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    • 专利摘要:
    The present invention provides a cationic electrodeposition coating composition capable of obtaining a coating film having excellent anticorrosive properties without containing heavy metal-based rust preventive agents such as lead compounds due to environmental influences. That is, the present invention is a cationic electrodeposition coating composition comprising a water-soluble or water-dispersible phosphonium group-containing compound having a group represented by the following formula (1). Where R is the same or different and represents an alkyl group or a hydroxyalkyl group, at least one of R being a hydroxyalkyl group.
    公开号:KR20020073406A
    申请号:KR1020020013752
    申请日:2002-03-14
    公开日:2002-09-26
    发明作者:노지리히로유키
    申请人:닛본 페인트 가부시끼가이샤；
    IPC主号:
    专利说明:

    Cationic electrodeposition coating composition comprising a phosphonium group-containing compound {CATIONIC ELECTRODEPOSITION COATING COMPOSITION COMPRISING PHOSPHONIUM GROUP-CONTAINING COMPOUND}
    [1] The present invention relates to a cationic electrodeposition coating composition, and more particularly, to a cationic electrodeposition coating composition containing a phosphonium group-containing compound as a so-called organic inhibitor exhibiting a corrosion inhibiting effect.
    [2] Since the cationic electrodeposition paint can be coated even in detail, it can be applied in detail and automatically and continuously. Therefore, the cationic electrodeposition paint has a large and complicated shape, such as an automobile body, and has a high degree of corrosion resistance. It is widely used as a coating method. In addition, since the use efficiency of paint is very high compared with other coating methods, it is economical and it is widely spread by the industrial coating method.
    [3] Cationic electrodeposition paints generally used in automobiles and the like include acid neutralizing amine-modified epoxy resins and block isocyanate curing agents, and lead compounds are used as rust inhibitors. However, in recent years, development of the cationic electrodeposition paint which does not use a lead compound from the viewpoint of environmental protection has advanced.
    [4] As a cationic electrodeposition paint that does not use a lead compound, Japanese Patent Laid-Open No. 93-306327 discloses the inclusion of an amine-modified epoxy resin and a block isocyanate curing agent containing an oxazolidone ring. This technique aims to improve rust resistance by oxazolidone ring.
    [5] In addition, Japanese Patent Application Laid-Open No. 2000-38525 discloses a cationic electrodeposition coating composition composed of a resin composition having an epoxy resin as a skeleton and containing a sulfonium group, a propargyl group, and an unsaturated double bond. This is also a cation electrodeposition coating composition having a high uniform electrodeposition property without using a lead compound, and is intended to form a coating film having a sufficient film thickness on the back surface of a to-be-painted object having a complicated shape, and to secure the rust resistance of the back surface.
    [6] Compared with the use of the lead compound, the corrosion resistance of these cationic electrodeposition coating compositions is not sufficient. Accordingly, there is a demand for a rust preventive agent for improving corrosion resistance without containing heavy metals.
    [7] On the other hand, Japanese Patent Application Laid-Open No. 94-287776 discloses using tetrakis (hydroxymethyl) phosphonium sulfate as a corrosion inhibitor for copper. This is added to the target water system for the purpose of preventing corrosion of a pipe or the like made of copper or a copper alloy used in the heat storage water system.
    [8] However, when it is added and used in a cationic electrodeposition paint, since it has high water solubility, compatibility with the resin component which comprises a coating film worsens, and an anticorrosive effect cannot fully be exhibited.
    [9] An object of the present invention is to provide a cationic electrodeposition coating composition capable of obtaining a coating film having excellent anticorrosive properties without containing heavy metal-based rust preventive agents such as lead compounds due to environmental effects.
    [10] The inventors have found that a compound having a phosphonium group having a specific structure in which at least one hydroxyalkyl group is bonded, when added to a cationic electrodeposition coating composition, does not contain heavy metal-based rust preventive agents such as lead compounds, and thus has a coating film having excellent corrosion resistance and corrosion resistance. The present invention has been found to be obtainable.
    [11] That is, the present invention is a cationic electrodeposition coating composition comprising a water-soluble or water-dispersible phosphonium group-containing compound having a group represented by the following formula (1).
    [12] Formula 1
    [13]
    [14] Where
    [15] R is the same or different and represents an alkyl group or a hydroxyalkyl group, at least one of R being a hydroxyalkyl group.
    [16] The present invention is also a cationic electrodeposition coating composition comprising an epoxy compound as a basic skeleton and containing a water-soluble or water-dispersible phosphonium group-containing compound having a phosphonium group bonded to one or more hydroxyalkyl groups.
    [17] The present invention is also a cationic electrodeposition coating composition comprising an epoxy compound and a water-soluble or water-dispersible phosphonium group-containing compound obtained by reacting a phosphine compound having at least one hydroxyalkyl group.
    [18] Hereinafter, the present invention will be described in detail.
    [19] The cationic electrodeposition coating composition of the present invention contains a water-soluble or water-dispersible phosphonium group-containing compound. The said phosphonium group containing compound is added as an anticorrosive and a rust preventive agent.
    [20] Phosphonium group-containing compounds
    [21] The phosphonium group-containing compound has a group represented by the formula (1).
    [22] In Formula 1, R is the same or different and represents an alkyl group or a hydroxyalkyl group. The alkyl group and the hydroxyalkyl group preferably have 6 or less carbon atoms. When carbon number exceeds 6, water solubility is inferior and it may not be able to obtain a water-soluble or water-dispersible thing.
    [23] The alkyl group may be linear or branched, and examples thereof include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, t-butyl group and hexyl group. Examples of the hydroxyalkyl group include hydroxymethyl group, hydroxyethyl group, hydroxypropyl group, hydroxybutyl group and hydroxyhexyl group. As the hydroxyalkyl group, a hydroxypropyl group is more preferable.
    [24] At least one of said R is a hydroxyalkyl group. From the viewpoint of hydration, it is preferable that all three R's are hydroxyalkyl groups.
    [25] In this invention, it is especially preferable that the said phosphonium group is a tris (hydroxypropyl) phosphonium group.
    [26] The phosphonium group-containing compound is water-soluble or water-dispersible. If it is not water-soluble or water-dispersible, the solubility with respect to a cationic electrodeposition coating composition will fall, and use, such as a dispersing resin, is needed and handling property is inferior. Preferably, it is water soluble.
    [27] The phosphonium group-containing compound has an epoxy compound as a basic skeleton and contains a phosphonium group bonded to at least one hydroxyalkyl group. "Epoxy compound as a basic skeleton" as used herein means that the functional group such as the phosphonium group is present directly or through an ester bond or an ether bond at the front end of the epoxy group of the epoxy compound ring-opened. It is. For this reason, it does not matter whether an epoxy group exists.
    [28] It is preferable that the said phosphonium group containing compound has a number average molecular weight of 300-10,000 from a compatibility point with water. If it is less than 300, a phosphonium group containing compound may melt | dissolve in water from a coating film, and may not exhibit anticorrosiveness. When it exceeds 10,000, the phosphonium group-containing compound may not be water-soluble or water-dispersible. More preferably, it is 2000-6000.
    [29] It is preferable that the said phosphonium group containing compound is 0.3-3meq / g in quantity of phosphonium group. If it is less than 0.3 meq / g, the amount of the phosphonium group may be too small to secure corrosion resistance. When it exceeds 3 meq / g, the hydration property may be too high, and the phosphonium group-containing compound may be dissolved in water from the coating film, thereby preventing the corrosion resistance. More preferably, it is 0.3-2 meq / g.
