JP3436552B2 - Water-based coating composition containing acrylic silane and polyurethane - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION The present invention is directed to water-based coating compositions and especially water-based coatings comprising acrylic silane polymers and polyurethanes.

Water-based dispersions of polyurethanes are known as shown in Drexler et al., US Pat. No. 4,489,135, published Dec. 18, 1984. Aqueous dispersions of acrylic silane polymers are known, for example, as shown in Noren, U.S. Pat. No. 4,384,013, issued May 17,1983. A method for making an aqueous dispersion of an acrylic polyester is disclosed in Osborn, published on Dec. 9, 1975.
U.S. Pat. No. 3,925,295 and Osmond et al. U.S. Pat. No. 3,935,1 issued Jan. 27, 1976.
It is shown in No. 55. However, none of the compositions shown in the art produce a topcoat that is specifically needed for finishing or repairing automobile and truck exteriors.

To date, solvent-based topcoats have been used to repair and reapply automotive and truck exteriors. Topcoats of these solvent-based compositions provide the required color balance, cure at ambient temperatures, have excellent adhesion to substrates, and are required for automotive and truck exteriors. It gave properties such as gloss, hardness, and image clarity. It has been suggested to use water-based paints to reduce solvent emissions. None of the known water-based paints produces topcoats with the required properties for automotive and truck applications.

Color coats for cars and trucks /
Water-based color coats for clear coat topcoats, i.e. topcoats having a pigmented and colored layer and a top transparent layer, are now used for their initial production. It's starting. For repairing such topcoats, it is highly desirable and usually desirable to use a water-based topcoat that matches the original color, especially when metal flake pigments are present in the color coat. Is necessary.

[0005]

SUMMARY OF THE INVENTION About 10 to 10 dispersed in an aqueous carrier.
Includes 30% by weight film-forming binder and about 7
A water-based coating composition having a pH of -10, wherein the binder is a blend of dispersed acrylic silane polymer and dispersed polyurethane and approximately a. 60-90% by weight, based on the weight of the binder,
1 based on the weight of acrylic silane polymer, acrylic silane polymer of polymerized monomer of alkyl methacrylate, alkyl acrylate or mixtures thereof.
10% by weight of silane-containing alkyl acrylate or methacrylate, sufficient monoethylenically unsaturated acid to give the polymer an acid number of 2-100, and sufficient hydroxyalkyl acrylate to give the polymer a hydroxyl number of up to about 100. Or hydroxyalkyl methacrylate (wherein this polymer is -40 to + 25 ° C)
Glass transition temperature and 500,000 to 3,000,000
Has a weight average molecular weight of 0, and the acid groups of the polymer have been reacted with ammonia or amines) and
b. 10-40% by weight, based on the weight of the binder,
A coating composition comprising a polyurethane selected from the group of polyester urethane, polyether urethane or polyacrylourethane. This composition produces an automotive grade clear coat and / or pigmented colored coat and can be used as a primer composition. Articles coated with a clear coat, which may or may not be the composition of the present invention, and a pigmented color coat of the coating composition of the present invention, and methods for producing these coated articles. Also
It is part of the present invention.

DETAILED DESCRIPTION OF THE INVENTION The coating composition of the present invention is stable for extended periods of time, has a very low VOC content (volatile organics content) and is used for automobiles and trucks. Can be colored by all existing commercial pigments that are hard, glossy,
Creates a topcoat that is both weather resistant and durable. In particular,
The composition comprises various substrates such as prepainted substrates, cold rolled steel, phosphated steel, conventional primers such as typically crosslinked epoxy polyesters and various epoxy resins. A certain electrodeposition primer, steel material coated with an alkyd resin repair primer,
It has excellent adhesion to plastic substrates such as glass fiber reinforced polyesters, reaction injection molded urethanes and partially crystalline polyamides. A clear coat can be applied to the layer of pigmented composition to provide a clear / pigmented coat topcoat. The coating composition used for the clear coat may be the coating composition of the invention or another comparable water or solvent based coating composition.

The coating composition according to the invention can also be used as a primer on cold-rolled steel, treated steel such as phosphate-treated steel or the plastic substrates mentioned above. This primer is
It is provided with a topcoat, for example a surface which will adhere to the topcoat of the coating composition of the invention as described above.

The coating composition of the present invention comprises about 10
It has 30% by weight of a film-forming binder and, correspondingly, about 90-70% by weight of an aqueous carrier containing predominantly water but often a small amount of organic solvent for the binder. This composition may be used as a clear coating composition which may contain very small amounts of pigments to eliminate yellowing-like colors. Generally, the composition is pigmented and about 1: 100-200:
The pigment is included at a pigment to binder weight ratio of 100.

