• 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:
    Binders for cathodically depositable aqueous coating compositions comprising the reaction product, having an NCO-value of zero, of (A) polymers carrying reactive hydroxyl groups and having a hydroxyl number of at least about 40 mg KOH/g; and (B) compounds carrying per molecule an average of 0.8 to 1.5, and preferably 1.0, free isocyanate groups and at least one teritary basic aliphatically bound nitrogen atom. Optionally, the reaction product of (A) and (B) can include as (C) a compound carrying an average of 0.8 to 1.5, and preferably 1.0, free isocyanate groups and from 1 to 3 olefinic double bonds.
    公开号:SU1071224A3
    申请号:SU782671001
    申请日:1978-10-11
    公开日:1984-01-30
    发明作者:Пампоухидис Георгиос；Хениг Хельмут
    申请人:Вианова Кунстхарц Аг (Фирма)；
    IPC主号:
    专利说明:

    The invention relates to the preparation of a binder for coatings deposited on a cathode, and can be used in various industrial areas. A method is known for preparing a binder for cathode-x-ray coated coatings by reacting the isocyanate component with a compound containing an active hydrogen atom in an inert atmosphere. in relation to the isocyanate solution flj. However, use upon receipt. Coatings freeamine increases the toxicity of the process. In addition, the resulting coatings are not corrosion resistant. . The purpose of the invention is to obtain corrosion-resistant coatings. This goal is achieved in that, according to crtocoCy, the formation of a bond for cathode deposited coatings by reacting the isocyanate component with a compound containing an active hydrogen atom; in an inert isocyanate-containing solvent as a compound containing an active atom; hydrogen (A |), use a copolymer with a hydroxyl number equal to 50-250 mg KOH / based on acrylic or methacrylic acid ester with mono-alcohol and acrylic or methacrylic acid mono-ester with dihydric C, -C, or tripropylene glycol, styrene and / or acrylamide / and / or. dimethylaminoethyl methacrylate. and as the isocyanate component, a compound of the formula (B R n -C, HO-C-NH-X-NCO, K (- | CHj, -JC Kj., L) is additionally introduced a compound of the formula (with G O {(Cf CC-Of Y-0-C-lMH-X-NCO, where n 1-3,, (. X is an aromatic, aliphatic or cycloaliphatic radical; Y is a mono- or dialkylene radical with 2 carbon atoms and 2 , 5-4.5 hydroxyl equivalents of the copolymer (M 1.5-1.8 mol of the component is used (B and 1.02, 6 Mole of the component (C) and the reaction is carried out at the BO-C 0 until the isocyanate groups disappear. As di- or polyisocyanates these include: aromatic isodianates of the 2,4- or 2-type, b-toluene diaisocyanate and mixtures thereof, 4,4-diphenylmethane diisocyanate or cycloaliphatic isocyanates such as isophoric isocyanate, cyclohexane-1,4-diisocyanate, as well as aliphatic isocyanates, for example, trimethylhextectylmethyl acetate. - diisocyanate, tris-hexamethylene tri 3 octane atat.The interaction between the amine and the diisocyanate or polyisocyanate occurs at, preferably at 20-50 s. The weight ratios of the reagents are chosen in such a way that the compounds forming the compound contain 0.8-1.5, predominantly one free isocyanate group (they are designated as the main isocyanate preproductive L) In order to promote the thermal crosslinking of cathode deposited coatings, the reaction products are and other compounds that contain an average of 0.81, 5 free isocyanate groups and 1 to 3 olefinic unsaturated double 1e bonds per molecule. These compounds are prepared by a separate step from the above diisocyanates and and polyisocyanates with reagents (which, along with at least one hydrogen atom reactive with the isocyanate, also contain 1–3 olefinic double bonds. Suitable unsaturated compounds are, for example, hydroxyalkyl acryl ethers of acrylic or methacrylic acid, triztilenglykolemmonetacrylate , triethylol propane methacrylate, allyl alcohol, tripropylene glycol monoabietat, oleyl alcohol or h1-oleyl alcohol. The interaction of a diisocyanate or a polyisocyanate and an olefinic unsaturated compound reactive towards the isocyanate takes place in a medium of a solvent inert towards the isocyanate at 1010 ° C, preferably at 50-80 ° C, in the presence of hydraulic compounds as a catalyst. The weight ratios of the reaction components are selected in such a way that the resulting compounds contain 0.8-1.5, preferably one free isocyanate group per molecule (This compound is referred to as olefin-unsaturated isocyanate forprog / duct). The hydroxyl-containing polymers used are further modified. This process is carried out in such a way that the above copolymers containing hydroxyl groups are preferably dissolved in solvents that are inert with respect to the isocyanate, are treated preferably with a quantity of basic isocyanate pre-product and
    olefinated non-isocyanate pre-product at 10-100 ° C, preferably at 50-80 ° C, as required, in the presence of organically tin compounds as a catalyst until the NCO content is almost zero.
