• 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:
    (1) 40 to 85% by weight of a polymer dispersion based on (meth)acrylate esters and (meth)acrylic acid, optionally styrene and/or alkylstyrenes, (2) 5 to 40% by weight of a water soluble and/or water dispersible partially or completely etherified amine-formaldehyde condensate, (3) 10 to 40% by weight of a solution polymer water soluble upon neutralisation with bases consisting of hydroxyalkyl(meth)acrylates, (meth)acrylates and optionally vinyl aromatic monomers selected on the basis of the glass transition temperatures of their homopolymers, (meth)acrylic acid, and optionally diesters of maleic or fumaric acid with C4-C10 monoalcohols, (4) 0-100% by weight (based on components (1), (2) and (3)) of one or more pigments and/or extenders, auxiliary solvents and additives. m
    公开号:SU1068039A3
    申请号:SU792776205
    申请日:1979-06-19
    公开日:1984-01-15
    发明作者:Цима Херберт；Госсак Курт
    申请人:Вианова Кунстхарц Аг (Фирма)；
    IPC主号:
    专利说明:

    Isorethination refers to water-soluble thermo-hardened coating compositions and can be used in the automotive industry and other technical fields.
    A known composition for coatings comprising an acrylic copolymer, a feiol-formaldehyde resin, and targeted additives C,
    However, coatings based on this composition have insufficient hardness and adhesion.
    The closest to the invention in technical essence and the achieved result is a water-soluble heat-curing composition for coatings, including an acrylic copolymer and a water-soluble or water-dispersible amino-formaldehyde resin, partially or completely esterified, with monohydroxy alcohols 2.
    However, the known composition does not spread well enough over the surface to be coated, forming at ETOG1 a coating of insufficient thickness (no more than 45 µm) and uniformity.
    The aim of the invention is to improve the flowability of the composition and to provide the possibility of increasing the thickness of the coating while maintaining its uniformity.
    The goal is achieved by the fact that a water-soluble thermosetting composition for coatings, including an acrylic copolymer and a water-soluble or water-dispersible amino-formaldehyde resin, partially or fully esterified with C-C-monohydric alcohols, contains as a acrylic copolymer a 45–50% aqueous dispersion copolymer vial composition. 35-86.5% by weight of acrylic and / or methacrylic acid ester with (, monoatomic or alcohols, 12-20% by weight, hydroxyethyl (meth) acrylate or mixture of hydroxyethyl acrylate with polypropylene glycol monomer that krylate, 1.5-3 wt.% methacrylic acid and 0-43 wt.% styrene, and 47.5-49.5% solution in an organic solvent selected from the group including diethylene glycol monobutyl ether, ethylene glycol monoethyl ether acetate, butanol, water-soluble after neutralization with the base of a copolymer containing 24-55 wt.% hydroxyalkyl acrylate or polypropylene glycol monomethacrylate with a glass transition temperature of their homopolymer -25 to -64 ° C, 39-70 weight,% alkyl (meth) acrylate with temperature, homopolymer glass transition - 56 - 70 ° and 6-8 wt.% (Meth) acrylic acid, or in -soluble after neutralization with bases copolymer containing 25 wt.% or hydroxyalkyl polipropilenglikolmonometakrilata with a glass transition temperature of the homopolymer -25 -64 ° C, 40-43 wt.% of alkyl (meth) akri5 lata with TE glass mepatypoy
    homopolymer -56 - -70 ° C, 6-7 wt.% (meth) acrylic acid and 26-28 wt. octylstyrene or dibutyl fumarate in the following ratio of components, wt. h:
    45-50% water dispersion of acrylic copolymer89-120
    5 47.5-49.5% solution of acrylic copolymer in organic solvent 30-60
    Water soluble or 0 water dispersible
    amino formaldehyde
    resin, partially or
    fully esterified With —C — monohydric alcohols15–30
    The composition may additionally contain pigments and / or fillers, corrosion inhibitors, curing catalysts and other targeted additives that are compatible with binders in an amount up to 100% by weight relative to the amount of binders „
    As pigments or fillers, all products known in the paint and varnish industry can be used in quantitative terms, depending on the desired color of the coating and its application.
    As a water-soluble or water-dispersible amino-formaldehyde resin, amino aldehyde condensates are used, partially or
    fully esterified, such
    as hexamethoxymethylmelamine, methylated and methanol-esterified melamine condensate, completely esterified with methanol and butanol (in the ratio) hexamethylolmelamine, esterified with 80% methanol and ethanol (1: 1 ratio) containing an average of 5.5 methyl groups
    5 per melamine molecule.