The film forming binder of the composition of the present invention comprises about 60-90% by weight acrylic silane polymer and correspondingly about 10-40% by weight polyurethane. Preferably, the binder comprises about 65-85% by weight acrylic silane polymer and 35-15% by weight polyurethane. Preferably, a solid color (solid colo
r) For compositions, ie compositions in which no metallic pigments such as aluminum flakes are used, the binder preferably comprises about 70% acrylic silane polymer and 30% polyurethane and has a metallic color. That is, for compositions containing aluminum flakes, the binder is about 80% acrylic silane polymer and 2%
Contains 0% polyurethane.

The acrylic silane polymer emulsifies a mixture of monomer, water, surfactant and polymerization catalyst, and charges the resulting emulsion into a conventional polymerization reactor, and these components in the reactor are charged. About 15
The polymer formed by conventional emulsion polymerization by heating to about 60-95 ° C. for minutes to 8 hours, and then the polymer formed is neutralized with ammonia or amine. The size of the polymeric particles of this latex is about 0.6-0.20.
It is micron. The polymer produced has an acid number of 2 to 100, a hydroxyl number of up to about 100, -40 to + 25 ° C.
Glass transition temperature of about 500,000 to 3,000,0
It has a weight average molecular weight of 00.

For solid color compositions it is possible to use acrylic silane polymers which do not contain hydroxyl groups, but for metallic color compositions said acrylic silane polymers must contain hydroxyl groups. And should have a hydroxyl number of about 5-100. Hydroxyl groups are needed to obtain a topcoat with a high quality metal-like appearance.

All molecular weights herein are measured by gel permeation chromatography using polymethylmethacrylate as a standard.

[0013] Typically useful catalysts are ammonium persulfate, hydrogen peroxide, sodium metabisulfite, hydrogen peroxide sodium sulfoxylate, and the like.

Typically useful surfactants are nonylphenoxypolyethyleneoxyethanol sulphate, allyldodecyl sulfosuccinate, alkylphenoxypolyethyleneoxyethanol, sodium lauryl sulphate and mixtures thereof. One preferred surfactant is a mixture of nonylphenoxypolyethyleneoxyethanol sulphate and allyldodecyl sulfosuccinate.

The acrylic silane polymer is about 1 to 1
It contains 0% by weight of polymerized silane-containing acrylate or methacrylate. Typically useful silane-containing acrylates or methacrylates have the following structural formula:

[Chemical 3] [In the formula, R represents CH ₃ , CH ₃ CH ₂ , CH ₃ O, or CH.
₃ CH ₂ O, R ₁ and R ₂ are CH ₃ or CH ₃ CH ₂ , and R ₃ is H, CH ₃ or CH ₃ C
Is either H _2, and n have the 0 or a positive integer not greater than 8].

The preferred silanes are γ-trimethoxysilylpropyl methacrylate and γ-trimethoxysilylpropyl acrylate.

The acrylic silane polymer is preferably
Included are sufficient polymerized hydroxyalkyl methacrylates or acrylates having 2 to 4 carbon atoms in the alkyl group to provide a polymer having a hydroxyl number of 5 to 100. Usually, about 2-10% by weight of hydroxyalkyl acrylate or methacrylate is used. Typically useful monomers are hydroxyethyl acrylate, hydroxypropyl methacrylate, hydroxybutyl methacrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate.
Other useful polymerizable components are the reaction products of alkyl methacrylates or acrylates with lactones. One ingredient of this type is believed to be the reaction product of hydroxyethyl acrylate and a lactone Un
"Tone" 100 manufactured by ion Carbide.

The acrylic silane polymer also contains about 2
Sufficient polymerized monoethylenically unsaturated carboxylic acid monomer is included to provide a polymer having an acid number of -100. Typically useful monoethylenically unsaturated acids are methacrylic acid, acrylic acid, itaconic acid, styrene sulfonic acid and salts thereof. Usually, these unsaturated acids are
It is used in an amount of about 0.1-10% by weight, based on the weight of the polymer.

The acid is neutralized with ammonia or amine and the pH of the resulting coating composition is adjusted to a pH of about 7-10. Typically useful amines are
Primary amines and secondary amines and are: aminoethylpropanol, allylamine, 1-amino-2-propanol, 3-amino-1-propanol, benzylamine, butylamine, sec. -Butylamine, tert. -Butylamine, cyclohexylamine, decylamine, dodecylamine, ethanolamine, ethylamine, 2-ethylhexylamine, heptylamine, hexylamine, isobutylamine, isopropylamine, methylamine, octylamine, pentylamine, propylamine, ethylenediamine and the like. Typically useful secondary amines are 2,2-dimethyloxazolidine-1,4,2,2-dimethanoloxazolidine-
1,4,2-methyl-1--2-methanoloxazolidine-1,4,2,2-diethyloxazolidine-1,4,
Dibenzylamine, dibutylamine, dicyclohexylamine, didodecylamine, diethanolamine, diethylamine, 2,2-diethylhexylamine, dihexylamine, disopropanolamine, dimethylamine, dioctylamine, dipentylamine, dipropylamine, 2-ethylamino Ethanol, 2 (2-hydroxyethylamino) -2- (hydroxymethyl) -1,
3-propanediol, 2-methylaminoethanol,
2- (2-aminoethylamino) ethanol, 3,3-
Diamino-dipropylamine, diethylenetriamine,
N-methylethylenediamine and the like.

