed; 丨 to 3 minutes is better" can be formed 18 to 25 micron thick film layer - the general thickness of the film should be proportional to the contact time In addition, after the surface of the coating is stopped from contact with the composition of the auto-sinking chamber and the other strips are added to the strip, the reagent can also be separately attached to the water after washing the strip. Deionized water is used to rinse the gold to form a coating surface to provide a good product f, but if a water bath containing metal ions such as nitrate is used, it can provide better anti-aliasability, such as US Patent No. 09/ 578,935 'Application on May 25, 2002; Case No. 6〇/252, 799, 2 Year of the Rooster on November 22nd. The washing reaction described in Case No. 60/252,799 can be applied in the automatic sinking The surface of the cloth is provided with the same properties. (10) The conventional automatic shed cleaning technique can also be used in the present invention. Finally, the post-treatment of the rinsing wet coating _ layer table φ heating and the automatic smear film is suitable to be higher than The temperature of the Hurt is such that the temperature is sufficient to affect the epoxy resin curing agent reaction in the thin layer of the automatic chamber. In general, the end is. (3) 3 〇 (The heating temperature of rc is silk surface and solidified coating, the time is (4) 6G minutes; the better temperature is 130 ° C to 240 ° C, the time is 1 〇 to 5 〇 minutes. 21 1 1303645 ..., can be as needed This is done in multiple steps. For example, in the first stage, the first 5 to 15 minutes, the coating substrate is heated to 55. The peak temperature is reached to remove the residual moisture of the coating, and the second stage is 3 At 5 minutes, the bottom of the paint is heated to the peak temperature of the boot to the enamel. This peak temperature arrives within 10 minutes after the completion of the first heating stage. The automatic precipitation composition of the present invention can be used to treat iron, resignation, Ferroalloy and zinc alloy metal surfaces, as well as alloy components such as automotive steel components, automotive components such as shock absorbers, sockets, leaf springs, suspension components and bearing frames, etc., or factory equipment components such as tow rails, etc. Automatic slab coating It is especially suitable for use in metal indoor equipment that is easily worn or bumped, such as filing cabinets, filing cabinets, desks, etc. EXAMPLES The ingredients of the supplement composition according to the present invention are prepared as follows: g) Acrylic resin suspension 260.15 Crosslinker 8.53 Surfactant 4. 44 Epoxy resin suspension 691.32 Pigment 28.55 Deionized water 7. 00 Total 1000.00 22 1303645 Acrylic resin used for Rohm and Haas products MAINC〇TE TL_5 (4ι .5 % solids), with a pH of 7.5, a viscosity of 200 to 1000 cps, and a solid weight of 17 〇〇. MAINCOTETL 5疋 is derived from the 归 单体 。 。 。 。 。 。 。 。 The product 2, 2, 4-trimethyl-i, 3-pentanediol monoisobutyric acid (film-forming auxiliary). The surfactant is the sulfonation of Rodia Chemical's trademark RHODAPEX CO-436. Ammonium salt of nonylphenol ethanol (58% active). Epoxy resin suspension is undyed AUTOPHORETIC, the product of the surface technology department of Han Hanger Company, including the iso- oxime oxygen tree turning agent contains 60· 〇% of the solid granules. The procedure for preparing the epoxy resin suspension is described in the application for the next day of May, 2, application No. 09/578, 935. The pigment is a carbon black suspension (solid weight) 41·0 gram), is the trademark of Binnay and Smith Company AQMBLACK 255 The above ingredients were added according to the following steps: The acrylic acid; the blush suspension was injected into the living body, the crosslinking agent was added during rapid stirring, the crosslinking agent was added after adding the crosslinking agent for five minutes, and the epoxy was added two hours later. ^^lipid suspension, add the pigment after 3 minutes, and continue to stir until the carbon black is also completely suspended in the mixture (about a minute). Extract the composition to the required percentage, then add water to reach The required percentage is 37. 0. The final product passed through a 30 micron filter. The ratio of the acrylic resin to the epoxy resin and the epoxy resin curing agent (mainly solid in the suspension) is 3 Torr to 7 Torr. The autoprecipitated composition prepared in the supplement composition was as follows, with the composition cloth filling 243·24 g, water 450. 00 g and AUTOPHORETIC starter three 23 1303645 hundred 75. 00 a g (this is Hankai The surface technology department of the company contains automatic catalysts and other ingredients. These ingredients are in the middle of the container - and the appropriate water is added to achieve the desired percentage value. According to the above steps, the easy-to-obtain lacquer acrylic resin and the AUTOTOPEETIC 901 ¥ oxygen tree master automatic settlement development ship (this is the product of the surface technology department of the poor Xi'an McDee Sun Yihan company) The ACT cold rolled steel plate was coated with a _ series coating to demonstrate the quality impact of the acrylic resin on the surface of the cured auto-settling coating. The control of the automatic > drop composition is as follows: · Redox value LINEGUARD 101 1 Instrument reading total number of solid particles (NV percentage) Wet coating particle starter titration 325-375 millivolts 150-200 microamperes 5.5-6.5 % (target is 6.0%) 30-50% (target is 35%) 22-32 ml temperature 20-22〇C (68-72〇F)