    [30] It is preferable that the said phosphonium group containing compound further has an acid anion as a counter anion. The acid anion is not particularly limited, but anions of organic acids such as formic acid, acetic acid, lactic acid, propionic acid, butyric acid, dimethylpropionic acid, dimethylolbutanoic acid, N-acetylglycine, N-acetyl-β-alanine, sulfamic acid and the like are preferable. .
    [31] The phosphonium group-containing compound may further have a hydrocarbon group including an unsaturated bond. Moreover, you may further have a block isocyanate group. When adding what has a hydrocarbon group and / or a block isocyanate group containing an unsaturated bond to a cation electrodeposition coating composition, crosslinking with resin or a hardening agent advances and the adhesiveness and anticorrosive property of the obtained coating film can be improved more.
    [32] The hydrocarbon group containing the unsaturated bond may be linear or branched, and the position and number of the unsaturated bond are not particularly limited. From the viewpoint of compatibility with water, the hydrocarbon group containing the unsaturated bond is preferably 2 to 30 carbon atoms, and more preferably 2 to 24 carbon atoms.
    [33] One of the isocyanate groups of the polyisocyanate compound is -NHCO- to which hydrogen is added, and the remaining isocyanate group is blocked with a blocking agent. This block isocyanate group is bonded to the phosphonium compound on the CO-side of said -NHCO-.
    [34] As said polyisocyanate compound, For example, Alkylene diisocyanate, such as trimethylene diisocyanate, trimethyl hexamethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate; Cycloalkylene diisocyanates such as bis (isocyanate methyl) cyclohexane, cyclopentane diisocyanate, cyclohexane diisocyanate and isophorone diisocyanate; Aromatic diisocyanates such as tolylene diisocyanate, phenylene diisocyanate, diphenylmethane diisocyanate and diphenyl ether diisocyanate; Aromatic fatty diisocyanates such as xylylene diisocyanate and diisocyanate diethylbenzene; Polymerized polyisocyanates such as diisocyanates such as triisocyanates such as triphenylmethane triisocyanate, triisocyanate benzene and triisocyanate toluene and tetraisocyanates such as diphenyldimethylmethane tetraisocyanate and tolylene diisocyanate; The various polyisocyanate compounds and low molecular weight active hydrogen-containing organic compounds such as ethylene glycol, propylene glycol, diethylene glycol, trimethylol propane, hydrogenated bisphenol A, hexanetriol, glycerin, pentaerythritol, castor oil and triethanolamine are reacted with each other. The terminal isocyanate containing compound etc. which are obtained are mentioned.
    [35] Examples of the blocking agent include phenolic blocking agents such as phenol, cresol, xylenol, chlorophenol and ethylphenol; lactam block agents such as ε-caprolactam, δ-valerolactam, γ-butyrolactam, and β-propiolactam; Active methylene blocking agents such as ethyl acetoacetate and acetyl acetone; Methanol, ethanol, propanol, butanol, amyl alcohol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monomethyl ether, propylene glycol monomethyl ether, benzyl alcohol, methyl glycolate, butyl glycolate, diacetone alcohol, Alcohol blocking agents such as methyl lactate and ethyl lactate; Oxime block agents such as formaldehyde, acetaldehyde, acetoxime, methyl ethyl ketoxime, diacetyl monooxime and cyclohexane oxime; Mercaptan-based blocking agents such as butyl mercaptan, hexyl mercaptan, t-butyl mercaptan, thiophenol, methylthiophenol and ethyl thiophenol; Acid amide block agents such as acetic acid amide and benzamide; Imide-based blocking agents such as succinic acid imide and maleic acid imide; And imidazole-based blocking agents such as imidazole and 2-ethyl imidazole.
    [36] The phosphonium group-containing compound can be obtained by reacting an epoxy compound with a phosphine compound having at least one hydroxyalkyl group.
    [37] The epoxy compound which becomes the said raw material will not be specifically limited if it has one or more epoxy groups in a molecule | numerator, For example, Nonylphenyl glycidyl ether etc. as a monofunctional epoxy compound; Epibis epoxy resin which is a reaction product of bicyclic phenol compounds, such as bisphenol A, bisphenol F, bisphenol S, and epichlorohydrin as a polyfunctional epoxy compound; Chain extension thereof with diols such as difunctional polyester polyols and polyether polyols, bisphenols, dicarboxylic acids, diamines and the like; Epoxidized polybutadiene; Novolac phenolic polyepoxy resins; Novolac cresol type polyepoxy resins; Polyglycidyl acrylate; Polyglycidyl ethers of aliphatic polyols or polyether polyols such as triethylene glycol diglycidyl ether, tetraethylene glycol diglycidyl ether and polyethylene glycol diglycidyl ether; And polyglycidyl esters of polybasic carboxylic acids. Especially, the polyfunctional epoxy compound which has 2 or more epoxy groups is preferable, More preferably, the polybis of an epibis epoxy resin, a novolak phenol type polyepoxy resin, a novolak cresol type polyepoxy resin, an aliphatic polyol, or a polyether polyol Glycidyl ether.
    [38] The epoxy compound preferably has a number average molecular weight of 240 to tens of thousands. If it is less than 240, since the hydration property of the phosphonium group containing compound obtained becomes high and does not remain in a coating film, anticorrosiveness may not be obtained. When it exceeds tens of thousands, the resulting phosphonium group-containing compound may be difficult to be water-soluble or water dispersible. More preferably, it is 300-10,000.
    [39] It is preferable that the said epoxy compound is 50-1500 epoxy equivalent. When it exceeds 1500, the amount of the phosphonium group of the phosphonium group-containing compound obtained may become small, and the corrosion resistance may not be secured. If it is less than 50, the hydration property of the phosphonium group containing compound obtained may become so high that a phosphonium group containing compound may melt | dissolve in water from a coating film, and may not exhibit anticorrosive property. Preferably, it is 100-1000.
    [40] The epoxy compound can use what was modified.
    [41] As a modification method of the said epoxy compound, the method of ring-opening addition of alcohol and / or a carboxylic acid to some epoxy group is mentioned, for example.
    [42] When the said modification is intended to consume the epoxy group and to adjust the quantity of the phosphonium group in the phosphonium group containing compound which is a target substance, when it aims at introduction of a functional group and adjustment of a physical property by modification, and Although both may be aimed at, the modification method can be suitably selected according to a use and usage.
    [43] The alcohol and the carboxylic acid are not particularly limited when the purpose of modification is to adjust the amount of the phosphonium group in the phosphonium group-containing compound. However, what does not adversely affect the phosphonium salt finally obtained is used. When aiming at introducing a functional group or adjusting physical properties by the modification, the alcohol and / or carboxylic acid has a saturated hydrocarbon group having 6 or more carbon atoms; The thing which has unsaturated bond, such as unsaturated triple bond or unsaturated double bond, etc. are mentioned.
    [44] Preferably, when modifying by having a hydrocarbon group containing an unsaturated bond, the phosphonium group containing compound which has a hydrocarbon group containing the said unsaturated bond can be obtained by this.
    [45] The alcohol which has the said unsaturated bond is not specifically limited, For example, what has unsaturated triple bonds, such as a propargyl alcohol; Allyl alcohol, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, hydroxybutyl acrylate, hydroxybutyl methacrylate, methacryl alcohol, etc. And those having an unsaturated double bond.