The remaining components of the acrylic silane polymer are polymerized alkyl acrylates and / or methacrylates, preferably having about 1 to 12 carbon atoms in the alkyl group. Blend these ingredients,
Obtain the desired polymer glass transition temperature. Typically useful monomers are methyl methacrylate, ethyl acrylate, propyl acrylate, propyl methacrylate,
Butyl methacrylate, isobutyl methacrylate, butyl acrylate, isobutyl acrylate, hexyl acrylate, hexyl methacrylate, 2-ethylhexyl methacrylate, 2-ethylhexyl acrylate, lauryl methacrylate and the like. It is also possible to use up to about 20% by weight of styrene to form the acrylic silane polymer.

Up to about 10% by weight methacrylamide or allyl methacrylate, based on the weight of the acrylic silane polymer, can be used.

The following are particularly useful acrylic silane polymers: about 40-50% by weight methyl methacrylate, 40-50% by weight 2-ethylhexyl acrylate, 2-6% by weight γ-trimethoxysilylpropyl methacrylate. An acrylic silane polymer containing 2-5 wt% hydroxyethyl acrylate and 1-3 wt% methacrylic acid; about 25-35 wt% methyl methacrylate, 10-20 wt% styrene, 40-50 wt% 2. -Ethylhexyl acrylate, 2-6% by weight
Γ-trimethoxysilylpropyl methacrylate, 2
~ 5 wt% hydroxyethyl acrylate and 1-3
Acrylic silane polymer containing wt% methacrylic acid;
30-40% by weight of methyl methacrylate, 10-20
Step I of wt% styrene, 40-50 wt% butyl acrylate and 1-5 wt% γ-trimethoxysilylpropyl methacrylate and 25-30 wt% methyl methacrylate, 10-15 wt% styrene, 30-
40 wt% butyl acrylate, 6-10 wt% γ
-Trimethoxysilylpropyl methacrylate, 8-1
2 wt% hydroxyethyl acrylate and 5-9 wt% methacrylic acid grafted acrylic silane graft copolymer in Stage II; 10-30 wt% methyl methacrylate and 70-90 wt% butyl acrylate Stage I and 70 Step II of -80 wt% butyl acrylate, 6-10 wt% γ-trimethoxysilylpropyl methacrylate, 8-12 wt% hydroxyethyl acrylate and 5-9 wt% methacrylic acid.
A two-step acrylic silane graft copolymer; and a three-step acrylic silane in which step I and step II each consist of methyl methacrylate, allyl methacrylate, butyl acrylate, and step III consist of methyl methacrylate, butyl acrylate and γ-trimethoxysilylpropyl methacrylate. Graft copolymer Graft polymer.

The typical polyurethane used in the coating composition of the present invention is in the form of an aqueous dispersion having a particle size of less than 0.1 micron. These polyurethanes are produced by reacting polyesters, polyethers, polylactones or polyacrylics having terminal hydroxyl groups with diisocyanates in a molar ratio such that the resulting intermediate product has terminal isocyanate groups. The isocyanate group of this intermediate product is then reacted with a compound having a group that is reactive towards the isocyanate group and having at least one group capable of forming an anion. This group is subsequently neutralized with a tertiary amine to form a water dispersible polyurethane, and the resulting polyurethane is then chain extended in water with a diamine by reaction of the diamine with the unreacted isocyanate groups of the polyurethane. . A method for making such polyurethanes in an aqueous dispersion comprises:
December 1984, incorporated herein by reference
US Pat. No. 4,48, Drexler et al., Issued May 18,
No. 9,135.

A typical polyester urethane is produced by making a polyester polyol from a polyol and a dicarboxylic acid or anhydride. Useful acids include succinic acid, adipic acid, suberic acid, azelaic acid, sebacic acid, phthalic acid, isophthalic acid, maleic acid and anhydrides of these acids. Useful diols are
Includes ethylene glycol, butylene glycol, neopentyl glycol, hexanediol or mixtures of any of these. This polyester polyol,
It is reacted with a suitable diisocyanate at a polyol to diisocyanate molar ratio of about 1: 2 to produce an isocyanate terminated product.

