• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    a) dialkyl in an aqueous acid-free aqueous dispersion or solution of one or more of the hydroxycarboxylic acid salts of bismuth (III) having a weight ratio of tin to bismuth of 1: 3 to 3: 1 in terms of metals; Disperse the tin oxide, b) by mixing a formulation obtained with one or more cationic binder vehicles having a weight ratio of hydroxycarboxylic acid salt of bismuth (III) to which dialkyltin oxide is added to the cationic binder vehicle of 0.5: 1 to 6: 1 An acid-free, water-soluble catalyst paste containing a solid content of 30 to 70% by weight obtainable and a cationic binder vehicle diluted with dialkyltin oxide and water and used for negative electrode immersion lacquer.
    公开号:KR20000005150A
    申请号:KR1019980707815
    申请日:1997-04-02
    公开日:2000-01-25
    发明作者:헬무트 훼니히；가브리엘레 비터너；클라우스죄르그 클라인
    申请人:칸 볼프강；헤르베르츠 게엠베하 운트 콤파니 카게；
    IPC主号:
    专利说明:

    Acid-free catalyst pastes, their preparation and use in negative electrode immersion coatings
    FIELD OF THE INVENTION The present invention relates to acid-free catalyst pastes, methods for their preparation and their use in cathodic elctro-dip coating (CEC).
    In general, a metal catalyst is used to crosslink the CEC coating layer to lower the baking temperature. In this regard, organotin catalysts are commonly used, with dialkyltin oxides being preferred, in particular dibutyltin oxide (DBTO) being more preferred due to its readily available and affordable price. However, the successful use of this in CEC coating requires adjustment of the DBTO. Its control may consist of a separate preparation step, for example chemical conversion of DBTO to dibutyltin dicarboxylate.
    Thus, EP-A-0 509 437 introduces CEC coating media which are crosslinked by blocked isocyanates. They further comprise dialkyltin dicarboxylates derived from aromatic carboxylic acids as crosslinking catalysts and bismuth or zirconium compounds as subcatalysts. As bismuth compounds, bismuth hydroxide, trioxide, nitrate, benzoate, citrate, oxycarbonates and silicates can be used.
    DE-A-39 40 781 contains 0.05 to 5 moles of organic acids commonly used for the neutralization of negative electrode depositable electroimmersion coatings per mole of DBTO at a moisture content of 5% by weight or less relative to the sum of DBTO, solvent, acid and water. A process for the preparation of catalyst pastes containing dibutyltin oxide is described by primary dispersion of DBTO with solvent and subsequent dispersion of the mixed powder obtained with powdered binder vehicle and water. The temperature preferable for primary dispersion is the range of 50-80 degreeC. During the manufacture of the CEC coating media, this catalyst paste is resistant to organic acids. However, low acid content is required in CEC coating media because they promote low current consumption and wrap reactions during cathodic lacquer deposition.
    It is an object of the present invention to provide a catalyst paste containing dialkyltin oxides, in particular tin derived from DBTO. The preparation of the catalyst paste should be very simple and the coating media produced using the present catalyst paste should reduce the acid content of the drag by the paste.
    The object of the present invention is surprisingly acid-free, made up of a water-soluble catalyst paste comprising a cationic binder vehicle which is 30 to 70% by weight solids and diluted with dialkyltin oxide and water, the paste being It is obtained through the following process.
    a) dispersing dialkyltin oxide in a water-soluble dispersion or solution of an acid-free one or more of the hydroxycarboxylic acid salts of bismuth (III) having a weight ratio of tin to bismuth in the metal ratio of 1: 3 to 3: 1. Process
    b) mixing a formulation obtained with one or more cationic binder vehicles in which the weight ratio of hydroxycarboxylic acid salt of bismuth (III) to which dialkyltin oxide is added to the cationic binder vehicle is from 0.5: 1 to 6: 1. fair.
    The invention also relates to a process for producing a catalyst paste characterized by the above steps a) and b).
    In particular, the process of the invention is very suitable for the production of catalyst pastes containing DBTO and / or dioctyltin oxide (DOTO), for example as dialkyltin oxides.