    [46] The carboxylic acid which has the said unsaturated bond is not specifically limited, For example, what has unsaturated triple bonds, such as propargyl acid; Acrylic acid, methacrylic acid, ethacrylic acid, crotonic acid, maleic acid, phthalic acid, itaconic acid; Half esters such as maleic acid ethyl ester, fumaric acid ethyl ester, itaconic acid ethyl ester, succinic acid mono (meth) acryloyloxyethyl ester, and phthalic acid mono (meth) acryloyloxyethyl ester; Synthetic unsaturated fatty acids such as oleic acid, linoleic acid and ricinolic acid; Natural unsaturated fatty acids, such as linseed oil and soybean oil, are mentioned.
    [47] In addition, when modifying by having a hydrocarbon group containing an unsaturated triple bond, it is preferable to use propargyl alcohol from the availability and the ease of reaction.
    [48] On the other hand, alcohols and / or carboxylic acids having a saturated hydrocarbon group having 6 or more carbon atoms include 2-ethylhexanol, nonylphenol, ethylene glycol mono-2-ethylhexyl ether, and propylene glycol for the purpose of controlling molecular weight, improving heat flowability, and the like. Saturated hydrocarbon alcohols such as mono-2-ethylhexyl ether; Saturated hydrocarbon type carboxylic acids, such as stearic acid and octylic acid, are mentioned.
    [49] When the said epoxy compound has the hydroxyl group produced by ring-opening of an epoxy group, urethane modification by the half block isocyanate with respect to the hydroxyl group is also possible. Thereby, the phosphonium group containing compound which has the said block isocyanate group can be obtained. In this case, a block isocyanate group is couple | bonded with the thing remove | excluding the hydrogen atom from the said hydroxyl group.
    [50] The half-block isocyanate is one in which the isocyanate group of the polyisocyanate compound described above is blocked with a blocking agent except one.
    [51] The reaction conditions in the modification are usually several hours at room temperature or from 80 to 140 ° C. Moreover, the well-known component required in order to advance reaction, such as a catalyst and a solvent, can be used as needed. The completion | finish of reaction can be confirmed by the measurement of an epoxy group equivalent, and the functional group introduce | transduced can be confirmed by non-volatile matter measurement and instrumental analysis of the obtained resin composition.
    [52] The phosphine compound reacted with the epoxy compound is one having at least one hydroxyalkyl group.
    [53] The phosphine compound may be obtained by reacting phosphine (PH 3 ) with an alcohol such as allyl alcohol. In addition, it is also possible to use a commercial item, such as hishicholine P-500 (made by Nippon Chemical Co., Ltd .; tris (hydroxypropyl) phosphine) from the simplicity of acquisition.
    [54] Examples of the phosphine compound include tris (hydroxypropyl) phosphine, tris (hydroxyethyl) phosphine, tris (hydroxymethyl) phosphine, dihydroxybutyl (butyl) phosphine and the like. Since the phosphonium group-containing compound is preferably a phosphonium group is a tris (hydroxypropyl) phosphonium group, in this case, tris (hydroxypropyl) phosphine is used as the phosphine compound.
    [55] The said phosphonium group containing compound can be obtained by making the said epoxy compound and the said phosphine compound react. The reaction is generally carried out by coexistence of acid compounds. Since the said acid compound becomes a counter anion in the said phosphonium group containing compound after reaction, the above-mentioned organic acid is used as said acid compound.
    [56] Specifically, the reaction can be performed by adding a mixture solution of phosphine / acid / water to the epoxy compound and heating it. When the said epoxy compound is a solid, it is preferable to heat and melt previously.
    [57] In the above reaction, the amount ratio is 0.8 to 1.2 equivalents, preferably 0.9 to 1.1 equivalents, and 1 to 20 equivalents of water, when the equivalent of the epoxy group of the epoxy compound is 1.
    [58] As for the mixing ratio of the said phosphine and the said acid compound, about 0.8 to 1.2 times of an acid compound is preferable with respect to phosphine in a molar ratio normally.
    [59] The said reaction solvent is not specifically limited, For example, the thing of the ether type mixed with water and arbitrary ratios is preferable.
    [60] The reaction is thought to proceed almost quantitatively and the phosphonation rate can be adjusted by controlling the amount of phosphine to the epoxy group. It is also assumed that the phosphonated non-phosphonated epoxy group is ring-opened by water.
    [61] Although the phosphonation rate with respect to the said epoxy group can be selected according to the use and the usage-amount which the obtained phosphonium group containing compound is used, it is preferable that it is 30% or more, More preferably, it is 50% or more.
    [62] The reaction temperature is not particularly limited as long as the raw material and the resulting phosphonium group-containing compound are not decomposed, and examples thereof include room temperature to 90 ° C, and a temperature of about 75 ° C is preferable.
    [63] The reaction may be carried out until the acid value is measured to confirm that it does not change to 5 or less, and then cooled to obtain a phosphonium group-containing compound. It is usually used diluted with water to a suitable concentration of about 50%.
    [64] The phosphonium group-containing compound obtained as described above can be confirmed by molecular weight measurement by GPC using a high polar solvent such as dimethylformamide, and the amount of phosphonium can be measured by potentiometric titration.
    [65] The phosphonium group-containing compound was obtained by reacting an epoxy compound with a phosphine compound having at least one hydroxyalkyl group as described above, and it was confirmed that the phosphonium group-containing compound had a phosphonium group represented by the formula (1).
    [66] Cationic Electrodeposition Coating Composition
    [67] The cationic electrodeposition coating composition of this invention contains the said phosphonium group containing compound. The said phosphonium group containing compound functions as a so-called organic inhibitor which exhibits a corrosion inhibitory effect in a cationic electrodeposition coating composition.
    [68] It is preferable to add the said phosphonium group containing compound at 0.5 to 10 weight% with respect to the resin solid content of a cationic electrodeposition coating composition. If it is less than 0.5 weight%, the anticorrosive property of the obtained coating film may be inferior, and even if it exceeds 10 weight%, the further effect may not be desired, and curability may fall, and it may adversely affect coating film physical properties. More preferably, it is 2-7 weight%.
    [69] Although the said cationic electrodeposition coating composition is not specifically limited, If it is a conventionally used cationic electrodeposition coating material, the electrodeposition coating film which has favorable anticorrosive property can be obtained by adding the said phosphonium group containing compound, but an amine modified epoxy resin and a block as a base resin are provided. By using an isocyanate curing agent (hereinafter also referred to as cationic electrodeposition coating composition [1]) or a sulfide-modified epoxy resin having an unsaturated hydrocarbon group (hereinafter also referred to as cationic electrodeposition coating composition [2]), Since the anticorrosive property of the coating film obtained can be improved further, it is preferable.
    [70] Cationic electrodeposition coating composition [1]
    [71] The said cationic electrodeposition coating composition [1] contains an amine modified epoxy resin and a block isocyanate hardening | curing agent as a basic resin.
    [72] The said amine modified epoxy resin can be manufactured by ring-opening the epoxy ring which the epoxy resin which is a starting raw material has with amines, such as a primary amine, a secondary amine, and a tertiary amine salt.
    [73] As an epoxy resin which is the said starting raw material, what was illustrated as the polyfunctional epoxy compound mentioned above is mentioned.
    [74] In the said cationic electrodeposition coating composition [1], the oxazolidone ring containing epoxy resin of Unexamined-Japanese-Patent No. 93-306327 is preferable as said epoxy resin. Uniform electrodeposition property and the anticorrosive property of the coating film obtained can be further improved by the said oxazolidone ring containing epoxy resin.
