Source: http://www.google.de/patents/US5763528
Timestamp: 2013-05-20 21:51:42
Document Index: 398423476

Matched Legal Cases: ['ART 1', 'ART 2', 'ART 1', 'ART 2', 'ART 1', 'ART 2', 'ART 1', 'ART 2']

Patent US5763528 - Coating compositions containing non-aqueous dispersed polymers having a high ... - Google PatenteSuche Bilder Maps Play YouTube News Gmail Drive Mehr » Erweiterte Patentsuche | Webprotokoll | Anmelden Erweiterte Patentsuche PatenteA coating composition of a film forming binder and an organic liquid carrier; wherein the binder contains about (a) 10-90% by weight, based on the weight of the binder, of a dispersed gelled acrylic polymer having a glass transition temperature of at least 20 (i) a core of comprising polymerized ethylenically...http://www.google.de/patents/US5763528?utm_source=gb-gplus-sharePatent US5763528 - Coating compositions containing non-aqueous dispersed polymers having a high glass transition temperature Ver�ffentlichungsnummerUS5763528 APublikationstypErteilung Anmeldenummer08/767,919 Ver�ffentlichungsdatum9. Juni 1998Eingetragen17. Dez. 1996 Priorit�tsdatum17. Dez. 1996Auch ver�ffentlicht unterEP0946663A1EP0946663B1WO1998027173A1 ErfinderRobert John BarsottiLaura Ann LewinChristopher ScopazziUrspr�nglich Bevollm�chtigterE. I. Du Pont De Nemours And CompanyBarclays Bank Plc, As Collateral AgentU.S. Coatings Ip Co. LlcE.I. De Pont De Nemours And Company US-Klassifikation525/63428/423.1525/123525/69525/66Internationale KlassifikationC08G18/63C09D5/46 UnternehmensklassifikationC08G18/633 Europ�ische KlassifikationC08G 18/63MReferenzenPatentzitate (27)Nichtpatentzitate (6) Referenziert von (36)Externe LinksUSPTO USPTO-Zuordnung EspacenetCoating compositions containing non-aqueous dispersed polymers having a high glass transition temperatureUS 5763528 A Zusammenfassung A coating composition of a film forming binder and an organic liquid carrier; wherein the binder contains about
(a) 10-90% by weight, based on the weight of the binder, of a dispersed gelled acrylic polymer having a glass transition temperature of at least 20
We claim: 1. A coating composition comprising about 40-90% by weight of film forming binder and 10-60% by weight of an organic liquid carrier; wherein the binder comprises about (a) 10-90% by weight, based on the weight of the binder, of a dispersed gelled acrylic polymer having a glass transition temperature of at least 20 (i) 30-70% by weight based on the weight of the polymer, of a core comprising polymerized ethylenically unsaturated monomers which is not soluble in the organic liquid carrier and having chemically grafted thereto (ii) 70-30% by weight based on the weight of the polymer of substantially linear stabilizer polymeric components that are soluble in the organic liquid carrier comprising polymerized ethylenically unsaturated monomers and having a weight average molecular weight of about 500-20,000 determined by GPC (gel permeation chromatography) using polystyrene as the standard and having a glass transition temperature of 20 wherein the monomers of the core and the stabilizer polymeric components are individually selected from the group consisting of alkyl methacrylates, alkyl acrylates, wherein the alkyl groups have 1-12 carbon atoms, hydroxy alkyl methacrylate, hydroxy alkyl acrylates, wherein the alkyl groups have 1-4 carbons atoms, styrene, alpha methyl styrene, vinyl toluene, glycidyl methacrylate, glycidyl acrylate, isobrnyl methacrylate, isobrnyl acrylate, alpha-beta ethylenically unsaturated monocarboxylic acids and any mixtures thereof and the core, stabilizer polymeric components or both contain at least 3% by weight of polymerized ethylenically unsaturated monomers selected from the above group having functional components that are capable of reacting with component (c) and optionally with component (b); (b) 0-70% by weight, based on the weight of the binder, of an oligomer having functional components capable of reacting with component (c); and (c) 10-50% by weight, based on the weight of the binder, of an organic polyisocyanate crosslinking agent.