    The solutions used for preparing the catalyst pastes according to the invention, including colloidal solutions or dispersions, are referred to as "aqueous preparations" below.
    Examples of water-soluble preparations of the hydroxycarboxylates of bismuth (III) used are the reaction of bismuth (III) oxide and / or hydroxides with hydroxycarboxylic acids at 1.0-3.0 carboxyl groups per mole of bismuth in molar ratio in the presence of water. It includes what can be manufactured by. Preferred hydroxycarboxylic acids for the reaction with bismuth (III) oxide and / or hydroxide are aliphatic hydroxycarboxylic acids, preferably aliphatic hydroxycarboxylic acids having 3 to 8 carbon atoms, and lactic acid and dimethylolpropionic acid. Is particularly preferred. One or more hydroxycarboxylic acids may be used in the mixture. It is preferable to use a water-soluble preparation of hydroxycarboxylic acid salt of bismuth (III) containing 2 to 25% of bismuth by weight in terms of metal, particularly bismuth containing 2 to 25% by weight of bismuth ( III) Water-soluble preparations of dimethylolpropionate and / or lactate are more preferred.
    Dialkyltin oxides, such as DBTO, are dispersed in the presence of a water soluble preparation of the hydroxycarboxylate of bismuth (III). In view of this, the weight ratio of tin to bismuth is in the range of 1: 3 to 3: 1 in terms of metal. The dispersion process in step A) may exhibit additional and desirable effects in the presence of a portion of the cationic binder vehicle. When a binder vehicle containing a basic group is used as the cationic binder vehicle, which is a basic group neutralized by an acid, it is preferably used in partial amount in the process a) in the unneutralized state. For example, up to 70% by weight of the amount of binder vehicle used in step b) can be used in conjunction with step a).
    Conventional binder vehicles suitable as CEC paste resins are preferably used for this purpose as cationic binder vehicles and are referred to hereinafter as "grinding resins" for simplicity. However, they may also be other binder vehicles, such as those used in negative electrode immersion lacquers for coating formation, as described below as examples of binder vehicles for CEC coating media. Most of them are characterized by having excellent wettability with good solubility in water.
    These are resins containing basic groups and resins which are neutralized with acid and then dispersed in water. EP-A-0 183 025 or EP-A-0 469 497 describes examples of preferred paste binder vehicles.
    The dispersing operation in step a) is effected by adding or not dispersing resin so that the proper viscosity of the mixture can be obtained, that is, the liquid substance which is not overflowed is mixed in a mixer such as a dissolver. It can manufacture. Appropriate viscosity can be obtained depending on the amount of water added.
    In general, a dispersion time of, for example, 0.5 to 5 hours is preferred. The preferred temperature during the dispersion operation is 40 ° C. or lower, more preferably 30 ° C. Although preferable minimum temperature is 20 degreeC, it is possible also at this temperature or less.
    The dispersion obtained in step a) is more dispersed and, if desired, is added to the grinding resin as a whole with sufficient acidic grinding resin and water-containing grinding resin to maintain a very small moisture content, e.g. at least 30 grinding resins. The balance of% is subdivided in step b). In this process, the acid is added stoichiometrically for the neutralization of all basic groups that can be neutralized in the grinding binder vehicle and, for example, as a deficiency, preferably 40 to 95%, more preferably 40 to 80% of the maximum stoichiometry. Add. The addition of acid does not need to be added if the grinding resin contains only cationic groups but not basic groups.
    For neutralizing the ground resin, organic acids such as formic acid, acetic acid, lactic acid and dimethylolpropionic acid are particularly preferred acids.
    It is very convenient to add pulverized resin, acid and water to the dispersion, without mixing for a long time and mixing directly after the dispersion process in step a). As an example, milled resin is added first followed by a mixture of acid and water or a mixture of milled neutralized resin and water. In particular, the water uses water which is just deionized.
    Thus, this homogeneously mixed mixture can be ground to a powder of the desired thickness, for example, in a mill such as a bead mill or a multi-cage mill. The most desirable residence time in process b) can be readily determined by one skilled in the art after several tests. This depends on the throughput of the work, the size of the cage, the consumption and quantity of temperature and the grinding media. This process produces a uniform and hazy pigment paste. This catalyst paste is stable during storage in the desired non-overflowing form.
