• 专利附录
  • 专利说明
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    • 专利摘要:
    PURPOSE: A method for coating substrates, preferably with metal is provided which prevents the contamination of a coated surface and minimizes the occurrence of a flaw on the surface. CONSTITUTION: A method for coating substrates, preferably with metal, is characterized by cleaning the surface of the substrates, optionally by applying an inorganic and/or organic pre-treatment agent, a primer, an enamel by spraying, dipping, scraping, laminating or coating, whereby the enamel contains an amin-modified epoxide resin and an appropriate cross-linking agent.
    公开号:KR20000057389A
    申请号:KR1019990704944
    申请日:1997-12-02
    公开日:2000-09-15
    发明作者:에곤 베그너；울리케 클라우젠-마이링；브린크하우스 카를-하인츠 그로쎄；로타르 얀델；볼프강 브렘저；구이도 빌케；도로테 드레숴；라이너 뷔르스팅하우스；귄터 오트
    申请人:베른하르트 클루트；바스프 코팅스 악티엔게젤샤프트；옌스 피셔；한드룽스베볼매크티그테르 프로쿠리스트；
    IPC主号:
    专利说明:

    Preferably a method for coating a substrate of a metal {Method for Coating Substrates, Preferably with Metal}
    The invention preferably relates to a method of coating a substrate of a metal.
    Numerous conventional methods of surface treated strips and metal sheets have already been developed at the beginning of the century. Subsequently, significant advances have been made in Europe in the 1930's using wide strips of electrogalvanizing (tin plates) and hot dip galvanizing. Since 1959, when the first hot dip galvanizing plant has been in operation, the supply of surface-treated thin metal sheets in Germany has increased, and in the 1970s and 1980s standard and numerous other variants began to be supplied.
    Recently, the use of such flat products with metallic covers and / or organic coatings has been increased by the metal sheet processing industry. Advances in plant technology, material fields and processing methods have led to the development of the transition from component processing to pretreated metal sheets or a combination of the two. Always complex requirements for materials have created the need to combine the advantages of steel as a substrate material (eg strength, formability and weldability) with special new properties such as corrosion resistance and decorative appearance.
    The field of application of metal sheets coated by these methods (so-called coil coatings) is very diverse. In the construction sector there are numerous applications. Coated metal sheets are also used in the interiors of walls, furniture, lamps and appliances. In addition, the range of applications in automobile manufacturing is increasing. Truck bodies and "bolt" automotive parts are often made of pre-coated materials. Caravans and motor groove bodies are manufactured from coated metal sheets with almost no exception.
    Based on the area of application, various requirements are imposed on the coating of the metal sheet. In particular, great flexibility and formability must be combined with the pronounced adhesion by the coating. This is particularly necessary when the coated material has to be arcuate with a small radius, for example when manufacturing a vehicle body.
    At the same time, it is necessary to provide a material for further processing that meets the most stringent requirements of thickness, color tone, surface quality and loading behavior. These properties must also be maintained when bending and cutting the material.
    Coating materials that can be used for coil coating are known, for example, from US Pat. Nos. 4,692,382 and 4,692,383. These patents relate to mixtures based on isocyanates and phosphorylated polyepoxides. In view of the above requirements, the properties of these coatings are still not completely satisfied. This applies especially to scribe marks and bottom film corrosion at the edges. In addition, there is a continuous sticking problem.
    It is an object of the present invention to clean the substrate surface, to apply an organic or inorganic pretreatment composition if necessary, to apply a primer coat, to coat the coating by spraying, dipping, knife coating, roller coating or brushing if necessary and subsequently baking. It is therefore desirable to provide a method (without the above mentioned disadvantages) of coating a metal substrate.
    This object is surprisingly achieved by the preparation of primers comprising amine modified epoxy resins.
    The invention is also coated with one or more coats to clean metal surfaces, apply organic or inorganic pretreatment compositions as needed, apply primer coats, apply top coat by spraying, dipping, knife coating, roller coating or brushing and A metal substrate is preferably provided which can then be prepared by baking the coating and laminating the removable sheet on the coating film if necessary.
    The advantages achieved by the present invention can be seen first of all in that the primer of the present invention exhibits minimal surface scratches in any case and no sticking problem occurs. The primers of the present invention surprisingly show excellent antifouling, and the good surface properties of the baked coat are maintained even in the presence of a material that causes surface scratches.
    In addition, the substrate coated according to the present invention is of high and uniform quality and has the advantage of exhibiting excellent properties in terms of moldability, durability, chemical resistance, corrosion resistance and weathering stability. Thus, the coated material is particularly suitable for segments in which a small radius of curvature is required. Thus, the coated material itself is particularly suitable for the manufacture of a vehicle body. The same applies to the flexibility and tack of the coating. Moreover, the coated substrate meets all requirements in terms of thickness, color tone, surface quality and behavior under loading. Resistance to lower film corrosion (creep) at scribe marks and edges is a particular advantage.
    <Board>
    Because of their diverse uses, a wide range of substrate materials are used for coil coating. Subsequent machining steps should be considered as the first criterion for selection. Sharpening, bending and deep drawing require specific quality and strength as guaranteed by steel alloys or aluminum alloys. Another important selection criterion is the field of use below.
    In many cases the substrates are pretreated, especially if they are metallic substrates. Suitable pretreatment compositions are all organic and inorganic products known to those skilled in the art. One example is the application of a phosphate coat to a substrate. Bulk non-corroded steel products can be processed by coil coating without further pretreatment. For high humidity and climate stresses, electro galvanized or hot dip galvanized materials are used. Even in these processing steps, standards of different quality are produced according to the intended application. In addition to steel, aluminum is also an important substrate material.
    In the case of metal covers, zinc and aluminum and alloys thereof are preferred. One or two letter symbols correspond to European standards. Z represents zinc (Zn), A represents aluminum (Al), F represents iron (Fe), N represents nickel (Ni), S represents silicon (Si), E represents electrolysis, and OC represents coated organics. Alloy covering is important because of its potential. In addition to standard galvanizing, the high-grade aluminum variant Galfan and Galvalume play an important role here.
    The most important coating methods are described below.
    1. Melt dip, impregnation of strips with molten coating metal (which can be used as a metal of relatively low melting point). In this method, the strip flows directly from the heat-cooling furnace into a hot melt, which is between about 420 and 660 ° C. depending on the metal under inert gas. Immediately after the excess metal is ejected over the upward strip to form the desired adduct on both sides, the surface formation is controlled and the coated strip is cooled. A small amount of aluminum (about 0.2%) is added to limit the formation of an alloy layer at the boundary between the steel and zinc coatings. The high aluminum coating of the high temperature immersion aluminized metal sheet has a similar effect. Moreover, previously small amounts of lead (about 0.1%) have been greatly reduced due to the formation of large zinc blooms known in the case of hot dip galvanized metal sheets, or a process which is actually free of lead is adopted.
    Thermal post-treatment of the freshly galvanized strip at about 520 ° C. results in a “zinc plating” run where necessary, where the pure zinc coating is entirely coated with a zinc / iron alloy with a matte gray appearance (delta phase = FeZn 7) . Corresponding). Occasionally, one side of both sides of the strip is free of a pure zinc coating by brushing, and the variant hot dipped galvanized on substantially one side as a product is known under the name "Monogal".