24 1 LINEGUARD 101 reads as a product of Hankel's Surface Technology Division. Table 1 summarizes the observations. The cured autoprecipitate coating gloss decreases as the concentration of the acrylic resin increases. The anti-corrosion properties exhibited in the 168-hour spray salt test were not affected by the added acrylic resin. After 168 hours of the Cleveland moisture test, all surfaces exhibited Vf9-sized bubbles and 5b adhesion. 1303645 Table 1 Example number acrylic resin propylene earning resin wt% 8 gloss (60 degree gloss) 6 sprinkling salt 168 hours ^ I1 0 90+ 2.5mm (0J6mil) 2 10 85 L8mm (0.67mil) 3 A 20 35 2.6mm ( 0J9miI) 4 ¥~ 10 65 1,9mm (0.68mil) 5 20 80 1.8mm (0.67mil) 6 5 90. 11mm (0J5mil) 7 C 10 85 l *9mm ( OiSmil ) 8 C"~ 20 55 2.3mm ( 0.73mil) 9 ^~W~ 10 80 l.8mm (O.90mil ) 10 20 50 1,8mm ( 0*98mil) 1 control group 2 AQUAMAC 705, Acrylic resin 3 MAINCOTE AE-58, Solomon Haas offers acrylic resin 4 MAINCOTE TL-5, Rohm and Haas offers acrylic resin 5 NEOCRYL A633, Xinka provides acrylic resin 6 gloss measurement for each change 2 degrees 7 sprinkle salt test every change 2 degrees measurement 8 solid weight The calculation of green is epoxy resin with epoxy tree compounding agent and acrylic resin [Simple description] [Main component symbol description] 25

Claims (1)

1303645 X. Patent application scope: 1. Automatic self-sinking; hall composition, which contains · (a) water; (f------------------------------------------------------------------------------------------------------------------------------- Epoxy resin prepared by reacting with a chain extender containing a group of two thieves and oxygen thieves; (a bismuth-type suspension of the two olefinic acid resins; a molecule selected from the group consisting of two or more molecules which can react with a gas, a hydrazine or a hydrazine, and a molecule containing two or more protected condensed cyanate groups; /, wherein C-trees are (The ratio of Wei resin and epoxy tree to ship is between 5:95 and 60:40. 2,f:m is the automatic compound of the first item, and more than one type is prepared from polyglycerol. An epoxy tree wax and a chain extender containing a related functional group such as milk root, citric acid, carboxylic acid ketone, etc. 3.=^Special=Scope automatic sinking composition of item i, wherein the automatic phlegm group 5 The polynonol phenol is bisphenol A. 4. The η, shouting composition of the character according to the first item of the scope of the patent application, wherein the autoprecipitate group is a glycidyl ether desired from the cashew nut Derived. 5· According to the application of the patent scope of the 丨 丨 丨 之 为 为 为 为 _ 26 26 26 26 26 26 26 26 26 26 26 26 26 26 26 26 26 26 26 26 26 26 26 26 26 26 26 26 26 26 26 26 26 26 26 Epoxy resins have the following chemical structure: The trick is: And η is an integer of 0 or 1 to 5 。. 7. The autoprecipitated composition of claim 1, which also contains an added surfactant, an automatic catalysis catalyst, a dye, a curing agent, a flow control agent, and a related mixture. 8. The autoprecipitated composition of claim 1, which comprises at least one of the above autoprecipitated catalysts. 9. The automatic precipitation composition according to claim 1, wherein at least one or more epoxy resin curing agents are cured isocyanic acid. 10. According to the application of the automatic sedimentation compound of the article, the epoxy resin, acrylic resin and Wei resin curing agent, the ratio of the acrylic resin to the Weishu trace epoxy resin curing agent is 5 to 95. Or 60 to 4 inches. 27 1303645, adding more than one surfactant and crosslinker. 12·- kinds of metal forks, coated by the automatic sluice composition of the scope of the patent application. 13. A method of forming a coating film on an iygx mass by contacting the automatic smear composition of the first application of the patent application with a metal substrate for a sufficient time to form an epoxy on the genus A cured coating film layer of a resin, a bupropion resin, and an epoxy resin curing agent. 14. According to the method described in Item 13 of the patent lag, more than one type of automatic precipitation catalyst needs to be added to the autoprecipitate. 15. According to the method described in the application No. 13, the epoxy tree shut-off agent is reacted at (10) it to 240 °C. A method for producing an automatic composition according to the scope of the patent document, characterized in that it comprises the following steps: (a) adding (10) an acid resin to a human or a mixture of a surfactant and a curing agent mixture The additive wherein the aforementioned surfactant weight is from the composition of the acrylic resin, and the front crucible is a mixture of (4) to _ to form a treated acrylic resin suspension; and (8) After the reduction of the obtained (4), the anti-slip secret liquid and the epoxy resin suspension containing water, epoxy resin and epoxy resin curing agent are the above-mentioned acrylic resin: (epoxy resin + epoxy resin) The curing agent) ratio is 5: 95~, for example, a mixture of people to form an automatic precipitation composition. U 17. The method according to claim 16 wherein the acrylic resin is contacted with more than one surfactant and coalescent in step 28 1303645, step (a). 18. The method of claim 16, wherein the epoxy resin suspension additionally comprises a surfactant and the acrylic resin suspension is contacted with the surfactant in step (a). 1 19. The method of claim 16, wherein the epoxy resin suspension additionally comprises a coalescent and the acrylic resin suspension is contacted with the coalescent in step (a). 29