    The amount of the main isocyanate pre-product is chosen in such a way that the basicity of the binder composition after neutralization with acid Causes sufficient water dispersibility at a pH of 4-8, preferably 5-7.
    The interaction of hydroxy-containing copolymers, the main isocyanate pre-product and the olefin-unsaturated isocyanate pre-product can occur in any order, separately or together.
    Lowering the temperature of hot drying or obtaining special corrosion protection makes it possible to use additional known cross-linking agents or urea-melamine or phenol-resin; one or more dehydrated condensates.
    Takiesmol are obtained by known methods: alkaline condensation of f Rmaldehygid or compounds, ylJHX forked dehydrate, with urea, melamine, benzoguanamine, acetoguanes, phenol6m cresol, p-tert-butyl phenol, bnsphenol A, etc.,
    The methylol compounds may be esterified as necessary with alcohols.
    The main nitrogen atoms of the proposed film breakdown process are neutralized partially or completely with organic and / or inorganic acids, etc. The degree of neutralization in some cases depends on the properties of the binder used. The acid is added in such a quantity that the film-forming agent can be diluted with water at a pH of 4-8, preferably 5-7.
    The concentration of the binder in water depends on the parameters of the method during processing by means of electrical submersion and is in the range of 3-30 weight. preferably 5-15 wt.%. The composition may also contain various additives such as pigments, fillers, surface active substances, etc.
    When a coating is applied, the composition containing this binder comes into contact with a conductive anode and cathode, and the surface of the cathode is covered with a layer of coating (film). It is possible to apply a coating on various electrical wires of a more sub-surface, in particular on metallic materials such as steel, aluminum, copper and the like, as well as on metallized polymeric materials or other materials already
    provided with electrically conductive film-forming.
    After deposition, the film-forming agent is rinsed with water as needed. It is cured at elevated temperature. For curing, temperatures of between 130 and 200 ° C are used, preferably between 15 ° C and 190 s. The cure time is 5-30 minutes, preferably 10-25 minutes.
    Getting preprodukty.
    (A) - Polymers containing hydroxyl groups.
    In a reaction vessel equipped with a stirrer, a thermometer, an inert gas supply and a reflux condenser, about 1/5 of a solution consisting of 666 parts by weight is heated with stirring until refluxing. ethyl glycol acetate, if necessary, depending on the monomer introduced, 30 weight parts. nitrile azoisobuty acid and 50 weight.h. dodecyl mercaptan, and the remaining portion of this solution is added dropwise within 1-2 hours. Then, with refluxing, the mixture is stirred until the calculated (theoretical) amount of the solid phase is reached (about 4 h).
    Component A1, parts:
    N-butyl acrylate 500
    2-Oxyethylacrylate 400
    Styrene.100
    Component A2, parts:
    N-butyl acrylate 400
    4- Oxybutyl acrylate 500
    Styrene100
    Component A3, parts by weight:
    n-butyl acrylate 360
    2-Hydroxyethylmethacrylate400
    Tripropylene glycol monomethacrylate 140
    Styrene100
    Component A4, parts:
    "- Butyl.acrylate 300 2-Oxyethylacrylate 250
    4-Oxybutyl acrylate 290-Acrylamide 40
    Styrene120
    (B) - Basic isocyanate pre-products.