    The composition of the galvanic coating is very close to the eutectic mixture in the zinc-aluminum system. The composition metal is about 0.05% cerium / lanthanum.
    2. Electrolytic deposition of coatings from sulphate based aqueous solutions generally takes place according to the parody method. Here, the strips flow horizontally, vertically, or more rarely radially, past the soluble or insoluble anode. In this way, different additions or single sided depositions per side are possible. In the case of ZnNi alloy galvanizing, the electrolysis parameters are adjusted to obtain the desired composition.
    As can be seen, zinc can be applied by two methods. However, the operating characteristics associated with the coating structure and some methods are different.
    A general feature of all treatment methods is that the manufacturing sequence consists of pretreatment of the strip surface (for coil coating), substantial treatment and post treatment, for example by formation of chemical conversion coats such as deoiling and phosphorylation. For example, the (alloy) galvanized strip can alternatively be oiled, chemically post-treated or organically sealed.
    <primer>
    The primer of the present invention is applied to the substrate treated in the manner described above, if necessary, preferably with a coat thickness of 5 to 10 μm. It is then possible to first pass drying and then to apply a top coat having a thickness of generally about 20 μm after drying. To protect against mechanical damage, this surface may in some cases be further laminated at high temperatures with a temporary protective sheet. In parallel with the coating on the front side, the back side is covered, and again an appropriate protective film is applied.
    The function of the primer is to follow application in a thin coat, first producing very good composite adhesion to the substrate, and secondly to ensure adhesion between coats to subsequent top coats. The operational quality and the corrosion protection of the coated material are eventually based on the exact combination of these adhesive properties. Thus, different primers are used in different fields of use. Conventional primers are based on high molecular weight saturated polyester resins in combination with active anticorrosion pigments to increase tack and corrosion properties.
    Different applications require different grades of primer. For example, the construction sector requires moderate deformation properties, good to good surface hardness, and the exterior sector requires good corrosion resistance and weathering stability. Recently, there have also been attempts to use pre-coated metal sheets for the manufacture of car bodies in which certain requirements must also be met. These requirements are surprisingly met by primers comprising amine modified epoxy resins.
    Both self crosslinked and crosslinked amine modified epoxy resins are known. Preference is given to using externally crosslinked amine modified epoxy resins. Preferably, according to the invention an epoxy-amine adduct is used in combination with a blocked polyisocyanate.
    An amine modified epoxy resin is (A) modified or unmodified polyepoxide, (B) primary and / or secondary amines and / or salts thereof and / or salts of tertiary amines, and if necessary (C) means cationic products of the reaction of polyols, polycarboxylic acids, polyamines or polysulfides.
    By polyepoxide is meant a compound comprising two or more epoxide groups in the molecule.
    For the preparation of amine modified epoxy resins, suitable compounds as component (A) are all compounds which comprise at least two epoxide groups in the molecule. Preference is given to compounds which comprise two epoxide groups in the molecule and which have a relatively low molecular weight of 750 or less, preferably 400 to 500.
    Particularly preferred component (A) is a mixture of diepoxide compounds or diepoxides having a weight of epoxide equivalent of less than 2000, and (b) a monofunctional group reacts to the epoxide under certain reaction conditions and The presence or absence of component (b) and catalyst using component (a) comprising a thiol group, or a mixture of such compounds, in a molar ratio of 10: 1 to 1: 1, preferably 4: 1 to 1.5: 1. Compounds that can be prepared by reacting at 100 to 190 ° C. under German Patent Publication No. 35 18 770.
    More particularly preferred compound (A) is carried out at 100 to 195 ° C. in the presence or absence of a catalyst, alternatively initiated by an initiator in which a monofunctional group having an alcoholic OH group, phenolic OH group or SH group is reacted, diepoxy A mixture of diepoxide compounds and / or diepoxide compounds alone or with one or more monoepoxide compounds to form an epoxy resin, wherein the de-compound and the initiator are incorporated in a molar ratio of 2: 1 to 10: 1. Compounds which can be prepared by polyaddition reactions (see German Patent Publication No. 35 18 732).
    Polyepoxides which are used to prepare particularly preferred component (A) and which can also be used as component (A) per se are polyphenol polyglycidyl ethers prepared from polyphenols and epihalohydrin. It can be very particularly preferred to use, for example, bisphenol A and bisphenol F as polyphenols. Moreover, 4,4'- dihydroxy benzophenone, 1, 1-bis (4-hydroxyphenyl) ethane, 1, 1-bis (4-hydroxyphenyl) isobutane, 2, 2-bis (4- Hydroxy-tert-butyl-phenyl) propane, bis (2-hydroxynaphthyl) methane, 1,5-dihydroxynaphthalene, and phenolic novolak resins are suitable. Other suitable polyepoxys are, for example, ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,4-propylene glycol, 1,5-pentanediol, 1,2,6-hexanetriol , Polyglycidyl ethers of polyhydric alcohols such as glycerol and 2,2-bis (4-hydroxycyclohexyl) propane and also neopentyl glycol.
    In a preferred embodiment, the modified polyepoxy resin is prepared by heating together bisphenol A, bisphenol A diglycidyl ether and bisphenol A / ethylene oxide adduct and forming the modified product by an amine catalyst.
    Also, for example, polyglycidyl esters of polycarboxylic acids such as oxalic acid, succinic acid, glutaric acid, terephthalic acid, 2,6-naphthalenedicarboxylic acid and dimerized linoleic acid can be used. Typical examples are glycidyl adipate and glycidyl phthalate.
    Also suitable are polyepoxide compounds obtained by epoxidizing hydantoin epoxide, epoxidized polybutadiene, and olefinically unsaturated aliphatic compounds.
    Modified polyepoxide refers to polyepoxides in which some reactive groups react with modified compounds. An example is the modification of an epoxy resin with a monophenol or thiol compound.
    Other examples of modified compounds are
    a) carboxyl containing compounds such as saturated or unsaturated monocarboxylic acids (e.g. benzoic acid, linseed oil fatty acid, 2-ethylhexanoic acid, versaic acid), aliphatic, alicyclic and / or of various chain lengths Aromatic dicarboxylic acids (eg adipic acid, sebacic acid, isophthalic acid or dimer fatty acids), hydroxyalkylcarboxylic acids (eg lactic acid, dimethylolpropionic acid), and also carboxyl containing polyesters , or
    b) amino containing compounds, for example diethylamine or ethylhexylamine or diamines having secondary imino groups, for example N, N'-dialkylalkylenediamines, such as N, N'-dimethylethylenediamine, N, N'-dialkylpolyoxyalkyleneamines such as N, N'-dimethylpolyoxypropylenediamine, cyanoalkylated alkylenediamines such as bis-N, N'-cyanoethylethylenediamine, bis-N, Cyanoalkylated polyoxyalkyleneamines such as N'-cyano-ethylpolyoxypropylenediamine, polyaminoamides such as versamide, for example diamines (e.g., containing terminal amino groups) Methylenediamine), monoglycidyl ethers or monoglycides of polycarboxylic acids, in particular dimer fatty acids and monocarboxylic acids, in particular reaction products of fatty acids or α-branched chain fatty acids such as 1 mole of diaminohexane and versatonic acid Dill esters, especially glycidyl Reaction products with 2 moles of ester, or
    c) hydroxyl containing compounds such as neopentyl glycol, bisethoxylated neopentyl glycol, neopentyl glycol hydroxypivalate, dimethylhydantoin-N, N'- diethanol, 1,6-hexanediol, 2,5-hexanediol, 1,4-bis (hydroxymethyl) cyclohexane, 1,1-isopropylidene-bis (p-phenoxy) -2-propanol, trimethylolpropane, pentaerythritol or amino alcohol Triethanolamine, methyldiethanolamine or hydroxyl containing alkyl ketimines, for example aminomethyl-1,3-propanediol methylisobutyl ketimine or tris (hydroxymethyl) aminomethane cyclohexanone ketimine And also polyglycol ethers, polyester-polyols, polyetherpolyols, polycaprolactone-polyols, polycaprolactam polyols of various functional groups and molecular weights, or
    d) saturated or unsaturated fatty acid methyl esters which react with the hydroxyl groups of the epoxy resin in the presence of sodium methoxide
    to be.