    The manufacture of aqueous dispersions of acrylic copolymer (component 1) is carried out by emulsion polymerization in the presence of anionic, and also, if necessary, non-anionic emulsifiers and radical initiators. As anionic emulsifiers, hydrocarbon sulfonates, such as dodecyl benzene sulfonate, sodium lauryl sulfate, sodium tridecyl sulfate or ethoxylyl fatty alcohol sulfates, such as sodium lauryl ethoxylate sulfate or substituted with oxide, ethylene and then sulfated octylphenol are used. In addition, emulsifiers of the type of ethoxylated alkylphenol in a mixture with anionic emulsifiers are preferably used. To increase storage stability, other emulsifiers may be added at the end of the polymerization.
    The compositions of component 1 are presented in table. one,
    The acrylic copolymer solution in an organic solvent (component 2) is a solution of a polymerizate with an acid number of at least 26 mg KOH / G, which, after partial neutralization by inorganic or organic bases of the existing carboxyl groups, becomes water soluble. These polymers have extremely low glass transition temperatures.
    Preparation of polymerizate solutions is carried out using radical polymerization in an inert organic solvent, such as ethyl acrylate, ethyl glycol acetate, butanol, glycol ether, especially diethylene glycol monobutyl ether. Heated to 80 ° C, the solvent is fed to the corresponding reaction vessel for 6 hours, where it is in advance A prepared mixture of monomers and initiator (predominantly azodiisobutyrate dinitrile). The reaction temperature is 80 ° C. Similarly, a portion of the total mixture may be in the reaction vessel, and the residue is added during the reaction. After the end of the solvent supply, a different initiator (/ -1-3 parts) is added and the temperature is maintained at about 80 ° C for 2 hours. The mixture is kept for another 1 h. Carboxyl groups of the polymer solution are completely or partially neutralized by means of amines to translate into water-soluble form. Predominantly tertiary alkyl- or alkanolamines. To prepare solvent-free polymerization solutions, the solvent can be removed from the dilute aqueous solution by distillation, if necessary, by an azeotropic method and / or in vacuo.
    The resulting compositions of component 2 are presented in table. 2
    The composition is prepared as follows.
    The solution of component 2 is mixed with dimethylethanolamine until the sample mixed with distilled water in a ratio of 1: 1 has a pH value of about 9. Dehydrated neutralized solution of the resin is ground in case of using pigments, for example, with titanium dioxide on a three-drum mechanism and mixed with the aminophore maldehyde resin (component 3). This mixture is slowly and with vigorous stirring introduced into the aqueous dispersion (component 1), brought with dimethylethanolamine
    0 to pH 7, and at the same time, if necessary, diluted with deionized water. After thorough mixing, a hardener is added, if necessary (for example, 1ep,
    5 A 10% solution of p-toluenesulfonic acid, neutralized with dimethylethanolamic), and also, if necessary, a corrosion inhibitor. Finally, the initial mixture is made up with a deionized
    water to spray viscosity of about 20 St (according to DIK 53211). Spray varnish is applied to the cleaned steel sheet and burned for 30 minutes at 160 ° C.
    Examples of specific performance (1-10) illustrating the invention are presented in table. 3
    Example 11. 734 parts of a solution of component 2A are diluted.
    0 1006 parts of deionized water, -divided with dimethyl ethanolamine to pK, 5, and the butanol available is distilled with one part of water. A 30% solution of the resin is obtained, the pH value of which is set with dimethylethanolamine equal to 9.
    , 83 parts of the resin solution are ground on a three-roll mechanism with
    80 parts of TiO (rutile) and 25 parts of diethylene glycol monobutyl ether and mixed with 25 parts of the methylated and methanol-esterified condensate
    g melamine. The mixture is slowly and with vigorous stirring introduced into -111 parts of the aqueous dispersion of component 1, brought to pH 7-7.5 with dimethylethanolamine, and if necessary, deionized water is added at a time. After thorough mixing, add 3 parts of a 10% aqueous solution of p-toluenesulfonic acid, neutralized with dimethylethanolamine, and 0.3 part of a corrosion inhibitor. Component ratio 1-3 of the binder system is 50:25: 25%, respectively.
    0 The initial mixture is made up with a deionized water at a spray viscosity of 20 St (according to DTH 53211), sprayed onto a clean steel sheet for 30 minutes.
    burned at 160 C.