The diisocyanates which can be used are: toluene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, ethylethylene diisocyanate, 2,3-dimethylethylene diisocyanate, 1-methyltrimethylene diisocyanate,
1,3-cyclopentylene diisocyanate, 1,4-cyclohexylene diisocyanate, 1,3-phenylene diisocyanate, 4,4′-biphenylene diisocyanate, 1,5-naphthalene diisocyanate, bis-
(4-isocyanatocyclohexyl) -methane, 4,
4'-diisocyanato diphenyl ether, tetramethyl xylene diisocyanate and the like.

The compounds having groups reactive with isocyanate groups and capable of forming anions are as follows: dihydroxypropionic acid, dimethylolpropionic acid, dihydroxysuccinic acid and dihydroxybenzoic acid. Other suitable compounds are polyhydroxy acids that can be prepared by oxidizing monosaccharides, such as gluconic acid, saccharic acid, mucic acid.
c acid) and glucuronic acid.

Suitable tertiary amines used to neutralize the above acids and generate anionic groups for water dispersibility include trimethylamine, triethylamine, dimethylaniline, diethylaniline and triphenylamine. is there.

Suitable diamines for extending the chain of the polyurethane to give N-alkylurea groups are: ethylenediamine, diaminopropane, hexamethylenediamine, hydrazine and aminoethylethanolamine.

A typical polylactone that can be used to form the polyurethane can be a lactone such as caprolactone reacted with a diol. Other useful lactones have the formula

[Chemical 4] [Wherein n is preferably 4 to 6, and Z is
Hydrogen, alkyl groups, cycloalkyl groups or alkoxy groups and containing no more than 12 carbon atoms]. The most preferred lactone is ε
-Caprolactone. Because it provides a coating that is readily available and has excellent properties. Typical useful aliphatic diols that can be used to form the polylactone are ethylene glycol, 1,3-propanediol, 1,4-butanediol and dimethylolcyclohexane.

Typical polyethers that can be used to form the polyurethane are those named as polypropylene glycols such as "Niax" polypropylene glycols 425, 2025, 3025 and 4025. These numbers indicate the molecular weight of polypropylene glycol. About 400-4500
Polypropylene glycol having a weight average molecular weight of can be used.

Typical hydroxyl-terminated polyacrylics that can be used to form the polyurethane include acrylic esters such as the alkyl acrylates or methacrylates described above and functional groups such as carboxyl, hydroxyl, cyano. Produced by ethylenic polymerization with ethylenically unsaturated monomers containing groups and / or glycidyl groups. Any of the alkyl acrylates and methacrylates mentioned above can be used. Typically useful functional monomers are acrylic acid, methacrylic acid, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, and any of the above mentioned hydroxyalkyl acrylates or methacrylates, glycidyl methacrylates or acrylates and 2-cyanoethyl acrylate. Alternatively, it is methacrylate or the like.

These polylactones, polyethers or polyacrylics are reacted as indicated above for polyesters to form aqueous polyurethane dispersions.

Typical pigments which can be used in the compositions of the invention are metal oxides such as titanium dioxide,
Zinc oxide, iron oxides of various colors, carbon black, filler pigments such as talc, clay, barite, carbonates, silicates, as well as a wide range of organic color pigments such as quinacridone,
Copper phthalocyanine, perylene, azo pigments, indanthrone blue, carbazole such as carbazole violet, isoindolinone, isoindlone, thioindigo red and benzimidazolinone.

When the coating contains a metallic pigment, an agent which suppresses the reaction between the pigment and water may be added.
Typical inhibitors are phosphated organic materials such as "Vircopet" 40 available from Mobil Chemical Co.

The pigments are first mixed with either an acrylic silane polymer or polyurethane or with another comparable polymer or dispersant by conventional techniques such as high speed mixing,
It can be incorporated into the coating composition by producing a mill pigment or pigment dispersion by sand grinding, ball mill mixing, attritor grinding or two roll mill mixing. This mill pigment is blended with the other ingredients used in the composition of the present invention.

The coating composition of the present invention may include from about 0.01 to 2% by weight, based on the weight of the binder, of a UV stabilizer, including UV absorbers, blockers and quenchers. Typical UV stabilizers include benzophenone, triazines, triazoles, benzoates, sterically hindered amines and blends thereof.

Thickeners and rheology control agents are added to the coating composition of the present invention to provide the desired spray viscosity.
It may be added in an amount of about 0.5 to 5% by weight of the coating composition. Typically, acrylic polymers such as polyacrylic acid, clays such as "Bentones" cellulosic materials or urethanes may be added.