    As component (B), primary and / or secondary amines and / or salts thereof and / or salts of tertiary amines can be used, with secondary amines being particularly preferred component (B).
    Preferably, the amine should be a water soluble compound. Examples of such amines are mono- and dialkylamines such as methylamine, ethylamine, propylamine, butylamine, dimethylamine, diethylamine, dipropylamine, methylbutylamine and the like. Likewise, alkanolamines such as methylethanolamine, diethanolamine and the like are suitable. Moreover, dialkylaminoalkylamines are suitable, for example, dimethylaminoethylamine, diethylaminopropylamine, dimethylaminopropylamine and the like. In many cases high molecular weight monoamines can also be used, but low molecular weight amines are used.
    Polyamines having primary and secondary imino groups can be reacted with epoxide groups in the form of their ketimines. Ketimines are prepared from polyamines in conventional manner.
    The amine may also include other groups as long as they do not interfere with the reaction of the amine with the epoxide group and do not cause gelation of the reaction mixture.
    The charge required for dilution in water can be generated by protonation with a water soluble acid (eg, boric acid, formic acid, lactic acid or acetic acid) or by reaction of an oxirane group with an amine salt.
    As the amine salt, tertiary amine salts can be used.
    The amine component of the amine acid salt is an amine which may be unsubstituted or substituted as in the case of hydroxylamine, these substituents should not interfere with the reaction of the amine acid salt with the polyepoxide and the reaction mixture should not gel. . Preferred amines are tertiary amines such as dimethylethanolamine, triethylamine, trimethylamine, triisopropylamine and the like. Examples of other suitable amines are specified in column 5, lines 3 to 7, column 42 of US Pat. No. 3,839,252.
    As component (C), polyols, polycarboxylic acids, polyamines or polysulfides or mixtures of compounds from these substance groups are used. Suitable polyols include diols, triols and higher polymerized polyols such as polyesterpolyols, polyetherpolyols.
    Suitable polyalkylene ether polyols for component (C) are
    H ----- [O ----- (CHR) n ] m ----- OH, wherein R = lower alkyl radical with or without hydrogen or various substituents, n = 2 to 6 and m = 3 to 50 or more). Examples are poly (oxytetramethylene) glycol, poly (oxyethylene) glycol and poly (oxypropylene) glycol (so-called polypropylene glycol).
    When a polyetherpolyol which can be obtained by reacting a cyclic polyol such as bisphenol A with an ethylene oxide or a mixture of alkylene oxide and ethylene oxide containing 3 to 8 carbon atoms is used as component (C) In particular, a particularly preferred cationic amine modified epoxy resin is obtained (see EP-A-74634).
    Likewise, polyesterpolyols can be used as the polymer polyol component. Polyesterpolyols can be prepared by polyesterizing organic polycarboxylic acids or their anhydrides with organic polyols containing primary hydroxyl groups. Polycarboxylic acids and polyols are typically aliphatic or aromatic dicarboxylic acids and diols.
    Diols used to prepare polyesters include alkylene glycols such as ethylene glycol, butylene glycol, neopentyl glycol and other glycols such as cyclohexanedimethanol.
    The acid component of the polyester consists mainly of low molecular weight carboxylic acids having 2 to 18 carbon atoms or anhydrides thereof in the molecule. Examples of suitable acids are phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, adipic acid, azelaic acid, sebacic acid, maleic acid and glutaric acid. Instead of these acids, it is possible to use their anhydrides in which they are present.
    It is also possible to use polyesterpolyols derived from lactones as component (C). These products are obtained by reacting ε-caprolactone with polyols. Such products are described in US Pat. No. 3,169,945.
    The polylactone polyols obtained by this reaction are characterized by the presence of repeating polyester units derived from terminal hydroxyl groups and lactones. These repeating molecular units are represented by the formula

    Wherein n is at least 4, preferably 4 to 6 and the substituents are hydrogen, alkyl radicals, cycloalkyl radicals or alkoxy radicals. Examples of these compounds that may be mentioned include

    Polycaprolactone diols.
    Also used as component (C) are aliphatic and / or alicyclic polyfunctional alcohols or carboxylic acids having a molecular weight of 350 or less. Advantageously, they have branched chain aliphatics, in particular having at least one neo structure.
    Suitable compounds include

    Wherein Y = OH, COOH, X = (CH 2 ) n , , ,
    a = 0, 1, b = 0, 1, I = 0-10, m, n = 1-10, R 1 , R 2 , R 3 = H, alkyl radicals of 1 to 5 carbon atoms). .
    Compounds that may be mentioned include diols, for example ethylene glycol, diglycol, dipropylene glycol, dibutylene glycol, triglycol, 1,2-propanediol, 1,3-propanediol, 2,2-dimethyl- 1,3-propanediol, 2,2-diethyl-1,3-propanediol, 2-methyl-2-ethyl-1,3-propanediol, 2-methyl-2-propyl-1,3-propanediol , 2-ethyl-2-butyl-1,3-propanediol, 1,2-butanediol, 1,4-butanediol, 2,3-butanediol, 2-ethyl-1,4-butanediol, 2,2-diethyl -1,3-butanediol, butene-2-diol-1,4. 1,2-pentanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, 2,5-hexanediol, 2-ethyl-1,3-hexanediol, 2,5-dimethyl-2,5-hexanediol, 1,3-octanediol, 4,5-nonanediol, 2,10-decanediol, 2-hydroxyethyl hydroxyacetate, 2,2-dimethyl-3 -Hydroxypropyl 2,2-dimethylhydroxypropionate, 2-methyl-2-propyl-3-hydroxypropyl 2-methyl-2-propylhydroxypropionate, 4,4'-methylenebiscyclohexane Ol and 4,4'-isopropylidenebiscyclohexanol. Some preferred diols include 2,2-dimethyl-1,3-propanediol, 3-methyl-1,5-pentanediol, 2,2-dimethyl-3-hydroxypropyl 2,2-dimethylhydroxypropionate And 4,4'-isopropylidenebiscyclohexanol.
    Suitable carboxylic acids include many dicarboxylic acids, for example oxalic acid, malonic acid, 2,2-dimethylmalonic acid, succinic acid, glutaric acid, adipic acid, hexahydrophthalic acid, maleic acid, fumaric acid, pimelic acid , Suberic acid, azelaic acid, sebacic acid, itaconic acid, citraconic acid and mesaconic acid.