    The catalyst paste according to the invention can be used in the absence of pigmented CEC coating media or pigments. If the catalyst paste is used in pigmented CEC coating media production, it is desirable to pigment the catalyst paste in a suitable way to prevent the formation of pigment paste which separates to the bottom. For this purpose, the necessary pigments and / or extenders are added to process b) in a preferably dispersed or such state in which the ground resin and water are neutralized with acid and mixed, and mixed together with the other components of the catalyst paste. In this operation, the ratio of the grinding resin, acid and water, and additives and solvents can be arbitrarily increased. The catalyst paste according to the present invention has a weight ratio of pulverized binder vehicle solids of 0.5: 1 to 6: 1. For the catalyst paste to which the pigment is added, the hydroxycarboxylic acid salt of bismuth (III) in which the pigment with the addition of the extender is combined with the dialkyl tin oxide is 0.3: 1 to 60: 1 in weight ratio. The term "pigment" as used herein refers to the sum of the dialkyltin oxide and bismuth (III) hydroxycarboxylic acid salts and optionally pigments and / or extenders. Solid content of the catalyst paste of this invention is 30 to 70 weight%.
    General inorganic and / or organic pigments are suitable as pigments and / or extenders, for example carbon black, titanium oxide, iron oxide, kaolin, talc or silica, phthalocyanine pigments and quinacridone pigments, and also zinc phosphates and lead silicates and The same corrosion resistant pigments are also included.
    Processes a) and b) can be carried out at low temperatures, preferably not to exceed a temperature of 40 ° C., with a minimum temperature of about 20 ° C. or lower.
    The catalyst paste according to the present invention may contain an organic solvent. These may be derived from crushed binder vehicles or may be added respectively in process a) or process b). Examples of such solvents include alcohols such as methanol, ethanol, cyclohexanol or 2-ethylhexanol, glycols such as ethylene glycol, propylene glycol, diethylene glycol or dipropylene glycol, methoxypropanol, ethoxypropanol, Glycol ethers such as methoxyethanol or diethylene glycol diethyl ether, ketones such as methyl isobutyl ketone, methyl ethyl ketone or cyclohexanone, or hydrocarbons. The amount of the solvent is preferably 10 to 50% by weight based on the solid content of the catalyst paste.
    The catalyst paste according to the invention may comprise, for example, conventional additives such as wetting agents and antifoaming agents. They are added in conventional amounts as those skilled in the art in the manufacturing process of process a) and / or process b).
    CEC coating medium, on the other hand, is neutralized with acid if necessary and diluted with water and then in admixture with the required CEC binder vehicle and optionally with admixtures with crosslinking agents and as a single-component material or preferably with CEC binder vehicle dispersions. Together as a two-component material, it can be prepared by conventional methods from the catalyst paste according to the invention. If the CEC coating medium is crosslinked by an external method, this CEC binder vehicle dispersion generally includes a crosslinking agent. The electrically conductive substrate can be coated with CEC coating media by conventional methods and the lacquer coating layer can be crosslinked, for example by heating.
    CEC coating media produced using the catalyst pastes according to the invention are water-soluble coating media with a solid content of up to 50% by weight, such as from 10 to 30% by weight. Solids include conventional binder vehicles and milling resins, pigments optionally present, and / or substituents which may be converted to cationic substituents or cationic groups and optionally present crosslinking agents as well as groups capable of chemically crosslinking. Or extenders and DBTO, bismuth (III) hydroxycarboxylic acid salts and other additives. Cationic groups are basic groups such as those derived from amino groups by neutralization with acids such as ammonium groups or other cationic groups such as quaternary ammonium groups. Examples of basic resins that can be used as the binder vehicle include primary, secondary or tertiary amino groups and for example 20 to 250 mg KOH / g of amines. It is preferable that the weight average molecular weight (Mw) of this resin is 300-10,000. Examples of such resins include aminomethacrylate resins, aminoepoxide resins, aminoepoxide resins containing double bonds at terminals, aminoepoxide resins containing primary OH groups, aminopolyurethane resins, amino Polybutadiene resins containing groups or modified epoxide resin-carbon dioxide amine reaction products. These basic groups exist in quaternary form or are converted to cationic groups by reaction with organic monocarboxylic acids such as lactic acid, formic acid or acetic acid, which can be readily carried out by conventional neutralizing agents such as those skilled in the art. do. This resin is self-crossing or used in combination with a known crosslinking agent. Examples of such crosslinkers include amino plastic resins, blocked polyisocyanates, crosslinkers containing double bonds at the ends, polyepoxide compounds, crosslinkers containing cyclic carbonate groups, or transesterification and / or transamidation. crosslinking agents containing groups capable of transamidisation.