TECHNICAL FIELD This invention relates to high solids solvent based coating compositions having a low VOC (volatile organic content) and in particular to a clear coating composition useful for refinishing clear coat/color coat finishes of automobiles.
BACKGROUND OF THE INVENTION Solvent based coating compositions useful as clear coats and refinishing clear coats composed of an acrylic polymer, a polyol and an organic polyisocyanate crosslinking agent that provide coatings of excellent quality are known in the art as shown in Lamb et al U.S. Pat. No. 5,286,782 issued Feb. 15, 1994. A dispersion of a first high molecular weight polymer having chemically reactive groups in an organic liquid and a second high molecular weight polymer having chemically reactive groups that are capable of reacting with the reactive groups of the first polymer and form useful coating compositions are disclosed in Yabuta et al U.S. Pat. No. 5,173,533 issued Dec. 22, 1992. Polyol blends of high and low Tg (glass transition temperature) polymers that are used to form coating compositions are shown in U.S. Pat. Nos. 5,098,956 and 5,098,952 both issued to Blasko et al on Mar. 24, 1992. There is a need for a low VOC coating composition that meets pollution regulations for the refinishing of automobiles and trucks that cures rapidly to a tack free coating and that can be later buffed to a high gloss finish. Such a combination of properties is not provided by the aforementioned prior art coatings.
SUMMARY OF THE INVENTION A coating composition containing about 40-90% by weight of film forming binder and 10-60% by weight of an organic liquid carrier; wherein the binder contains about
Preferably, the polymer contains about 30-70% by weight of the core and 70-30% by weight of substantially linear stabilizer polymeric components having a glass transition temperature of about 20 These linear stabilizer components are soluble in the organic carrier liquid used to form the coating composition and keeps the acrylic polymer dispersed in the liquid while the core is insoluble in this liquid. These macromonomers which form the polymeric components of the polymer comprises polymerized alpha-beta ethylenically unsaturated monomers and have one terminal ethylenically unsaturated moiety and have a weight average molecular weight (MW) of 500-20,000, preferably 1,000 to 10,000. About 25-75% (by weight), preferably 40-60%, of the macromonomer is copolymerized with 75-25%, preferably 60-40%, of a blend of other alpha, beta-ethylenically unsaturated monomers which form the core of the acrylic polymer. At least 3%, preferably 3-30% by weight, of the monomers have functional groups in the stabilizer or the core or in both having functional components that are capable of reacting with the polyisocyanate crosslinking agent.
The Tg (glass transition temperatures) of the acrylic polymer is calculated and has a Tg of at least 20 20 ##EQU1## where TGC- is the glass transition temperature of the polymer in degrees Kelvin;
Peroxy- and azo-initiators (0.5-5% weight on monomer) can be used in the synthesis of the macromonomers in the presence of 2-5,000 ppm (on total monomer) or Co (II) chelate in the temperature range between 70 2,2'-azobis (2,4 dimethylpentane nitrile), 2,2'-azobis (2-methylpropane nitrile), 2,2'-azobis (2-methylbutane nitrile), 1,1'-azo (cyclohexane carbonitrile) and 4,4'-azobis (4-cyanopentanoic) acid.
After the macromonomer is formed as described above, solvent is optionally stripped off and the core monomers are added to the macromonomer along with additional solvent and polymerization catalyst. Any of the aforementioned azo-type catalysts can be used as can other suitable catalysts such as peroxides and hydroperoxides. Typical of such catalysts are di-tertiarybutyl peroxide, dicumylperoxide, tertiaryamyl peroxide, cumenehydroperoxide, di(n-propyl) peroxydicarbonate, peresters such as amyl peroxyacetate and the like. Commercially available peroxy type initiators include, e.g., t-butylperoxide or Triganox t-butylperacetate or Triganox Triganox from AKZO.