    Component B1. In a three-necked flask with a reflux condenser and an inert gas supply in the complete absence of: moisture and intensive cooling, 174 g of toluene diisocyanate (a mixture of 80% 2.4 and 20% 2,6-isomers) is treated uniformly with 89 g of dimethylestanolamine — at 60% dilution with ethylene glycol monoethyl ether acetate. reactions should not exceed. The reaction is completed when the calculated value is reached (theoretical / isocyanate content 16% or lower; Component B2. 174 g toluene diisodisodianate Asses 80% 2.4 and 20% 2,6 isomers; 194 g ethylene glyc monoethyl ether They are mixed in a three-necked flask equipped with a reflux condenser and an inert gas supply with no liquid at all. With intensive cooling for 1 hour, 117 g of diethylethanolamine is added evenly at a lower temperature. The isocyanate content in the target product is 14.4% (c ) - olefinically unsaturated isociavate pre-products. Component G1. In a three-necked flask equipped with a reflux condenser and an inert gas supply, with the absence of moisture, 168 g of hexamethylene diisocyanate are mixed with 200 g of ethylene glycol monoethyl ether acetate and warm to 60 ° C. At this temperature, a mixture of 130 g of hydroxyethyl methacrylate stabilized with 0.1 g of hydroquinone is added dropwise. The reaction is completed after about 2 hours when the isocyanate content is 14.1%. Or much less. Component C2. In a three-necked flask with a reflux condenser and an inert gas feed, in the absence of moisture, 222 g of isophorone diisocyanate are mixed with 325 g of ethylene glycol monoethyl ether with a tatom and heated to. 116 g of hydroxyethyl acrylate is gradually added, and after the addition is completed, the temperature is raised to maintain this temperature in the reaction mixture until / until the isocyanate content reaches 12.5%. Component NW. 277 g of ethyl glycol acetate and 174 g of toluylene diisocyanate (a mixture of 80% 2.4% and 20% 2, b isomers) are charged to the reaction vessel and, in the absence of moisture, trimethylolpropane diacrylate is added for 1 hour at 25-35 to 242 g. Then the reaction mixture heated to 60-70 ° C and stirred at this temperature until the content of the isocyanate is about 10%. Component C4: Similar to component S3, but with the difference that 193 g of ethyl glycol acetate and 174 g of toluene diisocyanate and the solution are loaded. 116 g of hydroxyethyl acrylate are dropwise. Examples 1-9. In the reaction containers equipped with a stirrer, a funnel, a thermometer and a reflux condenser to a polymer containing a large number of hydroxyl groups (chagtic component A 7, as necessary in the presence of a solvent inert with respect to the isocyanate ((such as ethylene glycol monoethylg. ester ester)) added in the absence of moisture, the main isocyanate forproduct is a partial component BJ and then the reaction is completed at 40-100 C. Then the reaction product is treated with oi, / 3-.-olefin with an unsaturated isocyanate-product partial component C If so,. .. LLAO1h ..., Tg, when given, the mixture is allowed to react until the content is reached: ЫSO equal to zero. Treatment of component A with component B and component C can also be carried out in one stage at 40-100 ° C, this does not significantly affect the results obtained. In Table 1, the number of components and the reaction conditions are compared. Testing a sy jan. WBCs of the specified binders were used to prepare samples, each of 100 g of solid resin, treated with an appropriate quantity, acid, and diluted with stirring with deionized water to obtain 1000 g. From 10% solutions are coated with a direct current on a steel plate, connected as a cathode. The deposition time in all cases is 90 s, the coated substrates are then; washed with deionized -; water and cured at elevated temperatures. The average layer thickness of the hot-drying film is 1317 mm. The amount of acid in grams per 100 g of solid resin. Measured in 10% aqueous solution. An eternity hardness according to Konig Din 53157 Erichsen Dean Strength 53156. The stability is determined by the time it takes for rust or bubbles to form at a layer of water (40 ° C. Hdna. Heat resistance in AS m 117-64 , damage of 2 mm on the cross-section according to the indicated number of hours. For this test, a layer of pigmented bond dego coating is applied to the cleaned, unprepared steel sheet and the pigmented linkage per 100 parts by weight of solid resin contains 20 weights alumosilicate pi and 2 parts by weight. Table 2 compares the results obtained.
    Table. one
    All quantities are based on dry matter.
    The reactions of components B and C occur together.
    Tab. persons 2
    权利要求:
    Claims (2)
    [1]
    METHOD FOR OBTAINING A BINDER for cathode-deposited coatings by reacting an isocyanate component with a compound containing an active hydrogen atom in a solvent inert with respect to the isocyanate, with the aim that, in order to obtain corrosion-resistant coatings , as a compound containing an active hydrogen atom (A /, use a copolymer with a hydroxyl number equal to 50-250 mg KOH / g based on an ester of acrylic or methacrylic acid with a monoalcohol C ^ -Cg, and a monoester of acrylic or methacrylic acid with dihydric alcohol C ^ -C *, or tripropylene glycol ^ styrene and / or acrylamide, and / or dimethylaminoethylmeth. a component using a compound of formula (B)I o '_ s2N40-S-BK-X-KSO
    K where k 4 g of CH H C N and further administered a compound 'of Formula (C)
    Ύ 1 and o '(CH 2 = CC-0) n -Y-0-C-NH-X-NCO, where η = 1-3,
    L4H 7 -CH 3 ;
    X is aromatic, aliphatic, or cycloaliphatic. feces;
    Y is a mono- or dialkylene radical with the number of carbon atoms ι measures 2–6, I with 1.5–1.8 mol of the component used in 2.5–4.5 hydroxyl equivalents of the copolymer (A) (B / and 1 0-
    [2]
    2.6 mol component (C | and the interaction is carried out at 60-80 ° C until the disappearance of the isocyanate groups "
    I SU „1071224 A
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