    Bayes resins and crosslinkers used in CEC baths are EP-A-0 082 291, EP-A-0 234 395,
    EP-A-0 209 857, EP-A-0 227 975, EP-A-0 178 531, EP-A-0 333 327, EP-A-0 310 971, EP-A-0 456 270, US 3 922 253, EP-A-0 261 385, EP-A-0 245 786, EP-A-0 414 199, and EP-A-0 476 514. These resins may be used alone or in combination with each other.
    In addition to the additives incorporated for the catalyst pastes according to the invention, they also include additives common for CEC coating media. Examples include wetting agents, flow improvers, antifoams and solvents, including the additives and solvents already described in connection with the catalyst pastes according to the invention.
    The catalyst pastes according to the invention are simple and can be produced at low temperatures and do not draw free acids in the CEC coating media produced with them.
    Example
    Preparation of CEC Dispersions
    a) 832 parts of monocarbonate (trade name Epicote 828) of an epoxy resin based on bisphenol A and 712 parts of an easy-to-purchase polycaprolactone polyol (trade name CAPA 205) 830 imposed diglycol dimethyl ether, followed by epoxide It was reacted with 0.3% of BF 3 etherate at 70-140 ° C. until the number reached zero. 307 parts of a reaction product having an NCO content of about 12.8% by reaction of 174 parts of toluene diisocyanate (2 equivalents of NCO) with 137 parts of 2-ethylhexanol and 0.3% of benzyltrimethylammonium hydroxide (Triton B), 40 To the product (solid content: about 70%, 2 equivalents of carbonate) was added in the presence of 0.3% zinc acetylacetonate as catalyst at a temperature of ˜80 ° C. The batch was reacted to an NCO value of about 0 and then adjusted to about 70% solids with diglycol dimethylether.
    b) NCO content produced by the reaction of 348 parts of toluene diisocyanate (80% 2,4-isomer, 20% 2,6-isomer) with 274 parts of 2-ethylhexanol and 0.3% benzyltrimethylammonium hydroxide 618 parts of this reaction product, which is about 12.8%, was gradually added to 1759 parts of bicarbonate of an epoxy resin based on bisphenol A (trade name: Epicote 1001) at a temperature of 60 to 80 ° C. The reaction was left to have an NCO value of about zero. 622 parts of the reaction product produced by the reaction of 137 parts of 2-ethylhexanol with 174 parts of toluene diisocyanate (NCO content: about 12.8%) and 0.3% of benzyltrimethylammonium hydroxide were subjected to methoxypropanol at a temperature of 20 to 40 ° C. To 860 parts of bis-hexamethylenetriamine dissolved in 2315 parts was added. 4737 parts of reaction product b) and 3246 parts of reaction product a) (70% each to diglycol dimethyl ether) were added and the batch was reacted at a temperature of 60 to 90 ° C. The reaction was terminated at an amine number of about 32 mg KOH / g. The obtained product was distilled under vacuum to obtain about 85% solids.
    It was neutralized with 30 mmol of formic acid per 100 g of the resin and converted to a dispersion which was about 40% by weight solids with deionized water.