    Examples of dicarboxylic acids which are preferably used are 2,2-dimethylmalonic acid and hexahydrophthalic acid.
    Moreover, long chain dicarboxylic acid can be used as component (C). Examples of these are dimer fatty acids such as dimeric linoleic acid.
    Suitable polyamines as component (C) can be prepared, for example, by reacting primary amines and monoepoxides, and these secondary substituted diamines formed modify the epoxy resin in a suitable manner.
    As component (C) it is also possible to use primary-tertiary diamines or alkanolamines such as aminoethanol or aminopropanol.
    Suitable polyfunctional SH compounds are the reaction products of organic dihalides with sodium polysulfides, and other SH compounds include, for example, hydroxyl-containing linear polyesters, polyethers or polyurethanes with mercaptoacetic acid, 2-mer Reaction products with mercaptocarboxylic acids such as captopropionic acid, 3-mercaptopropionic acid, mercaptobutyric acid and the like.
    The cationic amine modified epoxy resins used are (A) polyepoxides, (B) primary and / or secondary amines and / or salts thereof and / or salts of tertiary amines, and (C) Similarly preferred primers are obtained in the case of reaction products of polyols, in particular polyester- and / or polyetherpolyols.
    The amine modified epoxy resin can be used as an external crosslinked synthetic resin or a self crosslinked synthetic resin, and the self crosslinked amine modified epoxy resin can be obtained by, for example, chemical modification of an amine modified epoxy resin. A self-crosslinking system can be obtained, for example, by reacting an amine modified epoxy resin with a partially blocked polyisocyanate, which possesses an average of one free isocyanate group per molecule and whose blocked isocyanate groups are only blocked at elevated temperatures. .
    Preferred coating materials are obtained when an externally crosslinked amine modified epoxy resin is used in combination with a suitable crosslinking agent.
    Examples of suitable crosslinkers include phenolic resins, polyfunctional Mannich bases, melamine resins, benzoguanamine resins, blocked polyisocyanates, and compounds containing two or more groups of the formula R 1 -O-CO-.
    The radical R 1 represents R 2 -O-CO-CH 2- , R 3 -CHOH-CH 2- , R 4 -CHOR 5 -CHOH-CH 2- , R 2 is alkyl, R 3 is H, alkyl , R 6 -O-CH 2 -or R 6 -CO-O-CH 2- . R 4 is H or alkyl, R 5 is H, alkyl or aryl and R 6 is alkyl, cycloalkyl or aryl.
    Preferred primers are obtained when blocked polyisocyanates and / or compounds containing two or more groups of the formula R 1 -O-CO- are used as crosslinking agents.
    As blocked polyisocyanates, the formed blocked polyisocyanates are stable at room temperature with hydroxyl and amino groups, but any desired polyisocyanate with which isocyanate groups react with compounds reacting at elevated temperatures, generally within about 90 ° C to about 300 ° C. Can be used. In the preparation of blocked polyisocyanates, any desired organic polyisocyanate suitable for crosslinking can be used. Preference is given to isocyanates containing about 3 to 36 carbon atoms, in particular about 8 to about 15 carbon atoms. Examples of suitable diisocyanates include hexamethylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 1-isocyanatomethyl-5-isocyanato-1,3,3- Trimethylcyclohexane and also 4,4'-diisocyanatodiphenylmethane (MDI), and its high molecular weight homologs, commonly known as fractions of MDI preparation. It is also possible to use polyisocyanates having higher isocyanate functional groups. Examples of these are trimerized hexamethylene diisocyanate and trimerized isophorone diisocyanate. Moreover, mixtures of polyisocyanates can also be used. In addition, organic polyisocyanates suitable as crosslinking agents in the context of the present invention may be prepolymers derived from polyols including, for example, polyetherpolyols or polyesterpolyols.
    For the blocking of polyisocyanates, any desired suitable aliphatic, cycloaliphatic or aromatic alkyl monoalcohols can be used, for example aliphatic alcohols such as methyl, ethyl, chloroethyl, propyl, butyl, amyl, hexyl, heptyl, Octyl, nonyl, 3,3,5-trimethylhexyl, decyl and lauryl alcohol, cycloaliphatic alcohols such as cyclopentanol and cyclohexanol and aromatic alkyl alcohols such as phenyl carbinol and methylphenyl carbinol .
    Other suitable blocking agents include hydroxylamines such as ethanolamine, oximes such as methyl ethyl ketone oxime, acetone oxime and cyclohexanone oxime, or amines such as dibutylamine and diisopropylamine. In suitable proportions, the polyisocyanate and blocking agent can also be used to use the partially blocked polyisocyanates described above.
    Examples of the compound containing two or more groups of the formula R 1 -O-CO- include bis (carboxymethyl) azelate, bis (carvalkoxymethyl) sebacate, bis (carbaalkoxymethyl) adipate, bis (car B-alkoxymethyl) decanoate, bis (carbalkoxymethyl) terephthalate, bis (2-hydroxybutyl) azelate and bis (2-hydroxyethyl) terephthalate.
    The crosslinking agent is generally used in an amount of 10 to 50% by weight, preferably 25 to 40% by weight, based on the amine modified epoxy resin. Therefore, the proportion of the epoxy resin is 90 to 50% by weight, preferably 75 to 60% by weight. To increase the flexibility and formability of the coating material it is also possible to add oligomeric polyols which are slightly volatile or non-volatile under baking conditions and which are incorporated as plasticizing segments in the film network during the crosslinking reaction. The amount of these oligomeric polyols in the ratio of the resin / crosslinker mixture may be up to 30% by weight, preferably from 2 to 12% by weight. Examples of these are polyether alcohols and polyester alcohols. One group of polyethers is represented by polypropylene glycol, polyethylene glycol and polypropylene / polyethylene mixed diols, and the other by polyetherols obtained by reaction of monophenols with ethylene oxide and / or propylene oxide. And polyethers prepared from bisphenol A and ethylene oxide and / or propylene oxide. In particular, Pluriol P600, Pluriol P900, Pluriol P2000 (manufactured by BASF), and also Plastilit 3060 (manufactured by BASF) and epoxylated bisphenol A are preferred. Preferred polyester alcohols are polycaprolactones, for example Capa 200 (manufactured by Interox) or PCP 200 (manufactured by Union Carbide).
    The resin / crosslinker / plasticizer mixture can be prepared as an organic solution by dilution with a suitable solvent. The first criterion for dilution is not the solids of the mixture, which can be between 80 and 50%, but a viscosity describing the flow behavior of the mixture. This viscosity is measured according to the flow out method in a DIN4 cup. For the composition of the present invention, the viscosity should be in the range between 150 and 50 seconds, with a preferred range of 110 to 70 seconds. Obviously, however, the highest solids possible are the objectives.
    More preferred dilution forms are formed by aqueous solutions / dispersions of the compositions of the described materials in which water represents the main solvent. For this purpose, basic amino groups from amine modified epoxy resins are converted to hydrophilic salts by neutralization with an acid before or during dilution with water. In one preferred embodiment, only some amino groups are neutralized (less than 100% neutralization). Less complete neutralization inhibits the formation of a clear aqueous solution, instead a colloidal dispersion is formed. For certain solids, the aqueous dispersion has a lower viscosity than that of a fully neutralized aqueous solution. By controlled selection of the degree of neutralization, it is possible in this way to obtain the maximum solids within a given viscosity. On the other hand, the degree of neutralization should be high enough to prevent the coating mixture from separating into two phases.