    [75] The said oxazolidone ring containing epoxy resin can be obtained by reaction of the diisocyanate compound or the bisurethane compound obtained by blocking the NCO group of the diisocyanate compound with lower monoalcohols, such as methanol and ethanol, and the above-mentioned epoxy compound. .
    [76] As mentioned above, the epoxy resin used as the said raw material can also use what was modified by ring-opening addition of alcohol and / or carboxylic acid to some epoxy groups, and what extended | stretched the chain with bifunctional polyol or dibasic acid.
    [77] Examples of the amines that can be used when opening the epoxy ring of the epoxy compound to introduce an amino group include butylamine, octylamine, diethylamine, dibutylamine, methylbutylamine, monoethanolamine, diethanolamine and N-methylethanol Primary, secondary, or tertiary amine salts, such as amine, triethyl amine salt, N, and N-dimethylethanol amine salt, are mentioned. Moreover, ketimine block primary amino group containing secondary amines, such as aminoethyl ethanolamine methyl isobutyl ketimine, can also be used.
    [78] These amines need to be made to react 80% or more with respect to an epoxy ring.
    [79] As for the number average molecular weight of the said amine modified epoxy resin, 600-4000 are preferable. If it is less than 600, physical properties, such as solvent resistance and corrosion resistance, of the obtained coating film may fall. When it exceeds 4000, the viscosity control of the resin solution becomes difficult, not only synthesis is difficult, but also operational handling such as emulsion dispersion of the obtained resin may be difficult. In addition, because of its high viscosity, the flowability during heating and curing is poor, which may significantly impair the appearance of the coating film.
    [80] It is preferable that the amino value of the said amine modified epoxy resin is 30-150, More preferably, it is 45-120. If it is less than 30, it is difficult to obtain a stable emulsion, and if it exceeds 150, there may be a problem in electrodeposition coating workability such as coulombic efficiency and re-dissolution property.
    [81] The block isocyanate curing agent is obtained by reacting a polyisocyanate compound having two or more isocyanate groups with a blocking agent which is added at an isocyanate group and is stable at room temperature but can regenerate free isocyanate groups when heated to a dissociation temperature or higher. What is normally used for can be used. Examples of the polyisocyanate compound and the blocking agent include those exemplified above.
    [82] The solid content weight ratio of the amine-modified epoxy resin and the block isocyanate curing agent is preferably 50/50 to 90/10, more preferably 60/40 to 80/20. If it deviates from the said ratio, there exists a possibility that a problem may arise in sclerosis | hardenability.
    [83] The cationic electrodeposition coating composition [1] further contains a neutralized acid for dispersing the component. As said neutralizing acid, inorganic acids, such as boric acid, hydrochloric acid, a sulfuric acid, phosphoric acid, are mentioned as an acid used for reaction with the said amine, in addition to the organic acid illustrated as the said acid compound. The amount of the neutralized acid depends on the amount of the amino group in the amine-modified epoxy resin, and may be an amount in which the amino group can be water-dispersible.
    [84] The cationic electrodeposition coating composition [1] may further include a pigment and a pigment dispersion resin. The pigment is not particularly limited as long as it is a pigment that is usually used, and examples thereof include colored pigments such as titanium dioxide, carbon black, and bengal; Extender pigments such as kaolin, talc, aluminum silicate, calcium carbonate, mica, clay, and silica.
    [85] In the said cationic electrodeposition coating composition [1], it is also possible to use combining the other rust preventing pigment with the said phosphonium group containing compound. Examples of the rust-preventive pigments include zinc phosphate, iron phosphate, aluminum phosphate, calcium phosphate, zinc phosphite, zinc cyanide, zinc oxide, aluminum tripolyphosphate, zinc molybdate, aluminum molybdate, calcium molybdate, and aluminum molybdate. .
    [86] Generally as said pigment dispersion resin, the modified epoxy resin etc. which have a cationic or nonionic low molecular weight surfactant, a quaternary ammonium group, and / or a tertiary sulfonium group are used.
    [87] After mixing a predetermined amount of the pigment dispersion resin and the pigment, the pigment by dispersing using a conventional dispersing device such as a ball mill or sand grind mill until the particle diameter of the pigment in the mixture is a predetermined uniform particle diameter A dispersion paste is obtained. The pigment dispersion paste may be used in an amount such that the pigment in the cationic electrodeposition coating composition becomes 0 to 50% by weight as a solid content.
    [88] In addition, the cationic electrodeposition coating composition [1] may further include conventional paint additives such as surfactants, antioxidants, ultraviolet absorbers, and curing accelerators.
    [89] The cationic electrodeposition coating composition [1] can be obtained by mixing an amine-modified epoxy resin, a block isocyanate curing agent, a phosphonium group-containing compound, a pigment dispersion paste, and an additive for paint, if necessary. Since the phosphonium group-containing compound is water-soluble, it is preferable to carry out in the following order. First, a neutralized acid is added by mixing an amine modified epoxy resin and a block isocyanate hardener. After adding a phosphonium group containing compound to this, it is disperse | distributed to the aqueous medium which is water alone or a mixture with a hydrophilic organic solvent, and a pigment dispersion paste can be mixed as needed, and a cationic electrodeposition coating composition [1] can be obtained. In addition, additives may be added to the system at any stage.
    [90] The said cationic electrodeposition coating composition [1] is cationic electrodeposition-coated with respect to a base material. The cationic electrodeposition coating itself is according to a method already known, and is generally set to 5 to 40% by weight, preferably 15 to 25% by weight, by dilution with deionized water, and further having a pH of 5.5. The electrodeposition bath consisting of the cationic electrodeposition coating composition adjusted in the range of from -8.5 to ordinary bath temperature is adjusted to 20 to 35 ℃, it can be carried out under the conditions of coating voltage 100 to 450V.
    [91] The film thickness of the said electrodeposition coating is 5-40 micrometers in dry film thickness, Preferably it is suitable in the range of 10-30 micrometers, It is preferable to set the said electrodeposition coating conditions so that it may become this film thickness. Moreover, baking of a coating film is generally suitable to perform in 100 to 220 degreeC, Preferably it is 140 to 200 degreeC in the time range for 10 to 30 minutes.
    [92] Cationic electrodeposition coating composition [2]
    [93] The said cationic electrodeposition coating composition [2] contains a sulfide modified epoxy resin which has an unsaturated hydrocarbon group as a basic resin.
    [94] The sulfide-modified epoxy resin is obtained by reacting an epoxy resin and a sulfide / acid mixture. The sulfide-modified epoxy resin is a skeleton, and a sulfonium group is bonded through a ring-opened epoxy ring.
    [95] As said epoxy resin, what was illustrated as the polyfunctional epoxy compound mentioned above is mentioned. It is preferable that they are novolak-type epoxy resins, such as a novolak phenol type epoxy resin and a novolak cresol type epoxy resin, from the point which can carry out polyfunctionalization to improve sclerosis | hardenability.
    [96] It is preferable that it is 400-15000, and, as for the number average molecular weight of the epoxy resin used as the said raw material, it is more preferable that it is 650-12000.
    [97] It is preferable that the number average molecular weights of the said sulfide modified epoxy resin are 500-20000. If it is less than 500, the coating efficiency of cation electrodeposition coating will worsen, and if it exceeds 20000, a favorable film will not be formed on the to-be-coated surface. More preferable number average molecular weight can be set according to the resin skeleton, and in the case of a novolak phenol type epoxy resin and a novolak cresol type epoxy resin, it is more preferable that it is 700-5000.