The coating composition of the present invention can be applied to plastic or metal substrates by conventional techniques such as spraying, electrostatic spraying, dipping, brushing and flow coating. The preferred method is spraying. After application, the composition may be dried at ambient temperature but baked at about 50-80 ° C. for about 5-45 minutes to produce a coating layer thickness of about 0.1-2.0 mils. . Generally, this layer is about 0.5 to 1.5 mils thick. Transparent coat /
For color coat systems, the clear layer, usually a solvent-based composition, is applied to a dry film thickness of about 1.5 to 2.5 mils. Aqueous-based clear coating compositions can also be used.

[0039]

The following example illustrates the invention. All parts and percentages are by weight unless otherwise noted. The molecular weight was measured by gel permeation chromatography using polymethylmethacrylate as a standard. Example 1 A coating composition is prepared by first forming an acrylic silane polymer latex and then mixing this latex with the other ingredients used in the coating composition. Latex A part 1 part by weight deionized water 1320.0 nonylphenoxy polyethyleneoxyethanol sulphate 10.0 part 2 ammonium persulfate 4.0 deionized water 40.0 part 3 methyl methacrylate monomer (MMA) 728.0 2-ethylhexyl acrylate Monomer (2-EHA) 728.0 γ-trimethoxysilylpropyl methacrylate (TPM) 64.0 Hydroxyethyl acrylate (HEA) 48.0 Methacrylic acid (MMA) 32.0 Nonylphenoxypolyethyleneoxyethanol sulfate 27.0 Deionized Water 954.0 Part 4 Aqueous ammonium hydroxide solution (28% aqueous solution) 30.0 Deionized water 30.0 Total 4015.0

Part 1 in a reaction vessel equipped with a heating mantle, stirrer, thermometer, reflux condenser and two addition funnels.
Was added. The resulting mixture was heated to 85 ° C with mixing. Portion 2 was placed in a container attached to an addition funnel. Portion 3 was emulsified with an Eppenbach homogenizer. 5% of the resulting emulsion was added to the reaction vessel and the temperature of the ingredients in this vessel was stabilized at 85 ° C. Then Portion 2 was added and held for 5 minutes, and then the rest of the Portion 3 emulsion was added at a uniform rate over a 90 minute time period. The temperature of the resulting polymerization mixture was maintained at 88-90 ° C during this addition. The polymerization mixture was held at the above temperature for about 1 hour. The polymerization mixture was cooled to 35 ° C. and then Part 4 was added to neutralize the latex.

The latex polymer produced had the following composition: MMA / 2-EHA / TPM / HEA / MAA in a weight ratio of 45.5 / 45.5 / 4/3/2. The polymer had a weight average molecular weight of about 250,000 to 1250,000, a hydroxyl number of 31, and an acid number of 24. This latex has a polymer particle size of 0.107 micron, a gallon weight of 8.61 lbs / gal, a pH of 9.2, a weight percent solids of 37.4 and 35.2.
It had a volume% solids.

Latex B was prepared using the above procedure, but with the following monomers: 30.5 / 15/45.
MMA / styrene / 2-EH in a weight ratio of 5/4/3/2
A / TPM / HEA / MAA.

An orange basecoat composition was prepared as follows.
Yes : A. Preparation of the dough: The following components were premixed and then ground in an attritor: parts by weight acrylic copolymer dispersion (50 parts of methyl methacrylate / butyl acrylate / methacrylic acid polymer neutralized by ammonia). % solids aqueous dispersion) 5.40 deionized water 19.67 opaque organic orange pigments (benz imidazolinone pigment) 13.50 total 38.57 B. Manufacture of undercoat: The following components were sequentially added to the kneading material composition (above) while mixing: parts by weight latex A (manufactured above) 39.34 polyether urethane latex (Neorez R-970- ICI resin-39% solids aliphatic polyether urethane having a particle size of about 0.1 micron 20.63 Flow control agent (calcium salt of complex organopolyphosphoric acid anhydride-Strodex PK-90-Dexter Chemical Co.) 0.13 thickener (acrylic copolymer emulsion polyacrylic acid-Acrysol ASE-60-Rohm & Haas Co.) 1.15 ammonium hydroxide solution (28% aqueous solution) 0.18 total 100.00 The coating composition has a solids content of 40.64% and a pigment / binder ratio of 50/100.

This orange basecoat was sprayed onto a primed cold rolled steel panel. The panels were then spray coated with a two component acrylic urethane clear coating composition and cured at ambient temperature for 21 days. The resulting basecoat had a dry film thickness of about 2.9 to 3.2 mils and the clearcoat had a dry film thickness of about 2.8 to 3.1 mils.