    Another criterion is the pH of the aqueous coating mixture. For certain levels of bases in amine modified epoxy resins, high degree of neutralization results in low pH, while low degree of neutralization means high pH. Although chemical / hydrolytic stability and physical sedimentation behavior are less threatening at low pH, the effluent viscosity of 150 to 50 seconds required in DIN4 cups can only be achieved at low solids. At high pH it is possible to achieve maximum solids under these conditions, but both the hydrolytic stability and the physical settling stability of the blocked polyisocyanate are greatly threatened. Therefore, the challenge is to select the degree of neutralization such that an optimal balance is achieved between the above mentioned requirements. For certain amine levels in the epoxy amine adduct, characterized by the level of bases in the mixture (MEQ bases in milliequivalents per gram of solid resin), the degree of neutralization is between 70 and 10%, preferably between 40 and 20%. It must exist. Acids used are organic acids and also derivatives of phosphoric acid. Examples of these are formic acid, acetic acid, propionic acid, valeric acid, lactic acid and also hypophosphorous acid.
    The primer of the present invention is used as an organic diluent or as an aqueous diluent. In the case of the aqueous diluent form, particular preference is given to using epoxies modified with monophenol or thiol compounds, and also reaction products with diols, dicarboxylic acids and similar compounds, if necessary.
    In the case of the organic diluent form, preference is given to using as a main resin a composition of matter consisting of an epoxy-amine adduct made elastic with ethoxylated bisphenol A together with a polyisocyanate crosslinker, for example diphenylmethane diisocyanate.
    Primers are prepared by a wide variety of well known methods. Synthetic resins are synthesized according to well known methods in organic solvents (e.g., German Patent No. C-27 01 002 and other patent documents cited on page 2). The synthetic resin solution or dispersion obtained in this way is transferred to the aqueous phase in a neutralized form.
    In addition, the pigment may be incorporated in the form of a pigment paste into the aqueous dispersion of the resin.
    The production of pigment pastes is commonly known and need not be further described herein (DH Parker, Principles of Surface Coating Technology, Interscience Publishers, New York (1965); RL Yates, Electropainting, Robert Draper Ltd., Teddington / England (1966); HF Payne, Organic Coating Technology, Volume 2, Wiley and Sons, New York (1961)).
    Pigment pastes are prepared, for example, using epoxy-amine adducts containing quaternary ammonium groups.
    The pigment paste may in principle comprise all pigments suitable for the coating material. Titanium dioxide is generally the sole or primary white pigment. However, other white pigments or enhancers, such as antimony oxide, zinc oxide, basic lead carbonate, basic lead sulfate, barium carbonate, porcelain, clay, calcium carbonate, aluminum silicate, silica, magnesium carbonate and magnesium silicate, are also used. Can be. Examples of colored pigments that may be used are cadmium yellow, cadmium red, carbon black, phthalocyanine blue, chrome yellow, toluidyl red and hydrated iron oxide.
    In addition to pigments, pigment pastes may also include plasticizers, fillers, wetting agents, and the like.
    The pigment paste is added to the aqueous dispersion of the synthetic resin in an amount such that the finished primer has the desired properties. In most cases the weight ratio between pigment and synthetic resin is from 0.05 to 0.5.
    In addition to synthetic resins and pigment pastes, the primers of the present invention may also include other conventional additives, such as cosolvents, antioxidants, surfactants, and the like.
    Solids of the primer of the present invention are preferably 7 to 35 parts by weight, particularly preferably 12 to 25 parts by weight. The present invention is also preferred by cleaning the substrate surface, applying an organic or inorganic pretreatment composition if necessary, applying a primer, applying the top coat by spraying, dipping, knife coating, roller coating or brushing and subsequent baking. A method of coating a metal substrate is provided.
    <normal course>
    Following application to the substrate, the primers of the invention are preferably coated on top. The application of the top coat can be done only after the application of the primer or wisely after the mechanical deformation / molding of the primer coated on the substrate is completed.
    In principle, all commercially available conventional top coats can be used. Such coating materials are known to those skilled in the art for a wide range of requirements profiles.
    Requirements for topcoats are first determined by the intended field of use. In the liquid phase, the top coat must first withstand high shear stresses in the course of roller application without performing any changes in the extended processing. A skillful blend of manufacturing and testing conditions perfectly achieves the desired hue and gloss. Lamination to the protective sheet further imposes the requirement of controlling the tack to this sheet. Typical coat thicknesses are generally about 20 μm. As the top coat, a commercially available coil coated polyester top coat or a coil coated polyurethane top coat (eg BASF Lake + Farben AG, data sheet) can be used.
    <Multicoat structure>
    The product of the present invention preferably comprises a primer and a top coat that are two coat structures. Film formation takes place between 200 and 260 ° C. in about 30 to 60 seconds and typical dry film thicknesses are 25 μm and 100 to 250 μm, respectively.
    On the coating film, printed and decorative sheets or removable protective sheets can be applied. Related sheets are mainly PVC and PVF sheets. These sheets are fixed under high temperature conditions using an adhesion promoter. The removable protective sheet is fixed under cold conditions or adhesively applied under high temperature conditions. In general, a (protective) coating of thickness 5-15 μm is applied to the back of the metal sheet with one or two coats.
    Particular features that may be mentioned are woven coatings and combinations of coatings and transparent sheets, which are mainly used in the household goods industry. 3 and 4 coat systems are especially manufactured for exterior applications.
    In the automotive industry, coil coated galvanized materials are used. The system involved in this case is preferably suitable for different requirements in the case of zinc-rich paints, weldable or non-welding primers (“pre-primed”) and body parts or accessories which are thin and 1 to 3 μm sealants. Thickener systems of less than one micrometer.
    Composite metal sheets in the form of three coats are produced with a total thickness of 0.8 to 2.0 mm in symmetrical or asymmetric cross sections. The metal top sheet used can be any type of metal sheet, including for example stainless steel or aluminum. Viscoelastic interlayers with high internal friction have a thickness of 25-50 μm. Type 1 with a high loss factor (as a measure of attenuation) for use between about -10 and +60 ° C, for example for horizontally opening bins doors and waste glass collection containers, depending on the required work area. And type 2 (particularly in the case of automotive accessories such as oil pans and valve caps) for use between about 50 and 130 ° C.
    <Field of use>
    The present invention also provides for use in coated commercials for manufacturing building accessories, furniture, appliance paneling, vehicle bodies, household items and lamp cases. Particularly preferred areas include those in which a small radius of curvature is required, for example in the case of a vehicle body.
    For many applications, it is sufficient to coat the surface with a single coat. In particular, the back side of the coated coil is covered with only a single coat. In this case, the backside coating materials used are the primers of the present invention because they have excellent tack and corrosion protection properties.
    It is also common to use a single coat coating material in the form of a primer of the present invention on the front face. For example, for some interior applications in the building sector it is sufficient to work with a single coat having a thickness of 20 to 22 μm. Also in the packing sector coils coated with only one coat are used.
    In the following text, the individual fields of use are described in more detail.
    <Building exterior>
    In the case of facades and roofs as well as building accessories, for example doors, doors and window frames, the primers of the invention are preferably applied with a first coat of 5-8 μm. The top coat is then used. After drying, polyethylene sheets are protected against mechanical damage in subsequent processing. Following the assembly of the components, this sheet is again removed from the object.