    [98] In the said cationic electrodeposition coating composition [2], the sulfonium group and the unsaturated hydrocarbon group are introduce | transduced into resin which makes the said epoxy resin a skeleton through the ring-opened epoxy group of the epoxy resin which forms the said skeleton. It is preferable that the said unsaturated hydrocarbon group is a propargyl group from a hardenability viewpoint, More preferably, it has an unsaturated double bond in addition to the propargyl group of Unexamined-Japanese-Patent No. 2000-38525. In addition, the unsaturated double bond is a carbon-carbon double bond.
    [99] In the sulfide-modified epoxy resin having an unsaturated hydrocarbon group, the resin having an epoxy resin as a skeleton may contain both a sulfonium group and an unsaturated hydrocarbon group in one molecule, but it is not necessary to do so, for example, a resin having only a sulfonium group in one molecule. The molecule and the resin molecule which have a sulfonium group and an unsaturated hydrocarbon group together may be mixed. In addition, in the case of having an unsaturated double bond in addition to the propargyl group, it may likewise contain all three kinds of sulfonium groups, propargyl groups and unsaturated double bonds in one molecule, but it is not necessary. One molecule may contain one or two of a sulfonium group, a propargyl group or an unsaturated double bond.
    [100] The sulfonium group is a hydration functional group of the cationic electrodeposition coating composition [2]. The sulfonium group is considered to undergo an electrolytic reduction reaction on the electrode when a predetermined voltage or current is applied in the electrodeposition coating process, resulting in the loss of the ionic group and irreversible inversion. For this reason, it is thought that the said cationic electrodeposition coating composition [2] can exhibit high uniform electrodeposition property.
    [101] In addition, in this electrodeposition coating process, an electrode reaction is caused, and it is thought that an electrolytic generating base will generate | occur | produce in an electrodeposition film by maintaining a sulfonium group which produced | generated the hydroxide ion. By generating this electrolytic generating base, the propargyl group with low reactivity by the heating which exists in an electrodeposition film can be converted into the allene bond with high reactivity by heating.
    [102] It is preferable that content of the said sulfonium group is 5-400 mmol per 100g of resin solid content of a cationic electrodeposition coating composition [2]. If it is less than 5 mmol / 100 g, sufficient uniform electrodeposition property and curability cannot be exhibited, and hydration property and bath stability will worsen. If it exceeds 400 mmol / 100 g, the deposition of the film on the surface of the workpiece becomes worse. More preferable content can be set according to a resin skeleton, For example, in the case of a novolak phenol type epoxy resin and a novolak cresol type epoxy resin, it is preferable that it is 5-250 mmol per 100g of resin solid content, and 10-150 mmol is more preferable.
    [103] It is thought that the said propargyl group can improve reactivity and comprise a hardening system by converting into an allene bond as mentioned above. Moreover, although the reason is not clear, the uniform electrodeposition property of a resin composition can be improved further by coexisting with a sulfonium group.
    [104] When it contains the said propargyl group, it is preferable that the content is 10-485 mmol per 100g of resin solid content of a cation electrodeposition coating composition [2]. If it is less than 10 mmol / 100 g, sufficient uniform electrodeposition property and hardenability cannot be exhibited, and if it exceeds 485 mmol / 100 g, there exists a possibility that it may adversely affect the hydration stability at the time of using as a cationic electrodeposition paint. More preferable content can be set according to resin skeleton, and, for example, in the case of a novolak phenol type epoxy resin and a novolak cresol type epoxy resin, it is preferable that it is 20-375 mmol per 100g of resin solid content.
    [105] When the sulfide-modified epoxy resin having the unsaturated hydrocarbon group has an unsaturated double bond in addition to the propargyl group, the unsaturated double bond can further improve curability because of its high reactivity.
    [106] It is preferable that content of the said unsaturated double bond is 10-485 mmol per 100g of resin solid content of a cationic electrodeposition coating composition [2]. If it is less than 10 mmol / 100 g, sufficient sclerosis | hardenability cannot be exhibited, and if it exceeds 485 mmol / 100 g, there exists a possibility that it may adversely affect the hydration stability at the time of using as a cationic electrodeposition paint. More preferable content can be set according to a resin skeleton, and, for example, in the case of a novolak phenol type epoxy resin and a novolak cresol type epoxy resin, it is preferable that it is 20-375 mmol per 100 g of resin composition solid content.
    [107] In addition, in the said cationic electrodeposition coating composition [2], when using what has an unsaturated double bond further, content of an unsaturated double bond is represented by the quantity corresponding to content of the epoxy group in which the unsaturated double bond was introduce | transduced. That is, even when a molecule having a plurality of unsaturated double bonds is introduced into the epoxy, for example, in a molecule such as a long chain unsaturated fatty acid, the content of the unsaturated double bond is the content of the epoxy group into which the molecule having the plurality of unsaturated double bonds is introduced. It shall be shown. This is because even if a molecule having a plurality of unsaturated double bonds in a molecule is introduced into one epoxy group, only one unsaturated double bond is considered to be involved in the curing reaction.
    [108] The total content of the sulfonium group and the unsaturated hydrocarbon group is preferably 500 mmol or less per 100 g of the resin solid content. When it exceeds 500 mmol, the resin may not be obtained in practice, or the desired performance may not be obtained. More preferable content can be set according to resin skeleton, and, for example, in the case of a novolak phenol type epoxy resin and a novolak cresol type epoxy resin, it is preferable that it is 400 mmol or less.
    [109] Moreover, it is preferable that the sum total content of a propargyl group and an unsaturated double bond exists in the range of 80-450 mmol per 100g of resin solid content. If it is less than 80 mmol, sclerosis | hardenability may become inadequate, and if it exceeds 450 mmol, content of a sulfonium group may become small and uniform electrodeposition property may become inadequate. More preferable content can be set according to resin skeleton, and, for example, in the case of a novolak phenol type epoxy resin and a novolak cresol type epoxy resin, it is more preferable that it is 100-395 mmol.
    [110] A curing catalyst may be introduced into the sulfide-modified epoxy resin having an unsaturated hydrocarbon group. For example, when a curing catalyst is used to form a propargyl group and acetylide, a part of the propargyl group may be acetylated to form a curing catalyst. It is possible to introduce in resin.
    [111] Preparation of the sulfide-modified epoxy resin having the unsaturated hydrocarbon group can be carried out as follows. That is, a compound having an unsaturated hydrocarbon group is first reacted with an epoxy resin having at least two epoxy groups in one molecule, and then a sulfonium group is introduced by reacting a mixture of sulfide and acid with the remaining epoxy group. As described above, by introducing the sulfonium group later, decomposition of the sulfonium group due to heating can be prevented.
    [112] As a compound which has the said unsaturated hydrocarbon group, the alcohol and / or carboxylic acid which has an unsaturated bond used for modification of an epoxy compound can be used. The compound having an unsaturated hydrocarbon group and its amount can be determined according to the type and amount of the unsaturated hydrocarbon group to be introduced.
    [113] The reaction can be carried out in the same manner as described for the denaturation. When the unsaturated hydrocarbon group contains a propargyl group and an unsaturated double bond, a compound having a propargyl group and a compound having an unsaturated double bond are used in the reaction, but the reaction order of each compound is irrelevant. In addition, these compounds may be reacted at the same time.