Trimers of diisocyanates also can be used such as the trimer of hexamethylene diisocyanate which is sold under the tradename Desmodur N-3390.
Isocyanate functional adducts can be used that are formed from an organic polyisocyanate and a polyol. Any of the aforementioned polyisocyanates can be used with a polyol to form an adduct. Polyols such as trimethylol alkanes like trimethylol propane or ethane can be used. One useful adduct is the reaction product of tetramethylxylidene diisocyanate and trimtheylol propane and is sold under the tradename of Cythane
The coating compositions of the present invention can also contain up to 40% of total binder of an acrylic polymer or polyester having a weight average molecular weight greater than 2,000 for improved appearance, sag resistance, flow and leveling and such. The acrylic polymer can be composed of typical monomers such as acrylates, methacrylates, styrene and the like and functional monomers such as hydroxy ethyl acrylate, glycidyl methacrylate, or gamma methacryly propyl trimethoxy silane and the like. Conventional polyesters can be used such as SCD Products Inc.
In the application of the coating composition as a clear coating to a vehicle such as an automobile or a truck, the basecoat which may be either a solvent based composition or a waterborne composition is first applied and then dried to at least remove solvent or water before the clear coating is applied usually by conventional spraying. Electrostatic spraying may also be used. The dry film thickness of the clear coating is about 0.5-5 mils. The clear coating is dried at ambient temperatures generally in less than 5 minutes to a tack and dust free state. Moderately higher temperatures up to about 40 the clear coating is sufficiently cured to be dust free and tack free the vehicle can be moved from the work area to allow for the refinishing of another vehicle.
Coating compositions of this invention can be applied by conventional techniques such as spraying, electrostatic spraying, dipping, brushing, flowcoating and the like. The preferred techniques are spraying and electrostatic spraying. In refinish applications, the composition is dried and cured at ambient temperatures but can be forced dried at elevated temperatures of 40 applications, the composition is typically baked at 100 0.1-3.0 mils thick. When the composition is used as a clearcoat, it is applied over the color coat which may be dried to a tack-free state and cured or preferably flash dried for a short period before the clearcoat is applied. The color coat/clearcoat finish is then baked as mentioned above to provide a dried and cured finish. The present invention is also applicable to non-baking refinish systems, as will be readily appreciated by those skilled in the art.
EXAMPLE 1 Preparation of a Macromonomer Composition To a 2-liter flask fitted with an agitator, condenser, heating mantle, nitrogen inlet, thermocouple and an addition port was added 325.2 grams butyl methyacrylate, 81.3 grams glycidyl methacrylate, 100 grams butyl acetate and 160 gms toluene. The mixture was agitated and heated to reflux (122 shot, a pre-mixed solution of 0.35 grams Vazo and 17.2 grams of a 0.17% solution of bis(boron difluoro diphenyl glyoximate) cobaltate(II) in methyl ethyl ketone. This was immediately followed by the addition of a pre-mixed soution of 285.4 grams butyl methacrylate, 71.3 grams glycidyl methacrylate, 1.35 grams Vazo and 86.6 grams toluene over 240 minutes while maintaining refulx (116 pre-mixed solution of 0.32 grams Vazo added over 60 minutes while maintaining reflux (116 C.). Following a 30 minute hold period, a pre-mixed solution of 0.32 grams Vazo maintaining refulx. The batch was then held at reflux for an additional 60 minutes at which time a solution of 0.23 grams t-butyl peroctoate and 31.39 grams butyl acetate was added and the reaction mixture was then cooled. The macromonomer thus prepared has a was then added over 300 minutes while maintaining reflux.