    The back side can be covered, for example, with the primers of the invention, and in the case of component preparation is completed using rigid polyurethane foams for insulation. Therefore, the adhesive properties of this kind of backside coating material with respect to polyurethane foam have to be optimized.
    For high temperature immersion galvanized and electrogalvanized galvanized substrates of standard steel, the primers of the invention can likewise be used. Preferably a CD 24 top coat of preferably 18 to 22 μm is applied according to the color tone on a primer coat having a thickness of 5 to 8 μm. Within the gloss range of 20 to 70 units, this phase has good hardness, represented by pencil hardness F, and flexibility of T 3.0 or less, measured at the bending point. In addition to these basic data which are important for other mechanical operations, the long term behavior of the finished component is also important. Weathering stability is achieved over a period of 5 to 10 years. This means that the gloss and color tone hardly change in this period, and that corrosion at edges and damage sites is only within a narrow range. Of course, since the pigments also exhibit different weathering behavior, the specific weathering data depends on the particular color tone under consideration.
    <Building construction>
    For the manufacture of ceiling parts, partitions, shelves, store designs, steel furniture and many other items, the primers of the present invention are generally applied to substrates that are primarily used. Preferably, a coat having a thickness of 5 to 8 μm is further coated with a top coat where a temporary protective sheet is further applied, if necessary.
    Especially for parts subjected to high mechanical stress, weaving coating systems can also be used. In this case, the sensitivity to mechanical damage is relatively low due to the peak and valley structures. The overall coat thickness is about 32-35 μm, depending on the degree of weaving the woven coating material itself requires 12-15 μm. In this case, a bending force of T 0.5 to T 2.5 is achieved depending on the system. Suitable areas of use in the interior sector include partitions, lining of ceiling parts, especially cold storage installations, and also shelf, warehouse and store design systems. However, these woven coating materials are also used in exterior applications for shutters, blinds, doors and doors.
    <White product>
    By white product is meant lamps and light fixtures and also household appliances such as refrigerators, freezers, washing machines, drying machines, dishwashers, microwave ovens and kitchen hoods.
    The system for lamp and light fixtures consists of white primers and tops according to the invention. This system is excellent in good surface hardness combined with normal deformation properties. Reflectivity important in lighting is especially optimized for this gloss class.
    Two-coat systems have been developed for long-array emitters with very complex bend radii. Here, good flexural forces are achieved at T 0 to T 0.5 for standard steel and aluminum. A special property of this system is that the coating material acts simultaneously as a primer and a top coat. The entire coating system consists of the primer of the present invention of 2 × 13 μm. In addition to its good mechanical-technical properties, this primer system is considered to be operable in excess of 70 m / min, if the setting of the equipment is suitable, despite the high gloss in units of more than 80.
    In the case of household appliances, in principle there is a difference between two different systems. If a smooth surface is required, the system is fabricated in the manner described above. In order to achieve a surface having a structure such as that of a conventional spray printed surface, the woven primer of the present invention is preferentially applied. Subsequently, a smooth top coat is applied onto the primer.
    In principle, the requirements for different household items are consistent with the subsequent use. In the case of refrigerators, care should be taken to ensure marking resistance by various foods, while the outer surface should be easily cleaned to remove spilled polyurethane foam used as insulation in the manufacture of refrigerators or freezers, and the coating on the washing machine surface should be Particularly good resistance to detergents is required. The requirements for dishwashers and dryers are similar to those for washing machines.
    The requirements for the entire, coated surface are very large in terms of surface hardness, good deformability and binding of chemical or food resistance, which binding is met to a certain extent by the primers used according to the invention.
    <Car production>
    Very different applications are needed in automobile construction. In this particular case it is necessary for the substrate, pretreatment and coating materials to be primary to one another in a very balanced manner.
    In this case, the above-described primers having special advantages can be used.
    <Manufacture process>
    Substrates, preferably consisting of steel or aluminum, pass through the entire continuous strip processing line at a limited speed. In so doing, it is introduced into a multi-step treatment consisting of cleaning, pretreatment, application of organic coatings, baking / drying in a through oven, and coiling of the coated product or cutting into panels.
    To be precise, in the case of a typical liquid coating, the sequence of operation is divided into 11 operations.
    The strip speed according to the invention is preferably in the range of 30 to 120 (m / min).
    In the following description the invention is described in more detail with reference to the drawings.
    In step (1), the metallic substrate material is released from the unwinding machine. The first part of the strip to be treated in step (2) is mechanically attached (sewn) to the end of the strip to be coated. In step (3) the strip is precleaned. In this step there is a stretch arrangement process to ensure a good planar position. Wash with acidic or alkaline solution. Subsequently, chemical pretreatment is performed.
    According to the subsequent treatment, washing, neutralization and drying are carried out in step (4). In step (5) a primer is applied and the strip is coated on one or both sides. The strip then passes through the first oven 5.
    The strip is then introduced to cooling step 7. It is then coated on top or on both sides in the apparatus 8.
    In the apparatus 9, the coating can alternatively be embossed or passed through a second oven and / or alternatively a protective sheet can be applied.
    It is then introduced to cooling step 10. Finally, quality control is performed in step 11 (visual surface observation, random sampling and testing). Finally, it is rewound and also cut into lengths (if split) or cut into panels and, if necessary, packed.
    The invention is described in more detail with reference to examples in terms of coating materials used below.
    All parts and percentages are by weight unless otherwise stated.
    <Examples 1 to 4>
    1. Preparation of the crosslinking agent (crosslinking agent A):
    In a reactor equipped with a stirrer, a reflux cooler, an internal thermometer and an inert gas inlet, 1133 parts of tolylene diisocyanate (2,4- and 2,6-isomer mixture 80:20) and 356 parts of MIBK were charged under a nitrogen atmosphere. 0.7 parts of dibutyltin dilaurate were added and 290 parts of trimethylolpropane were introduced in small portions at equal intervals over 4 hours while the internal temperature did not increase above 45 ° C. After 30 minutes, the NCO equivalent weight was determined to be 217 (based on the solid component). 722 parts of n-propyl glycol were added dropwise over 1 hour with further cooling. At the end of the addition, the mixture was heated to 100 ° C. and reacted for another 1 hour. At this moment, the NCO group could no longer be observed. The composition was then cooled and diluted with 500 parts of MIBK to give a solids of 70% (1 hour at 130 ° C.).
    2. Preparation of Crosslinker (Crosslinker B):
    2440 parts of triisocyanurate hexamethylene diisocyanate under nitrogen were placed in a suitable reaction vessel, which was diluted with 850 parts of methyl isobutyl ketone (MIBK). The mixture was heated to 50 ° C. and 1560 parts of di-n-butylamine was added at a rate such that the temperature was maintained at 0-70 ° C. with external cooling. At the end of the addition the temperature was increased to 75 ° C., maintained for 1 hour and 150 parts of n-butanol were added. Isocyanate equivalents and amine equivalents were each 20,000 or more. Solids of the product was 79.6% (1 hour at 130 ° C).