    [114] The sulfonium group is introduced into the remaining epoxy group in the epoxy resin composition containing the unsaturated hydrocarbon group thus obtained. The introduction of the sulfonium group is a method of introducing sulfide and sulfonation by reacting a sulfide / acid mixture with an epoxy group, or performing sulfonation of sulfide introduced by an acid or an alkyl halide after the introduction of sulfide. If necessary, it can be carried out by a method of performing anion exchange. The method using a sulfide / acid mixture is preferable from a viewpoint of the availability of reaction raw material.
    [115] The said sulfide is not specifically limited, For example, aliphatic sulfide, aliphatic-aromatic mixed sulfide, aralkyl sulfide, cyclic sulfide, etc. are mentioned, As a substituent couple | bonded with these sulfides, a C2-C8 thing is preferable. Specifically, for example, diethyl sulfide, dipropyl sulfide, dibutyl sulfide, dihexyl sulfide, diphenyl sulfide, ethylphenyl sulfide, tetramethylene sulfide, pentamethylene sulfide, thiodiethanol, thiodipropanol, thiodibutanol, 1 -(2-hydroxyethylthio) -2-propanol, 1- (2-hydroxyethylthio) -2-butanol, 1- (2-hydroxyethylthio) -3-butoxy-1-propanol and the like Can be mentioned.
    [116] As said acid, the organic acid and inorganic acid which were mentioned above are mentioned.
    [117] In the reaction, the ratio of the amount, the mixing ratio of sulfide and acid, the reaction conditions, and the introduction of the sulfonium group in the resin composition can be performed in the same manner as described for the reaction of the phosphine / acid compound.
    [118] It is not necessary to use a hardening | curing agent in the said cationic electrodeposition coating composition [2] because resin itself has curability. However, it can also be used in order to further improve the curability. As such a curing agent, for example, a compound having a plurality of at least one of a propargyl group and an unsaturated double bond, for example, a polyepoxide such as novolac phenol, a propargyl group such as propargyl alcohol, etc. in pentaerythrite tetraglycidyl ether The compound obtained by addition-reacting the compound which has a unsaturated double bond, such as a compound and acrylic acid, etc. which are mentioned can be mentioned.
    [119] A hardening catalyst can be used for the said cationic electrodeposition coating composition [2] in order to advance hardening reaction between unsaturated bonds. Such a curing catalyst is not particularly limited. For example, a ligand such as cyclopentadiene or acetylacetone, a carboxylic acid such as acetic acid or naphthenic acid, or the like is bonded to a transition metal such as nickel, cobalt, copper, manganese, palladium or rhodium. Can be mentioned. Among these, acetylacetone complexes of copper and copper acetate are preferable. It is preferable that the compounding quantity of the said curing catalyst is 0.1-20 mmol per 100 g of resin solid content of a cationic electrodeposition coating composition [2].
    [120] An amine can also be mix | blended with the said cationic electrodeposition coating composition [2]. By addition of the said amine, the conversion rate of the sulfonium group to the sulfide by the electrolytic reduction in electrodeposition process increases. The said amine is not specifically limited, For example, amine compounds, such as primary and tertiary monofunctional and polyfunctional aliphatic amine, alicyclic amine, and aromatic amine, are mentioned. Among these, water-soluble or water-dispersible ones are preferable, for example, alkylamines having 2 to 8 carbon atoms such as monomethylamine, dimethylamine, trimethylamine, triethylamine, propylamine, diisopropylamine and tributylamine; Monoethanolamine, dimethanolamine, methylethanolamine, dimethylethanolamine, cyclohexylamine, morpholine, N-methylmorpholine, pyridine, pyrazine, piperidine, imidazoline, imidazole and the like. These may be used independently and may use 2 or more types together. Among them, hydroxyamines such as monoethanolamine, diethanolamine and dimethylethanolamine are preferable because of excellent water dispersion stability.
    [121] The amount of the amine added is preferably 0.3 to 25 meq per 100 g of the resin solid content of the cationic electrodeposition coating composition [2]. If it is less than 0.3 meq / 100g, sufficient effect cannot be acquired about uniform electrodeposition property, and if it exceeds 25 meq / 100g, the effect by addition amount cannot be obtained and it is uneconomical. More preferably, it is 1-15 meq / 100g.
    [122] The said cationic electrodeposition coating composition [2] may also contain other components as needed. As said other component, what was illustrated by the said cationic electrodeposition coating composition [1] is mentioned.
    [123] Although the thing illustrated by the said cationic electrodeposition coating composition [1] about the pigment dispersion resin among the other components is mentioned, It is preferable to use the pigment dispersion resin which contains a sulfonium group and an unsaturated bond in resin. Such pigment dispersion resins containing sulfonium groups and unsaturated bonds, for example, react a sulfide compound with a hydrophobic epoxy resin obtained by reacting a bisphenol-type epoxy resin with a half-blocked isocyanate, or a monobasic acid and a hydroxyl group-containing dibasic salt. It can obtain by the method etc. which make a sulfide compound react in presence of a base acid.
    [124] The said cationic electrodeposition coating composition [2] can be adjusted by mixing the said component. In addition, the cationic electrodeposition coating composition [2] may be subjected to electrodeposition coating and baking based on the conditions exemplified in the cationic electrodeposition coating composition [1].
    [125] When electrodeposition coating is performed using the cationic electrodeposition coating composition of the present invention, the coating is not particularly limited as long as it is conductive, for example, metals such as iron, zinc and aluminum; Alloys of these metals; And molded articles of metals or alloys such as automobiles and parts thereof.
    [126] The cationic electrodeposition coating film formed of the above cationic electrodeposition coating composition may form a top coat after the intermediate coating film is formed thereon as necessary. In addition, the formation of the intermediate coating film and the top coating film can be applied to the coating materials and coating conditions used for exterior coating of automobiles and the like.
    [127] As described above, the present invention includes a water-soluble or water-dispersible phosphonium group-containing compound. When the phosphonium group-containing compound is added, the mechanism of improvement of the corrosion resistance of the metal substrate is not clear, but any bonding or interaction occurs between the metal and the phosphonium group to improve adhesion to the substrate. Therefore, it is estimated that durability and anticorrosiveness are improved. In addition, by using the cationic electrodeposition coating composition [1] containing an amine-modified epoxy resin and a block isocyanate curing agent as the cationic electrodeposition coating composition, an electrodeposition coating film having further improved corrosion resistance can be obtained. In addition, by using the cationic electrodeposition coating composition [2] containing a sulfide-modified epoxy resin having an unsaturated hydrocarbon group, the coating film having sufficient anticorrosive property to the back side of the coated object can be obtained because of excellent not only corrosion resistance but also uniform electrodeposition property. have.
    [128] Example
    [129] Although an Example is given to the following and this invention is demonstrated to it in more detail, this invention is not limited only to these Examples.
    [130] Preparation Example 1: Preparation of phosphonium group-containing compound (monofunctional epoxy compound base)
    [131] 325.0 g of NH-300P (nonylphenylglycidyl ether; manufactured by Sanyo Chemical Co., Ltd.) of epoxy equivalent 325 was added to the reaction vessel and heated to 100 ° C. Then, the aqueous solution which mixed 208.2 g of tris (3-hydroxypropyl) hischoline P-500 (phosphine; Nippon Chemical Co., Ltd.), 60.0 g of acetic acid, and 144.0 g of ion-exchange water was gradually added, and it was made into 75 degreeC. Maintained.