Preparation of Non-Aqueous Dispersion To a 2-liter flask fitted with an agitator, condenser, heating mantle, nitrogen inlet, thermocouple and an addition port was added 236.4 grams of the macromonomer composition prepared above, 301.9 grams heptane and 75.5 grams ethyl acetate. This mixture was agitated and heated to reflux (90 peroctoate in 41.9 grams heptane was then added as a shot. This was immediately followed by the addition of a pre-mixed solution of 62.9 grams styrene, 92.3 grams hydroxy ethyl acrylate, 100.7 grams methyl methacrylate, 83.7 grams glycidyl methacrylate, 4.2 grams allyl methacrylate, 75.5 grams methyl acrylate, 41.9 grams toluene, 25.8 grams heptane and 6.3 grams t-butyl peroctoate over 210 minutes maintaining reflux. The batch was then held at reflux for 60 minutes after which a pre-mixed solution of 21.4 grams toluene, 8.4 grams heptane and 4.2 grams t-butyl peroctoate was added over 30 minutes and the batch then held at reflux for 60 minutes. This was followed by distillation of 83.9 grams solvent and the batch then cooled to room temperature. The resulting composition has a percent weight solids of 52.6, viscosity 1400 centipoise at 50 rmp Brookfield and particle size 240 nanometers as measured by Coulter quasi-elastic light scattering and the polymer has a calculated Tg of 41
EXAMPLE 2 Preparation of Dispersant Polymer To a 5-liter flask fitted with an agitaor, condenser, heating mantle, nitrogen inlet, thermocouple and an addition port was added 893.6 grams xylene and the temperature raised to reflux (135 under nitrogen. A pre-mixed solution of 477.3 grams styrene, 492.6 grams butyl methacrylate, 483.9 grams butyl acrylate, 263.9 grams hydroxy ethly acrylate, 49.0 grams methacrylic acid, 327.2 grams isobornyl methacrylate, 127.1 grams t-butyl peracetate and 336.4 grams xylene were then added over 240 minutes while maintaining reflux temperature. The reaction mixture was then held at reflux for 30 minutes This was followed by the addition, in order, of a solution of 0.08 grams catechol in 0.89 grams isopropanol, 37.2 grams glycidyl methacrylate and 0.5 grams of 2-methyl, 2-N,N-dimethylamino propanol. The reaction mixture was held at reflux for 120 minutes and then cooled. The resulting percent weight solids were 63.6, Gardner viscosity T, number avearage molecular weight 3270 and weight average molecular weight 7740.
Preparation of Non-Aqueous Dispersion Polymer To a 2-liter flask fitted with an agitator, condenser, heating mantle, nitogen inlet, thermocouple and an addition port was added 256.3 grams of dispersant polymer prepared above, 30.6 grams isopropanol 8.6 gm. ethyl acetate, 70.6 grams mineral spirits and 151.3 grams heptane. This mixture was agitated and heated to reflux (90 nitrogen at which time a pre-mixed solution of 0.65 grams t-butyl peroctoate and 7.6 grams heptane was added as a shot. This was immediately followed by the addition of a pre-mixed solution of 64.6 grams styrene, 86.0 grams hydroxy ethylacrylate, 159.9 grams methyl methacrylate, 6.5 grams glycidyl methacrylate, 17.2 grams methacrylic acid, 75.5 grams methyl acrylate, 19.5 grams ethyl acetate, 38.4 grams heptane, 39.4 grams mineral spirits, 128.7 grams of dispersant polymer prepared above and 6.5 grams t-butyl peroctoate over 210 minutes maintaining the batch at reflux. The batch was then held at reflux for 45 minutes after which a pre-mixed solution of 18.5 grams butyl acetate and 2.1 grams t-butyl peroctoate was added over 30 minutes and the batch then held at reflux for 60 minutes. This was followed by the distillation of 82.5 grams solvent after which the batch was cooled to room temperature. The resulting composition has percent weight solids of 60.8, viscosity 440 centipoise at 5 rpm Brookfield and particle size 317 nanometers as measured by Coulter quasi-elastic light scattering and the polymer had a calculated Tg of 41
EXAMPLE 3 A coating composition was prepared by charging the following constituents into a mixing vessel:
______________________________________                      PARTS BYPART 1                     WEIGHT______________________________________Non aqueous Dispersion (prepared in Example 2)                      89.88Butyl Acetate              19.04Tinuvin                       2.19BYK                       0.28Tinuvin                       1.39bis(n-methyl-2,2,6,6-tetramethyl piperidinyl)sebacate1% dibutyl tin dilaurate in methyl ethyl ketone                      2.43PART 2Tolonate HDT-LV (Isocyanate trimer from Rhone-Poulenc)                      10.95Butyl Acetate              3.85Total                      130.01______________________________________
EXAMPLE 4 A coating composition was prepared by charging the following constituents into a mixing vessel:
______________________________________PART 1                 PARTS BY WEIGHT______________________________________Non aqueous Dispersion (prepared in Example 1)                  87.87Butyl Acetate          6.15Tinuvin                   2.26BYK                   0.29Tinuvin                   1.431% dibutyl tin dilaurate in methyl ethyl ketone                  2.51PART 2Tolonate HDT-LV (Isocyanate trimer)                  21.82Total                  122.33______________________________________
EXAMPLE 5 A tetra hydroxy oligomer was prepared as follows:
To a 12-liter flask fitted with an agitator, condense, heating mantle, nitrogen inlet, thermocouple and an addition port was added 2447.2 grams propylene glycol monomethylether acetate, 792.4 grams pentaerythritol and 1.36 grams triethyl amine. The reaction mixture was agitated and heated to 140 hexahydrophthalic anhydride was added over 6 hours. The reaction mixture was then held at 140 an infrared spectroscopic trace. An acid oligomer was formed.
To a 5-liter flask fitted with an agitator, condense, heating mantle, nitrogen inlet, thermocouple and an addition port was added 2798.4 grams of acid oligomer prepared above and 2.76 grams triethyl amine. The mixture was agitated and heated to 60 1,2-epoxy butane was then added over 120 minutes after which the temperature was raised to 105 until the acid number dropped to about 10 or less. The percent weight solids of the composition was 71.5, Gardner viscosity V, and the oligomer has a number average molecular weight 895 and weight average molecular weight 1022.
To a 12-liter flask fitted with an agitator, condenser, heating mantle, nitrogen inlet, thermocouple and an addition port was added 2434.5 grams propylene glycol monomethylether acetate, 1222.5 grams hexane diol and 1.37 grams triethyl amine. The reaction mixture was agitated and heated to 140 methyl hexahydrophthalic anhydride was added over 6 hours. The reaction mixture was then held at 140 observed on an infrared spectroscopic trace. An acid oligomer was formed.
The mixture was agitated and heated to 60 grams 1.2-epoxy butane was then added over 120 minutes after which the temperature was raised to 105 until the acid number dropped to about 10 or less. The resulting composition has a percent weight solids of 69.5, Gardner viscosity A, number average molecular weight 679 and weight average molecular weight 770.
______________________________________                    PARTS BYPART 1                   WEIGHT______________________________________Tetra hydroxy functional oligomer (Prepared above)                    14.61Oligomer A (Prepared above)                    11.341% Dibutyl tin dilaurate in methyl ethyl ketone                    0.7410% BYK                     0.37BYK Chemie in propylene glycol monomethyl etheracetate)Non aqueous dispersion (prepared in Example 1)                    10.35PART 2Tolonate HDT-LV (Isocyanate trimer)                    12.58Total                    49.99______________________________________
EXAMPLE 6 A coating composition was prepared charging the following constituents into a mixing vessel:
______________________________________                      PARTS BYPART 1                     WEIGHT______________________________________Tetra hydroxy functional oligomer (Prepared in Example 5)                      14.5Oligomer A (Prepared in Example 5)                      11.15Butyl acetate              9.231% Dibutyl tin dilaurate in methyl ethyl ketone                      0.7610% BYK                       0.38Non aqueous dispersion (prepared in Example 2)                      10.15PART 2Tolonate HDT-LV (Isocyanate trimer)                      13.82Total                      59.99______________________________________
The coating composition of this Example (applied as above) was also cured for 30 minutes @60 and cure.
An improvement in 1.5 units in resistance to 10% sulfuric acid (for 30 minutes @15 without non aqueous disperision (rating =14.5 versus 13 on a scale of 0-20 where 20 is the best rating).
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