    3. Preparation of Amine Based Main Resin:
    In a laboratory reactor equipped with a stirrer, reflux cooler, thermometer and inert inlet pipe, heated to a heat transfer oil, 1960 parts of a commercial epoxy resin (Epikote 1 001, manufactured by Shell) based on bisphenol A and having an equivalent weight of 490 were charged at 125 ° C. In the presence of 220 parts of nonylphenol and 111 parts of xylene. When the melt became clear, the residual adhered moisture was removed under vacuum for 20 minutes using a water separator. 3.5 parts of N, N-dimethylbenzylamine were then added and the reaction was carried out at 130 ° C. to an epoxide equivalent weight (EEW) 1080. The mixture was then cooled and diluted with 142 parts of butyl glycol and 254 parts of xylene. At 90 ° C., 147 parts of diethanolamine were added and the reaction was carried out for 1 hour. Subsequently, the reaction mixture was diluted with 107 parts of propylene glycol phenyl ether and 400 parts of isobutanol and further cooled. 46 parts of N, N-dimethylaminopropylamine were added at 70 ° C. and the mixture was heated to 90 ° C. and maintained at this temperature for 2 hours. Then cooled and discharged. The resin had a 70% solids and a viscosity of 3.8 dPas (40% concentration in propylene glycol methyl ether, cone and plate viscometer at 23 ° C.).
    4. Preparation Examples of the Primer of the Invention:
    Example 1 Organic Solution of Resin / Crosslinker Mixture (BM 1)
    916.7 parts of the resin (step 3) was added to 252 parts of crosslinker A (step 1), 220.5 parts of crosslinker B (step 2), 43.2 parts of plastilit (Plastilit, manufactured by BASF) and 43.2 parts of dibutyltin dilaurate (commercial solution) 4.2 Mixed with part. When the mixture was homogenized it was diluted with 639 parts of MIBK (theoretically 50% solids).
    <Example 2>: Aqueous resin / crosslinker mixture (BM 2)
    Resin (Example 1) 916.7 parts, Crosslinker A (Step 1) 252 parts, Crosslinker B (Step 2) 220.5 parts, Plastilite (manufactured by BASF) 3060 43.2 parts and Dibutyltin dilaurate (commercial solution) 4.2 The portions were mixed at room temperature. 2.1 parts of an antifoaming agent solution (Surfynol 104, a 50% concentration solution in butyl glycol) and 23.8 parts of glacial acetic acid were added, and the mixture was diluted with 682 parts of deionized water with stirring to give an outflow viscosity of 70 seconds (4 cups of DIN). It was made. Solids of the aqueous mixture were 46.0% (1 hour at 130 ° C). The solid fraction had 0.68 MEQ base and 0.17 MEQ acid (in each case milliequivalents / g).
    <Example 3>: Aqueous resin / crosslinker mixture (BM 3)
    The BM 2 described in Example 2 was repeated except that dibutyltin dilaurate was replaced with an equivalent amount of lead octoate solution. Solids content of the mixture was 45.2%. MEQ base was 0.67 milliequivalents / solid phase g and MEQ acid was 0.17 milliquivalents / solid phase g.
    <Example 4>: aqueous resin solution (BM 4)
    Into a laboratory reactor heated with heat transfer oil and equipped with a stirrer, reflux cooler, thermometer and inert inlet pipe, 1346 parts of commercial epoxy resin based on bisphenol A and having an equivalent weight of 188 and 612 parts of bisphenol A were added. Heated to 130 ° C. in presence. Then 2.2 parts of triphenylphosphine were added and an initial exothermic reaction was carried out at 130 ° C. to EEW 1123 or less. The reaction mixture was then diluted with 726 parts of butyl glycol and a mixture of 152 parts of lactic acid, 147 parts of N, N-dimethylethanolamine, 51 parts of propylene glycol phenyl ether and 51 parts of deionized water at 88% concentration was added at 80 ° C. After 90 minutes, when the reaction mixture had an acid value of 1.3 mg KOH / g, it was cooled and diluted with deionized water at room temperature until the outflow viscosity was less than 100 seconds in a DIN 4 cup. The resin solution had a solids content of 46.6% (1 hour at 130 ° C.) and a base content of 0.75 milliequivalents / g.
    <Example 5>
    a. Modified Epoxy Resin:
    The following example shows the preparation of an aminated epoxy resin comprising ethoxylated bisphenol A as the primary amino group and the flexible group. Bisphenol A, bisphenol A diglycidyl ether, and bisphenol A / ethylene oxide adduct were heated together to form a modified polyepoxy resin by amine catalysis. This was subsequently reacted with a mixture of secondary amines. At the end of the reaction, the product was diluted to 60% solids.
    Starting material parts by weight
    Epikote 828 682.4
    2. Bisphenol A 198.4
    3.Dianol 265 252.7
    4. Methyl Isobutyl Ketone 59.7
    5. Benzyldimethylamine 1.0
    6. Benzyldimethylamine 2.7
    7. Decettin 65.4
    8. Methanololamine 59.7
    9. Solvesso 150 55.2
    10. 1-phenoxy-2-propanol 43.0
    11.Butyl Glycol 299.0
    12.Solvesso 150 342.0
    1) Epicoat 828: A liquid epoxy resin prepared by reacting bisphenol A and epichlorohydrin having an epoxide equivalent weight of 188 (manufactured by Shell Chemical).
    2) Dianol 265: ethoxylated bisphenol A with OH of 222 (manufactured by Akzo)
    3) Diketimine: 75% concentration in diketimine, methyl isobutyl ketone from the reaction of diethylenetriamine and methyl isobutyl ketone.
    Epicoat 828, bisphenol A and dianol 265 were heated to 145 ° C. in a reactor under a nitrogen atmosphere. 1.0 part of benzyldimethylamine (catalyst) was then added and the reaction mixture was heated to a temperature between 160 ° C and 190 ° C. When the epoxide equivalent weight reached 640, the reaction mixture was cooled to 145 ° C. The remainder of the benzyldimethylamine was then added and the temperature maintained at 145 ° C. after about 2.5 hours until an epoxide equivalent weight of 1120 was achieved. Immediately after, the temperature was reduced to 100 ° C. by evaporative cooling. Then a mixture of secondary amines was added and the reaction was held at 115 ° C. for about 1 hour until the viscosity reached about 6 dPas (50% concentration dilution in methoxypropanol, ICI conical and plate viscometer). Then, phenoxypropanol and residual solvent were added to obtain a resin having a solid content of 60% and a viscosity of 20 dPas (50% concentration in butyl glycol, ICI conical and plate viscometer).
    b. Preparation of Polyurethane Crosslinkers:
    A polyurethane crosslinker was prepared from diphenylmethane diisocyanate by 4.3 moles of 6 moles of isocyanate first reacted with butyl diglycol and the remaining 1.7 moles with trimethylolpropane. The crosslinker was in the form of an 80% concentration solution in methyl isobutylketone and isobutanol (weight ratio 9: 1).