    [132] After confirming that the acid value was fixed to 5 or less, 251.5 g of ion-exchanged water was added, followed by cooling, and then taken out (non-volatile content (hereinafter also referred to as NV) = 60%, number average molecular weight 590, phosphonium group 1.7 meq / g) , Phosphonation ratio for epoxy group = 100%). In addition, the phosphonation rate with respect to an epoxy group was measured by potentiometric titration using 1 / 10N hydrochloric acid.
    [133] Preparation Example 2 Preparation of Phosphonium Group-Containing Compound (Novolak Type Epoxy Compound Base)
    [134] 2426.4 g of epoxy equivalent 202.2 YDCN-703 (cresol novolac-type epoxy resin; 12 nuclei; manufactured by Totogase Co., Ltd.) and 1257.0 g of ethylene glycol monobutyl ether were charged into a reaction vessel. It was heated to 130 ° C. under nitrogen atmosphere to dissolve uniformly.
    [135] Then, after cooling to 100 degreeC, the aqueous solution which mixed 1619.1g of hishicholine P-500, 432.0g of acetic acid, and 1728g of ion-exchange water is added gradually, and it keeps at 75 degreeC, cooling, and an acid value is 5 or less The reaction was continued until
    [136] After confirming that the acid value was fixed to 5 or less, 1492.5 g of ion-exchanged water was added and cooled (NV = 50%, number average molecular weight 4500, phosphonium group 1.6 meq / g, phosphonation ratio for epoxy group = 60%) .
    [137] Preparation Example 3 Preparation of Phosphonium Group-Containing Compound (Novolak-type Epoxy Resin Base with Unsaturated Group)
    [138] 2426.4 g of epoxy equivalent 202.2 YDCN-703 (cresol novolak-type epoxy resin; 12 nuclei; manufactured by Totogase Co., Ltd.) and 1682.4 g of an enzyme-treated linseed oil fatty acid were added and heated to 120 ° C. After uniformly dissolving, 7.28 g of ethyltriphenylphosphonium iodide was added thereto. After confirming that the acid value became 1 or less, 2426.4 g of ethylene glycol monobutyl ether was added.
    [139] Thereafter, an aqueous solution obtained by mixing 1349.3 g of hishicholine P-500, 360.0 g of acetic acid, and 3384.4 g of ion-exchanged water was slowly added, and maintained at 75 ° C.
    [140] After confirming that the acid value was fixed to 5 or less, the mixture was cooled and taken out (NV = 50%, number average molecular weight 5800, phosphonium group 1.0 meq / g, phosphonation ratio for epoxy group 50%).
    [141] Production Example 4: Preparation of phosphonium group-containing compound (epis type epoxy resin base (without unsaturated group))
    [142] 970.0 g of epicoat 1001 (bisphenol A epoxy resin; manufactured by Yucca Shell Epoxy) and 265.0 g of PCPO 200 (polycaprolactone diol; manufactured by Union Carbide) were added to the reaction vessel.
    [143] It was heated to 130 ° C. under a nitrogen atmosphere and 0.46 g of dimethylbenzylamine was added. The reaction mixture was further heated to 150 ° C. and maintained at this temperature for 3 hours. Thereafter, 607.6 g of ethylene glycol monobutyl ether was added and cooled to 110 ° C.
    [144] Thereafter, an aqueous solution in which 124.9 g of hishicholine P-500, 36.0 g of acetic acid, and 144.0 g of ion-exchanged water were added slowly, was maintained at 75 ° C.
    [145] After confirming that the acid value was fixed to 5 or less, 644.3 g of ion-exchanged water was added and cooled, and then taken out (NV = 50%, number average molecular weight 2800, phosphonium group 0.4 meq / g, phosphonation ratio for epoxy group = 60%).
    [146] Preparation Example 5 Preparation of Blocked Isocyanate
    [147] 92 g of 2,4- / 2,6-tolylene diisocyanate (weight ratio = 8/2) and methyl isobutyl ketone (hereinafter, abbreviated as MIBK) in a reaction vessel equipped with a stirrer, a cooler, a nitrogen introduction tube, a thermometer, and a dropping lot. 95 g and 0.5 g of dibutyltin laurate were added, and 21 g of methanol was further added dropwise with stirring. The reaction started from room temperature and heated up to 60 ° C by exotherm.
    [148] Then, after continuing reaction for 30 minutes, 57 g of ethylene glycol mono-2-ethylhexyl ethers were dripped from the dropping lot, and 42 g of bisphenol A-propylene oxide 5 mol adducts were further added.
    [149] The reaction was carried out mainly in the range of 60 to 65 ° C. and continued until absorption by the isocyanate group was lost while measuring the IR spectrum.
    [150] Preparation Example 6 Preparation of Basic Resin
    [151] 365 g of an epoxy equivalent of 188 epoxy resin synthesized from bisphenol A and epichlorohydrin was added to the blocked isocyanate obtained in Production Example 5, and the temperature was raised to 125 ° C. Thereafter, 1.0 g of benzyldimethylamine was added and reacted at 130 ° C until the epoxy equivalent was 410. Subsequently, 87 g of bisphenol A was added to the reaction vessel and reacted at 120 ° C., resulting in an epoxy equivalent of 1190. Thereafter, 11 g of diethanolamine, 24 g of N-methylethanolamine, and 25 g of ketimide (79 wt% MIBK solution) of aminoethylethanolamine were added thereto, and the mixture was reacted at 110 ° C for 2 hours. Thereafter, the mixture was diluted with MIBK until the nonvolatile content was 80% to obtain a basic resin.
    [152] Preparation Example 7 Preparation of Crosslinking Agent
    [153] 723 g of isophorone diisocyanate, 333 g of MIBK and 0.01 g of dibutyltin laurate were added to the reaction container provided with the stirrer, the cooler, the nitrogen inlet tube, the thermometer, and the dropping lot, and it heated up to 70 degreeC. After dissolving uniformly, 610 g of methyl ethyl ketoxim was dripped over 2 hours. After completion of the dropwise addition, the reaction was continued until the absorption by the isocyanate group disappeared while measuring the IR spectrum while maintaining the reaction temperature of 70 ° C (nonvolatile content: 80%).
    [154] Preparation Example 8 Preparation of Pigment Dispersion Paste
    [155] 60.0 g of pigment dispersion resin varnish (epoxy quaternary ammonium salt type pigment dispersion resin) as solids, 2.0 g of carbon black, 100.0 g of kaolin, 80.0 g of titanium dioxide, 18.0 g of aluminum molybdate and 56.0% of solids of pigment paste An amount of ion-exchanged water was added to a sand grind mill and dispersed until the particle size became 10 µm or less to obtain a pigment paste.
    [156] Examples 1-4
    [157] As solids, 627.2 g of the base resin obtained in Preparation Example 6 and 234.2 g of the crosslinking agent prepared in Preparation Example 7 were uniformly mixed, and then ethylene glycol mono-2-ethylhexyl ether was added in an amount of 3% based on the solid content. It was.
    [158] To this was added 2.09 g of glacial acetic acid and 11.2 g of formic acid, neutralized to a neutralization rate of 41.7%, and further diluted with ion-exchanged water. Then, MIBK was removed under reduced pressure until solid content became 36.0%, and the main emulsion was prepared.
    [159] 791.7 g of the obtained main emulsion, 30 g of the phosphonium group-containing compound obtained in Preparation Examples 1 to 4, 178.6 g of the pigment dispersion paste of Preparation Example 8, 999.7 g of ion-exchanged water, and 1% of dibutyltin oxide were added to the solids. By mixing, a cationic electrodeposition paint having a solid content of 20% was obtained.