The coating on the panel had the following properties: Appearance-Very Good 20 ° Gloss = 99.2 Dry Crosshatch and Tape Adhesion = 10 Moisture Resistance (38 ° C./100% Relative Humidity for 96 hours) : Crosshatch adhesion = 10 Blisters = 10 (Evaluation system 0-10, 10-best, 0-worst)

Silver Undercoat Composition A. Preparation of a millbase: The following ingredients were combined in the order shown and mixed for 15 minutes: parts by weight ethylene glycol monobutyl ether 5.10 inhibitor solution (phosphated organic material) 6.10 aluminum flakes Paste (65% solids in mineral spirits) 3.74 B.I. Manufacture of Undercoat: The following ingredients were added to the kneading material composition (above) in sequence with mixing: parts by weight deionized water 51.24 latex A (manufactured above) 27.90 polyether urethane latex (Neorez R-970-ICI resin described above) 7.82 Thickener (described above) 2.27 Ammonium hydroxide solution (28% aqueous solution) 0.33 Total 100.00 The resulting coating composition was It had a solids content of 17.84% and a pigment / binder ratio of 15/100.

The silver basecoat was sprayed onto a primed cold rolled steel panel. The panels were then spray coated with the clear coating composition described above and cured at ambient temperature for 21 days. The resulting basecoat had a dry film thickness of about 0.8 to 1.0 mil, and the clearcoat had a dry film thickness of about 2.7 to 2.9 mils.

The coating on the panel had the following properties: Appearance-Very good 20 ° gloss = 100 Dry crosshatch and tape adhesion = 10 Moisture resistance (96 ° C. at 38 ° C./100% relative humidity): Cloth Hatch adhesion = 10 Blisters = 10 (Evaluation system-same as above)

The orange and silver basecoat compositions were prepared using the same ingredients as above except latex A was replaced by latex B prepared above. Primed cold rolled steel panels were coated as above with these basecoats and then with a clear coating composition (described above) and dried as above. The resulting coated panel had a very good appearance and almost the same gloss, adhesion, moisture resistance and blistering properties as the panel produced above with the composition produced by Latex A.

Example 2 A coating composition is prepared by first forming a two-stage latex C of an acrylic silane polymer and then mixing this latex with the other ingredients used in the coating composition. Latex C part 1 part by weight deionized water 1250.0 nonylphenoxy polyethyleneoxyethanol sulphate 9.0 part 2 ammonium persulfate 3.5 deionized water 44.0 part 3 methyl methacrylate monomer (MMA) 206.0 butyl acrylate monomer ( BA) 846.0 Nonylphenoxy polyethyleneoxyethanol sulphate 15.0 Deionized water 750.0 Part 4 Ammonium sulfate 0.9 Deionized water 13.0 Part 5 Methacrylic acid monomer (MAA) 22.0 2-Hydroxyethyl acrylate (HEA) ) 30.0 γ-trimethoxysilylpropyl methacrylate monomer (TPM) 25.0 butyl acrylate monomer (BA) 233.0 nonylphenoxy polyethyleneoxyethanol sulphate 10.0 deionized water 272.0 Total 3729.4

Part 1 was added to a reaction vessel equipped as in Example 1. The resulting mixture was heated to 85 ° C with mixing. Portion 2 was placed in a container attached to an addition funnel. Portion 3 was emulsified with an Eppenbach homogenizer. 5% of the resulting emulsion was added to the reaction vessel and the temperature of the ingredients in this vessel was stabilized at 85 ° C. Then Portion 2 was added and held for 5 minutes, and then the rest of the Portion 3 emulsion was added at a uniform rate over a period of 60 minutes. The temperature of the resulting polymerization mixture was maintained at 88-90 ° C during this addition. The polymerization mixture was held at a temperature above about 15 minutes of adding Part 4. Emulsify part 5 as above and place in an addition funnel and maintain temperature at 88-90 ° C. 3
Added over 0 minutes. The polymerization mixture was cooled to ambient temperature.

The latex C polymer produced had the following composition: Stage I: MMA / BA-20 / 80 weight ratio Stage II: BA / TP at 75/8/10/7 weight ratio.
M / HEA / MAA Whole: MMA / BA / TPM / HEA / MAA 15 /
79 / 2.2 / 2.2 / 1.6 This polymer contains about 250,000 to 1250,000.
Had a weight average molecular weight of 23, a hydroxyl number of 23 and an acid number of 20. This latex has a polymer particle size of 0.092 microns, a gallon weight of 8.55 lbs / gal, a pH of 2.7, a% weight solids of 34.1 and 3%.
It had a% volume solids of 2.3.

Latex D was prepared using the above procedure, but with the following monomers: Step I: MMA / styrene / BA / TPM-35 / 1
6/46/3 wt% ratio Stage II: MMA / styrene / BA / TPM / HEA / MAA at 27/12/36/8/10/7 weight ratio Overall: MMA / styrene / BA / TPM / HEA / MA
A 33/15/44 / 4.2 / 2.2 / 1.6 This polymer contains about 250,000 to 12,50,000.
Had a weight average molecular weight of 23, a hydroxyl number of 23 and an acid number of 20. This latex has a polymer particle size of 0.089 microns, a gallon weight of 8.63 lbs / gal, a pH of 2.9, 34.0 wt% solids and 31.
It had 5% solids by volume.