    Starting material parts by weight
    Basonat A 270 1) 810.0
    2. Dibutyltin Dilaurate 0.5
    3. Butyl diglycol 696.6
    4. Methyl Isobutyl Ketone 287.2
    5. Trimethylolpropane 85.8
    6. Butanol 39.8
    7.Methyl isobutyl ketone 71.1
    1) Basonat A 270: trade name for diphenylmethane diisocyanate (manufactured by BASF)
    Components 1 and 2 were placed in the reactor. Component 3 was weighed while maintaining the temperature below 60 ° C. When the NCO equivalent weight reached 890, the batch was diluted with MIBK and TMP was added. The reaction was kept at 100 ° C. until conversion was complete. The reaction mixture was finally diluted with butanol and MIBK to 80% solids. The viscosity was 6 dPas (60% concentration in Solbenon PM, ICI conical and plate viscometer).
    c. Resin Crosslinker (BM 5)
    41.6 parts of the modified epoxy resin solution (Example 5, a.) And the polyurethane crosslinker (Example 5, b.) Were mixed at room temperature and the monobutyltin oxide solution (MBTO solution, 35% concentration, made by Atochem) 0.9 parts were added. The mixture was subsequently adjusted with butyl glycol to have a process viscosity of 80-100 seconds in a DIN 4 cup.
    5. Performance test
    The binders described above according to Examples 1 to 5 were applied to a hot dip galvanized steel panel (Bonder 1303, manufactured by Chemetall) using a coating bar (rod no. 10) and coil coating conditions with an average peak temperature of 216 ° C. Baked under.
    For comparison, prior art primers were tested.
    exam unit BM 1 BM 2 BM 3 BM 4 BM 5 CP21-0916 Control 1)Coat thickness Μm 5 5 5-6 3-5 4 5 MEK test 2) DS 13 11 15 2 15 15 Salt Spray Test 1008 Hours Scribe creep mm 0 0.5 0.5 0.5 0.8 1-2 Edge creep mm 3-4 1-3 1-3 2 2 1-2 T-bend 3) TO TO TO TO TO TO TO 1) Primer free from chromate for comparison (manufactured by BASF) 2) Crosslinking test: Value of double stroke (DS) using cotton pads wetted with methyl ethyl ketone until film breaks 3) Flexibility test according to ECCA T7
    The table shows that the scribe creep according to the invention is 0.8 mm or less, whereas in the comparative example it is 1 to 2 mm.
    <Example of Colored Coil Coating Primer>
    3.38 parts of modified epoxy resin of Examples 4, 5.a.
    Aerosil 200 100% 0.23 parts
    Finn talc M5 micro 4.16 parts
    Titanium Rutile RR2 EI.Arm16.96 Part
    Shieldex CP4-7394 Part 4.32
    Sicor ZNP / S 5.86 Part
    Solvesso 150 7.71
    Butyl Glycol 7.71 parts
    Was premixed in the dissolver for 10 minutes and then ground in a sand mill at 13-15 μm for 25 minutes. This raw coating paste was subsequently mixed with 9.25 parts of the modified epoxy resins of Examples 4, 5.a., 10.49 parts of the crosslinker of Examples 4, 5.b. and 0.93 parts of the monobutyltin oxide solution and the mixture was Thoroughly homogenized.
    The resulting primer is applied to a hot dip galvanized steel panel (Bonder 1303, Chemetall) and a galvanized steel plate (Granodine 108, chromed, Henkel) using a coating bar (rod no. 10), Baking at the peak temperature of 216 ° C. under these conditions.
    exam Hot immersed substrate Galvanized substrate Coat thickness [μm] 5 5 MEK [DS] 〉 30 〉 30 Salt Spray Test 1008 Hours Scribe creep [mm] < 2 0.5 Edge creep [mm] < 2 One T-bend 35 TO
    权利要求:
    Claims (10)
    [1" claim-type="Currently amended] Clean the substrate surface, apply organic and / or inorganic pretreatment compositions if necessary, apply primers comprising amine modified epoxide resins, and apply top coat by spraying, dipping, knife coating, roller coating or brushing Thereby preferably coating a substrate of metal.
    [2" claim-type="Currently amended] The method of claim 1 wherein the amine modified epoxy resin is
    A) modified or unmodified polyepoxides,
    B) primary and / or secondary amines and / or salts thereof and / or salts of tertiary amines, and if necessary
    C) of polyols, polycarboxylic acids, polyamines or polysulfides
    The reaction product.
    [3" claim-type="Currently amended] The method of claim 1 or 2, wherein the primer is present in organic or aqueous diluted form.
    [4" claim-type="Currently amended] 4. The process of claim 3 wherein the amine modified epoxy resin is a reaction product of an epoxy resin, amine and, if desired, diol and / or dicarboxylic acid modified with a monophenol compound or thiol compound.
    [5" claim-type="Currently amended] Coated with one or more coats, cleaning the substrate surface, applying an organic and / or inorganic pretreatment composition if necessary, applying a primer coat, and optionally top coat or plural by spraying, dipping, knife coating, roller coating or brushing Preferably by applying a top coat of the coating, then baking and, if necessary, laminating a removable sheet on the coated film, wherein the primers in the at least one coating film comprise an amine modified epoxy resin. .
    [6" claim-type="Currently amended] The method of claim 5 wherein the amine modified epoxy resin is
    A) modified or unmodified epoxides,
    B) primary and / or secondary amines and / or salts thereof and / or salts of tertiary amines, and if necessary
    C) of polyols, polycarboxylic acids, polyamines or polysulfides
    Coated substrate which is a reaction product.
    [7" claim-type="Currently amended] The coated substrate of claim 5, wherein the primer comprises a resin in organic or aqueous diluted form.
    [8" claim-type="Currently amended] 8. The coated substrate of claim 7, wherein the amine modified epoxy resin is a reaction product of an epoxy resin, an amine and, if desired, a diol and / or dicarboxylic acid, modified with a monophenol compound or thiol compound.
    [9" claim-type="Currently amended] The compound of claim 8, wherein component A is
    (a) a diepoxide compound or mixture of diepoxide compounds having an epoxide equivalent weight of less than 2000, and
    (b) a compound in which a monofunctional group reacts with an epoxide group under certain reaction conditions and comprises a phenol or thiol group, or a mixture of such compounds
    Is prepared by reacting component (a) with component (b) at 100 to 190 ° C in the presence or absence of a catalyst, using a molar ratio of 10: 1 to 1: 1, preferably 4: 1 to 1.5: 1. Coated substrate that can be.
    [10" claim-type="Currently amended] Use of a coated substrate according to any one of claims 5 to 9 for manufacturing building accessories, furniture, appliance paneling, vehicle bodies, household items and lamp cases.
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    同族专利:
    公开号 | 公开日
    BR9713844A|2000-02-29|
    WO1998024857A1|1998-06-11|
    AU5658498A|1998-06-29|
    AT254155T|2003-11-15|
    DE19650157A1|1998-06-10|
    EP0941295B1|2003-11-12|
    JP2001505481A|2001-04-24|
    CN1239981A|1999-12-29|
    EP0941295A1|1999-09-15|
    US6413642B1|2002-07-02|
    AU740515B2|2001-11-08|
    CA2274051A1|1998-06-11|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    法律状态:
    1996-12-04|Priority to DE1996150157
    1996-12-04|Priority to DE19650157.1
    1997-12-02|Application filed by 베른하르트 클루트, 바스프 코팅스 악티엔게젤샤프트, 옌스 피셔, 한드룽스베볼매크티그테르 프로쿠리스트
    2000-09-15|Publication of KR20000057389A
    优先权:
    申请号 | 申请日 | 专利标题
    DE1996150157|DE19650157A1|1996-12-04|1996-12-04|Process for coating substrates, preferably of metal|
    DE19650157.1|1996-12-04|
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