    Preparation of Catalyst Pastes
    a) 100.0 g pulverized resin according to EP-A-0 469 497, Example 1 (55% by weight), wetting agent based on 16 g polyethylene / propylene glycol, 24.0 g easy to purchase antifoam, and At a weight of 236.0 g, 20% of an aqueous solution of bismuth (III) hydroxycarboxylate [repared from 1 mole of bismuth (III) oxide and 1 mole of dimethylpropionic acid] was respectively mixed in the dissolver. 50.3 g of DBTO and 8.0 g of silica were added and the mixture was dispersed at 30 ° C. for 1 hour after adding 41.0 g of deionized water.
    b) Neutralize 94.5 g of the grinding resin according to EP-A-0 469 497, Example 1 (55% by weight) with 9.9 g of 5.3 N acetic acid, dilute with 180.0 g of deionized water and 3.8 g of carbon black 436.5 g of titanium oxide was added and the mixture was dispersed.
    The dispersion mixtures obtained in a) and b) were mixed and ground together in a bead mill under a temperature of 30 ° C. to prepare a catalyst paste with gray pigment. The catalyst paste prepared in this way was free acid.
    Manufacturing of CEC Coated Medium
    The weight ratio of CEC coating medium and pigment / binder vehicle at 20% by weight solids is 0.35: 1 for CEC dispersions, catalyst pastes and deionized water [igments = bismuth (III) hydroxycarboxylic acid salts, DBTO, silica, The sum of carbon black and titanium oxide; Binder vehicle = sum of CEC dispersion and solids derived from solid grinding resins.
    权利要求:
    Claims (9)
    [1" claim-type="Currently amended] a) dialkyl in an aqueous acid-free aqueous dispersion or solution of one or more of the hydroxycarboxylic acid salts of bismuth (III) having a weight ratio of tin to bismuth of 1: 3 to 3: 1 in terms of metals; Disperse the tin oxide,
    b) by mixing a formulation obtained with one or more cationic binder vehicles having a weight ratio of hydroxycarboxylic acid salt of bismuth (III) to which dialkyltin oxide is added to the cationic binder vehicle of 0.5: 1 to 6: 1 An acid-free water soluble catalyst paste containing a solid content of 30 to 70% by weight obtainable and a cationic binder vehicle diluted with dialkyltin oxide and water.
    [2" claim-type="Currently amended] a) dialkyltin oxides are converted to metals and dispersed in a solution of one or more of the acid-free dispersions of hydroxycarboxylic acid salts of bismuth (III) having a weight ratio of tin to bismuth of from 1: 3 to 3: 1; ,
    b) The obtained formulation is mixed with one or more cationic binder vehicles in which the weight ratio of hydroxycarboxylic acid salt of bismuth (III) to dialkyltin oxide to cationic binder vehicle is from 0.5: 1 to 6: 1. A process for producing an acid-free water soluble catalyst paste vehicle comprising a solid content of 30 to 70% by weight and a cationic binder diluted with dialkyltin oxide and water.
    [3" claim-type="Currently amended] The process according to claim 1 or 2, wherein step b) comprises a weight ratio of the sum of the pigments, extenders, dialkyltin oxides and hydroxycarboxylic acid salts of bismuth (III) to the cationic binder vehicle is 0.5: 1 to 6: 1. And a weight ratio of pigment and extender to dialkyltin oxide and hydroxycarboxylic acid salt of bismuth (III) in the presence of one or more pigments and / or extenders, wherein the weight ratio is 0.3: 1 to 60: 1. And a preparation method thereof.
    [4" claim-type="Currently amended] Catalyst paste and process according to any one of the preceding claims, characterized in that process a) and / or process b) is carried out in the presence of an organic solvent and / or at least one conventional lacquer additive.
    [5" claim-type="Currently amended] The catalyst paste according to any one of the preceding claims, wherein the dialkyltin oxide is dibutyltin oxide and a method of producing the same.
    [6" claim-type="Currently amended] The catalyst paste according to any one of the preceding claims, wherein the hydroxycarboxylic acid salt of bismuth (III) is a lactic acid salt or a dimethylolpropionic acid salt.
    [7" claim-type="Currently amended] The catalyst paste according to any one of the preceding claims, wherein the cationic binder vehicle is a conventional cationic paste resin or a binder vehicle for negative electrode immersion lacquer, and a method for producing the catalyst paste.
    [8" claim-type="Currently amended] Use of a catalyst paste in a negative electrode deposition immersion lacquer according to any one of claims 1 or 3 or 7 or according to any one of claims 2 or 3 to 7.