    Example 12. A solution of component 2 is mixed with 80 parts of hexamethoxymethyl melamine and heated for 5 hours with stirring until slight amounts of water and solvent are removed. The resulting resin is mixed with dimethylethynolamine until the sample, mixed with distilled water in a 1: 1 ratio, will matter. 50 parts of the dewatered neutralized resin solution (56%) are ground with 80 parts of TiO (rutile) on a three-roll mechanism and mixed with 11.8 hexamethoxymethylmelamine.
    This mixture was slowly and with vigorous stirring introduced into 111 parts of the aqueous dispersion of component 1 brought to dimethylethanolamine.
    to a pH of 7-7.5, and if necessary, at the same time diluted with deionized water. The ratio of components 1-3 binder system 56: 22: 22%, respectively,
    Data on the properties of the resulting coatings are presented in table. four,
    The proposed coating composition forms a uniform transparent glossy film with good physical and protective properties. At the same time, the composition has improved flowability and allows obtaining thick layers in which bubbles and acicular formation are not formed at regular times, which is especially important for uniform painting of cars with large horizontal and vertical surfaces.
    Table 1
    Methyl methacrylate 148 19 200 p-Butyl acrylate p-Butyl methacryl, 5lat99 2-Ethyl-hexylac, 34, 5-platy72 With -A-krylether (a) 66.0 Oxyethyl acrylate 141 1840 O1 seethylmethacrylate P oliprop or glycol monomethacrylate P oliprop or glycol monomethacrylate weight. 376-434) 50 Sh-hydroxyacrylates (b) 18 Methacrylic acid (s) 21 3 13 Styrene M) 105 13 200 Amount 786 100 503 Auxiliary substances tert Dodepilmercaptan3, 7 51 32 - - 151 30 55 19.5 12525 176 35 75 35 - 86, 555 94 12 7615 12 15 1.5 10 2 10 141 28 217 100 503 100 503 786 3.7 2.3
    Dodecylbenzene sulfonate.
    Polyethoxylated octiphenol (16 mol of ethylene oxide)
    1Vinyl sulfonate. Sodium
    Ammonium Peroxide Disulfate
    Ethoxylated sulphirane unoctylphenol (12 mol ethylene48
    Polyethylene glycol monomethacrylate (mol. Weight. 394-438)
    Progress Table 1
    1.5
    7,8
    3.9
    3.9
    1.5
    2.5
    1.5
    1.5
    table 2
    The compositions of component 2
    170
    170
    275
    125 EZ-hydroxy-acrylatosis (al) 34 G-Butyl acrylate 220. 2-Ethylhexyl acrylate - 140 Dodecyl methacrylate. . -, W-acrylates (S) .60 Acrylic acid Methacrylic acid 22 12 GG-acrylic acids (C1) b Octylstyrene Dibutyl fumarate - EI monomers (dl) - - I-monomers al-dl. 367 J 20 Solvent acetate ethylene glycol monoethyl zyfir - - yyethylene glycol monobutyl ether 220
    Butanol 367
    Content of dry matter,% 50 47.5
    Continuation of table 2
    49.5
    49.5
    49.5
    49.5 53434 ---- 290- - 29040 40 6 8 8 511 511 Oxyethylacrylate 170 - - - 2-Oxypropyl acrylate - - 170 4-Oxybutyl acrylate - “Polypropylene glycol monomethacrylate (mole, weight 376434/125) Polyethylene glycol monomethacrylate (mole, weight 376434/125) Polyethylene glycol monomethacrylate (mole, weight 376434/125) Polyethylene glycol monomethacrylate (mole, weight 376434/125) 394-438) - - X-hydroxyacrylates (al) - 34 34 h-Butylac 300 acrylate 220 300 2 - Ethyl hexyl acrylate - Dodecylmethacrylate, IZi-acrylate (I1) acrylate - 60 & 0 Acrylic acid Methacrylo 30 VA acid 30 IZr acrylic 6 acids (c 1) - 6 Octylstyrene Dibutyl fumarate-ZZ-monomers. (Dl) - ZI. monomers al-dl 500 - 500
    Continuation of table1Il 2 Solvent acetate ethylene glycol monoethyl ether Diethylene glycol monobutyl ether Butanol Dry matter content,%
    89 40
    60 30
    Hexamethoxymethylmelamine
    Continued tabl, 2
    Table 3
    120 60
    90 45
    110 55
    120 60
    50 25
    50 25
    50 25
    30 15
    25 25 11 9.5 0