A white basecoat was prepared by charging the following ingredients in the order shown into a mixing vessel and blending these ingredients thoroughly together: parts by weight titanium dioxide aqueous slurry (76% solids) 170.4. Deionized water 21.4 Butyl cellosolve (ethylene glycol monobutyl ether) 18.3 Polyurethane dispersion (described in Example 1) 133.6 Latex D (prepared above) 2509 Ammonium hydroxide solution (28% Aqueous solution) 2.6 Thickener (acrylic copolymer emulsion described in Example 1) 2.8 Total 600.0 The resulting coating composition has a solids content of 78% and a pigment / binder ratio of 100: 100. Was.

This white basecoat was sprayed onto cold rolled steel panels, phosphoric acid treated steel panels, glass fiber reinforced polyester panels, reaction injection molded urethane panels and partially crystalline polyamide panels. . The panels were then spray coated with the clear coating composition described in Example 1 and cured at ambient temperature for 30 days. The resulting basecoat has a dry film thickness of about 1.0 mil and the clear coat has a thickness of about 1.8 to
It had a dry film thickness of 2.0 mils.

The coating on the panel had the following properties: Appearance-Very good 20 ° gloss = 93 Dry crosshatch and tape adhesion = 10 Moisture resistance (96 hours at 38 ° C./100% relative humidity): Cross Hatch adhesion = 10 Blister = 10 (Evaluation system-same as Example 1)

A silver basecoat was prepared by adding the following ingredients to a mixing vessel: Parts by weight Part 1 Latex D (prepared above) 206.0 Polyurethane dispersion (described in Example 1) 59. 4 Deionized water 195.8 Thickener (described above) 53.3 Part 2 Aluminum paste (64% aluminum flakes in aliphatic hydrocarbon solvent) 22.1 Inhibitor solution (described in Example 1) ) 9.5 Butyl cellosolve 43.2 Part 3 Ammonium hydroxide solution (described above) 0.5 Thickener (described above) 10.2 Total 600.0 Part 1 in a mixing vessel in the order shown. Added and mixed. Part 2 was premixed and added to the mixing vessel and mixed and then Part 3 was added and mixed.

This silver basecoat was sprayed onto cold rolled steel panels, phosphoric acid treated steel panels, glass fiber reinforced polyester panels, reaction injection molded urethane panels and partially crystalline polyamide panels. . The panels were then spray coated with the clear coating composition described in Example 1 and cured at ambient temperature for 30 days. The resulting basecoat has a dry film thickness of about 1.0 mil and the clear coat has a thickness of about 1.8 to
It had a dry film thickness of 2.0 mils.

The coating on the panel had the following properties: Appearance-Very good 20 ° Gloss = 95 Dry crosshatch and tape adhesion = 10 Moisture resistance (96 hours at 38 ° C./100% relative humidity): Cloth Hatch adhesion = 10 Blister = 10 (Evaluation system-same as Example 1)

White basecoat compositions and silver basecoat compositions were prepared using the same ingredients as above except latex C was replaced by latex D prepared above. Primed cold rolled steel panels were coated as above with these basecoats and then with a clear coat and dried as above. The resulting coated panel had very good appearance and almost the same gloss, adhesion, moisture resistance and blistering properties as the panel made by the composition made by Latex C.

Front Page Continuation (72) Inventor Irene E. Conso New Jersey, USA 08085. Swedes rose. Colony coat. Earl Day Number 2. Box 307 (56) Reference JP-A-58-168664 (JP, A) US Patent 4384013 (US, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C09D 143/04, 175/04, 5/02 C08J 7/04

Claims (9)