    [160] Comparative Example 1
    [161] 833.3 g of the main emulsion obtained in Example 1, 178.6 g of the pigment dispersion paste of Preparation Example 8, 999.7 g of ion-exchanged water, and 1% of dibutyltin oxide were mixed with the solid to obtain a cationic electrodeposition paint having a solid content of 20%. It was.
    [162] Corrosion Resistance Evaluation
    [163] In the cationic electrodeposition paints obtained in Examples 1 to 4 and Comparative Example 1, a 150 x 70 x 0.8 mm cold rolled steel sheet chemically treated with surfdyne SD2500 (zinc phosphate treatment agent, manufactured by Nippon Paint Co., Ltd.) was immersed, and a dry film was coated. Cationic electrodeposition coating was carried out to a thickness.
    [164] To the obtained test plate, crosscut scratches were put with a knife so as to reach the base, and this was put into a salt spray tester at 35 ° C. for 1000 hours, and the rust or swelling width from the scratches was measured.
    [165] As a result of evaluating the maximum width | variety of rust or swelling on the basis of 6 mm, it was the pass using the paint of Examples 1-4, but it failed to use the paint of Comparative Example 1.
    [166] Preparation Example 9 Preparation of Resin for Cationic Electrodeposit Coating Containing Sulfonium Group, Propargyl Group and Long Chain Unsaturated Hydrocarbon Group
    [167] 100.0 g of YDCN-701 (cresol novolac type epoxy resin; manufactured by Totogase Co., Ltd.) of epoxy equivalent 200, 4, propargyl alcohol, and dimethyl in a reaction vessel equipped with a stirrer, a cooler, a nitrogen introduction tube, a thermometer, and a dropping lot. 0.2 g of benzylamine was added thereto, the temperature was raised to 105 占 폚, and reacted for 1 hour to obtain a resin containing a propargyl group having an epoxy equivalent of 445. To this was added 50.6 g of linoleic acid and 0.1 g of additional dimethylbenzylamine, and the reaction was further continued at the same temperature for 3 hours to obtain a resin containing a propargyl group having a epoxy equivalent of 2100 and a long chain unsaturated hydrocarbon group. Furthermore, 10.6 g of SHP-100 (1- (2-hydroxyethylthio) -2-propanol; manufactured by Sanyo Chemical Co., Ltd.), 4.7 g of glacial acetic acid, and 7.0 g of ion-exchanged water were added thereto, and the mixture was kept at 75 ° C for 6 hours. After reacting and confirming that the residual acid value was 5 or less, 62.9 g of ion-exchanged water was added to obtain a desired resin solution (69.3% nonvolatile matter, 23.5 mmol / 100 g varnish).
    [168] Examples 5-8
    [169] 1.013 g of nickel acetyl acetonate, 0.6 g of methylaminoethanol and 154.1 g of ion-exchanged water were added to 137.1 g of a resin for a cationic electrodeposition paint containing a sulfonium group, a propargyl group and a long-chain unsaturated hydrocarbon group obtained as a basic resin. After stirring for 1 hour with a high-speed rotary mixer, 370.5 g of ion-exchanged water and 10 g of the phosphonium group-containing compound obtained in Production Examples 1 to 4 were added thereto to prepare a solid content of 15% by weight to prepare an electrodeposition paint.
    [170] Comparative Example 2
    [171] 1.0 g of nickel acetyl acetonate, 0.6 g of methylaminoethanol and 154.1 g of ion-exchanged water were added to 144.3 g of a cation electrodeposition paint containing the sulfonium group, the propargyl group and the long-chain unsaturated hydrocarbon group obtained as the basic resin. After stirring for 1 hour with a high-speed rotary mixer, 373.3 g of ion-exchanged water was further added to prepare a solid content of 15% by weight to obtain an electrodeposition paint.
    [172] Corrosion Resistance Evaluation
    [173] Using the cationic electrodeposition paints obtained in Examples 5 to 8 and Comparative Example 2 to have a dry film thickness of 15 μm, the test plate was obtained in the same manner as in Example 1 for corrosion resistance evaluation except that baking was carried out for 25 minutes. At the same time, corrosion resistance evaluation was performed. As a result, the thing using the paint of Examples 5-8 was passed, but the thing using the paint of Comparative Example 2 was rejected.
    [174] From the above results, it was confirmed that the cationic electrodeposition paints of Examples 1 to 8 to which the phosphonium group-containing compound was added showed superior anticorrosive properties than those to which the compound was not added.
    [175] Since the cationic electrodeposition coating composition of the present invention contains a water-soluble or water-dispersible phosphonium group-containing compound, an electrodeposition coating film having excellent anticorrosiveness can be obtained. Since the said phosphonium group containing compound does not contain a heavy metal, it is environmentally friendly and has high compatibility with the resin component which comprises a coating film.
    权利要求:
    Claims (9)
    [1" claim-type="Currently amended] Cationic electrodeposition coating composition comprising a water-soluble or water-dispersible phosphonium group-containing compound having a group represented by the formula (1).
    Formula 1

    Where
    R is the same or different and represents an alkyl group or a hydroxyalkyl group, at least one of R being a hydroxyalkyl group.
    [2" claim-type="Currently amended] A cationic electrodeposition coating composition comprising an epoxy compound as a basic skeleton and containing a water-soluble or water-dispersible phosphonium group-containing compound having a phosphonium group bonded to at least one hydroxyalkyl group.
    [3" claim-type="Currently amended] A cationic electrodeposition coating composition comprising a water-soluble or water-dispersible phosphonium group-containing compound obtained by reacting an epoxy compound with a phosphine compound having at least one hydroxyalkyl group.
    [4" claim-type="Currently amended] The method according to any one of claims 1 to 3,
    A cationic electrodeposition coating composition comprising a phosphonium group-containing compound at 0.5 to 10% by weight relative to the resin solids of the cationic electrodeposition coating composition.
    [5" claim-type="Currently amended] The method according to any one of claims 1 to 4,
    A cationic electrodeposition coating composition further comprising an amine-modified epoxy resin and a block isocyanate curing agent.
    [6" claim-type="Currently amended] The method of claim 5,
    Cationic electrodeposition coating composition in which the amine-modified epoxy resin contains an oxazolidone ring.
    [7" claim-type="Currently amended] The method according to any one of claims 1 to 4,
    A cationic electrodeposition coating composition further comprising a sulfide-modified epoxy resin having an unsaturated hydrocarbon group.
    [8" claim-type="Currently amended] The method of claim 7, wherein
    The cationic electrodeposition coating composition whose unsaturated hydrocarbon group is a propargyl group.
    [9" claim-type="Currently amended] The method according to claim 7 or 8,
    The cationic electrodeposition coating composition whose epoxy resin is a novolak-type epoxy resin.
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    同族专利:
    公开号 | 公开日
    US20020132969A1|2002-09-19|
    CN1375527A|2002-10-23|
    JP2002265878A|2002-09-18|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    法律状态:
    2001-03-15|Priority to JP2001074572A
    2001-03-15|Priority to JPJP-P-2001-00074572
    2002-03-14|Application filed by 닛본 페인트 가부시끼가이샤
    2002-09-26|Publication of KR20020073406A
    优先权:
    申请号 | 申请日 | 专利标题
    JP2001074572A|JP2002265878A|2001-03-15|2001-03-15|Cationic electrodeposition coating composition comprising phosphonium group-containing compound|
    JPJP-P-2001-00074572|2001-03-15|
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