    30 20 111 50 111 50 50 25 50 25
    Continuation of table 3
    20
    25
    25
    15 15
    Continuation of table 3 100 50100 50 50 25 50 25 111 50 50 25
    17 Hexamethoxymethylmelamine Hexamethylamine melamine, fully esterified with methanol and butanol (4: 2) Melamine-formaldehyde condensate (5.5 methylol groups per melamine molecule) esterified with 80% methanol and ethanol (1: 1) Titanium dioxide (rutile modification) 10% - p-toluenesulfonic acid aqueous solution Corrosion inhibitor Layer thickness, t / gkm (dry film) 38, 40 40 Gloss according to Lange (60), 90-95 80-8590% Impact Koenig (DI.N 53157), 105 9095 Ygshatani St xylene 53.54 min. Erichsen stretch test (DIM 53156}, mm 7.3 6.36.5 Test a gift for Erihsenu 80 4060
    18
    1068039
    Continued table. 3 35 40 40 40 35 35-40 IN90-9590-989585-9090 10 10580758570 4 54.5453, 0 7.0 56.556.5 0 80508040 "Indicators | T. L H Determination of adhesion with a lattice notch (DIN 53151), point Og1 0-1 1 Formation of boiling fluff when heated, starting with film thickness, μm in horizontal position 85 70 65 in vertical 70 55 60-65 50 position
    Continued table. 4 Examples p ---- .-, L H And Im m 9 2 1-2 0-1 0-1 0-1 0-1 0-1 70 70 90 90 70 70 65-70 70 60 65 50-55 60
    权利要求:
    Claims (1)
    [1]
    WATER-DILUTABLE THERMAL CURING COMPOSITION FOR COATINGS, including an acrylic copolymer and a water-soluble or water-dispersible aminoformaldehyde resin, partially or fully esterified with C 1 -C-monohydric alcohols, is distinguished by the fact that it is dispersed in order to. Because of the composition and the possibility of increasing the thickness of the coating while maintaining its uniformity, it contains as an acrylic copolymer a 45-50% aqueous dispersion of a copolymer containing 35-
    86.5 wt.% Ester of acrylic and / or methacrylic acid with C ^ -C & monohydric alcohols, 1220 wt.% Hydroxyethyl (meth Acrylate or a mixture of hydroxyethyl acrylate with polypropylene glycol monomethacrylate, 1.53 wt.% Methacrylic acid and 0 -43 wt.% Styrene, and a 47.5-49.5% solution in an organic solvent selected from the group consisting of diethylene glycol monobutyl ether, ethylene glycol monoethyl ether acetate, butanol, a water-soluble copolymer after base neutralization containing 24-55 wt.% hydroxyalkyl acrylate or polypropylene glycol monomethacre silt with a glass transition temperature of their homopolymers 25-64 ° C, 39-70 wt.% alkyl (meth) acrylate with a glass transition temperature of homopolymer -56 - -70 ° C and 6-8 wt.% (meth) acrylic acid, or water-soluble after neutralization with bases of a copolymer containing May 25% oxyalkyl acrylate or polypropylene glycol monomethacrylate with a glass transition temperature of their homopolymer -25 -64 ° С, 40-43 wt.% alkyl (methacrylate with a glass transition temperature of a homopolymer -56 - -70 ° С, 6-7 wt. % (meth) acrylic acid and 26-28% by weight of octylstyrene or dibutyl fumarate d in the following ratio to components, m.h .:
    45-50% aqueous dispersion of acrylic copolymer · 89-120 ‘47, 5-4 9.5% solution of acrylic copolymer in an organic solvent 30-60
    Water-soluble or water-dispersible aminoformaldehyde resin, partially or fully esterified with C ^ -C ^ -atomic alcohols 15-30
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    同族专利:
    公开号 | 公开日
    IT7923534D0|1979-06-13|
    GB2025985A|1980-01-30|
    ES481683A1|1980-03-01|
    GB2025985B|1982-09-02|
    FR2429247B1|1985-12-13|
    AT355693B|1980-03-10|
    FR2429247A1|1980-01-18|
    IT1121795B|1986-04-23|
    DE2918067A1|1980-01-10|
    DE2918067C2|1987-04-23|
    ATA447778A|1979-08-15|
    引用文献:
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    法律状态:
    优先权:
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