    [9" claim-type="Currently amended] Characterized in that the electro-immersion lacquer comprises a catalyst paste prepared according to any one of claims 1 or 3 to 7 or according to claim 2 or 3 to 7. Coating method of electrically conductive substrate by negative electrode immersion coating.
    类似技术:
    公开号 | 公开日 | 专利标题
    EP0642558B1|1996-09-25|Catalyzed cationic paint binders, process for their preparation, and their use
    US4830722A|1989-05-16|Water-dilutable binders for cationic electrocoating finishes and a process for the preparation thereof
    CA1224588A|1987-07-21|Hydroxyalkyl carbamate-containing resins for cathodic electro-deposition and method of making the same
    KR950007991B1|1995-07-24|Glycidol-modified polyepoxidepolyoxyalkylenepolyamine adducts
    RU2445332C2|2012-03-20|Electroplating composition containing cyclic guanidine
    KR920001391B1|1992-02-13|Cationic electrocoating compositions
    KR950005505B1|1995-05-24|Process for the preparation of aminourethanes
    US3922253A|1975-11-25|Self-crosslinking cationic electrodepositable compositions
    CA2204434C|2000-07-04|Cationic resin and capped polyisocyanate curing agent suitable for use in electrodeposition
    US4017438A|1977-04-12|Ketimine-blocked primary amine group-containing cationic electrodepositable resins
    EP0961797B1|2003-04-09|Aqueous binding agent dispersion for cationic electro-dipcoat paint
    KR100366471B1|2005-01-24|Hardening of Electrophoretic Electrodeposited Coating Materials Using Bismuth Catalysts
    US5633297A|1997-05-27|Cationic resin containing capped isocyanate groups suitable for use in electrodeposition
    EP0920468B1|2000-05-17|Cationic electrocoating compositions, method of making, and use
    EP0256020B1|1990-11-14|Water-dilutable binders for cationic electrophoretic lacquers and method for production
    EP1425354B1|2005-03-16|Cathodic electrocoating compositions containing hydroxyl-carbonate blocked polyisocyanate crosslinking agent
    US4609691A|1986-09-02|Water-dispersible binders for cationic electrodepositable paints, and method for their production
    AU715805B2|2000-02-10|Electrodepositable coating composition containing bismuth and amino acid materials and electrodeposition method
    KR101162132B1|2012-07-03|Electrodeposition paint
    US6838506B2|2005-01-04|Cationically electrodepositable coating material
    EP0272665B1|1994-02-02|Aminourethanes, process for their preparation and their use
    US6664345B2|2003-12-16|Oxazolidone ring-containing epoxy resin
    US6265079B1|2001-07-24|Cationic electrodeposition coating composition
    KR0151552B1|1999-06-01|Electrocoated compositions of polyamines and self-condensed epoxy adducts and coatings prepared therefrom
    CA1256633A|1989-06-27|Process for the production of pigment grindingvehicles for use in water dilutable paints
    同族专利:
    公开号 | 公开日
    US6174422B1|2001-01-16|
    ZA9702841B|1997-10-31|
    ES2138866T3|2000-01-16|
    AT184901T|1999-10-15|
    WO1997038056A1|1997-10-16|
    JP4159604B2|2008-10-01|
    KR100401179B1|2004-04-03|
    ZA972841B|1997-10-31|
    EP0891398A1|1999-01-20|
    JP2000508357A|2000-07-04|
    EP0891398B1|1999-09-22|
    DE19613685C1|1997-09-11|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    法律状态:
    1996-04-05|Priority to DE19613685.7
    1996-04-05|Priority to DE1996113685
    1997-04-02|Application filed by 칸 볼프강, 헤르베르츠 게엠베하 운트 콤파니 카게
    2000-01-25|Publication of KR20000005150A
    2000-06-20|First worldwide family litigation filed
    2004-04-03|Application granted
    2004-04-03|Publication of KR100401179B1
    优先权:
    申请号 | 申请日 | 专利标题
    DE19613685.7|1996-04-05|
    DE1996113685|DE19613685C1|1996-04-05|1996-04-05|Acid-free catalyst paste, its production and use in cathodic electrocoating|
    [返回顶部]