(57) [Claims] 1. 10-3 dispersed in an aqueous carrier.
Consisting of 0% by weight of film-forming binder and 7 to
A water-based coating composition having a pH of 10, wherein the binder comprises: a. 60-90% by weight, based on the weight of the binder,
Acrylic silane polymers consisting essentially of polymerized monomers of alkyl methacrylates, alkyl acrylates or mixtures thereof, 1 to 10% by weight of silane-containing alkyl acrylates or methacrylates based on the weight of the acrylic silane polymer, 2 to 100% polymer.
Sufficient monoethylenically unsaturated acid to give an acid number of as well as a hydroxyl number of up to 100, -40 to +
Glass transition temperature of 25 ° C. and 500,000 to 3,000
Sufficient hydroxyalkyl acrylate or hydroxyalkyl methacrylate to give a weight average molecular weight of 0000, wherein the acid groups of the polymer are reacted with ammonia or amine, b. 10-40% by weight, based on the weight of the binder,
A coating composition consisting essentially of a dispersed polyurethane selected from the group consisting of polyester urethanes, polyether urethanes or polyacrylourethanes. 2. Acrylic silane polymer is a polymerized monomer of an alkyl methacrylate, an alkyl acrylate or a mixture thereof, each having 1 to 12 carbon atoms in the alkyl group, 2 to 10% by weight in the alkyl group. Hydroxyalkyl methacrylate or acrylate having 2 to 4 carbon atoms, 0.1 to 10% by weight
Of monoethylenically unsaturated carboxylic acid and 1 to 10% by weight
The coating composition of claim 1 consisting essentially of the silane-containing acrylate or methacrylate of. 3. A silane-containing acrylate or methacrylate has the following structural formula: [In the formula, R represents CH ₃ , CH ₃ CH ₂ , CH ₃ O, or CH ₃ CH ₂ O.
R ₁ and R ₂ are independently selected from the group consisting of CH ₃ or CH ₃ CH ₂ , R ₃ is selected from the group consisting of H, CH ₃ or CH ₃ CH ₂ . And n is 0 or a positive integer not greater than 8]. 4. Acrylic silane polymerizes the monomer in step I and adds and polymerizes the monomer in step II and then grafts onto the polymerized step I monomer, wherein the step I monomer is from 10 to 30. Consisting essentially of 70% by weight of methyl methacrylate and 70-90% by weight of butyl acrylate and 70% of stage II monomer
~ 80 wt% butyl acrylate, 6-10 wt% γ-trimethoxysilylpropyl methacrylate, 8 ~
12 wt% hydroxyethyl acrylate and 5-9
A graft copolymer produced by two-step polymerization consisting essentially of wt% methacrylic acid.
The coating composition described. 5. Acrylic silane polymerizes the monomer in step I and adds and polymerizes the monomer in step II and then grafts onto the polymerized step I monomer, wherein the step I monomer is 30-40. Wt% methyl methacrylate, 10-20 wt% styrene, 40
-50% by weight butyl acrylate and 1-5% by weight γ-trimethoxysilylpropyl methacrylate essentially consisting of 25-30% by weight of stage II monomer.
Methyl methacrylate, 10-15 wt% styrene, 30-40 wt% butyl acrylate, 6-10
Is a graft copolymer produced by two-step polymerization consisting essentially of wt% γ-trimethoxysilylpropyl methacrylate, 8-12 wt% hydroxyethyl acrylate and 5-9 wt% methacrylic acid.
The coating composition according to claim 1. 6. Acrylic silane polymerizes the monomer in step I, adds and polymerizes the monomer in step II and then grafts onto the polymerized step I monomer, and adds the monomer in step III and polymerizes Grafted onto the Stage I and Stage II monomers, wherein the Stage I and II monomers consist of methylmethacrylate, allylmethacrylate, butylacrylate and the Stage III monomers of methylmethacrylate, butylacrylate and γ-trimethoxy. The coating composition according to claim 1, which is a graft copolymer formed by a three-step polymerization of silylpropyl methacrylate. 7. The acrylic silane polymer comprises alkyl methacrylate, alkyl acrylate or mixtures thereof, as well as 1 based on the weight of the acrylic silane polymer.
10% by weight of the following structural formula: [In the formula, R represents CH ₃ , CH ₃ CH ₂ , CH ₃ O, or CH ₃ CH ₂ O.
R ₁ and R ₂ are independently selected from the group consisting of CH ₃ or CH ₃ CH ₂ , R ₃ is selected from the group consisting of H, CH ₃ or CH ₃ CH ₂ . And n is 0 or a positive integer not greater than 8] consisting essentially of polymerized monomers of a silane-containing alkyl acrylate, and the polyurethane essentially consisting of a polyol and a dicarboxylic acid or its anhydride polyester polyol. A polyester urethane consisting of an organic diisocyanate, which is then reacted with a hydroxy-containing carboxylic acid, the acid being neutralized with a tertiary amine, and the resulting product chain being extended by a diamine. The coating composition according to claim 1. 8. A substrate coated with a transparent coat layer adhered to a colored coat layer adhered to a substrate, wherein the colored coat layer is dispersed in an aqueous carrier.
A water-based coating composition comprising 0-30% by weight of a film-forming binder and having a pH of 7-10, wherein the binder comprises: a. 60-90% by weight, based on the weight of the binder,
Acrylic silane polymers consisting essentially of polymerized monomers of alkyl methacrylates, alkyl acrylates or mixtures thereof, 1 to 10% by weight of silane-containing alkyl acrylates or methacrylates based on the weight of the acrylic silane polymer, 2 to 100% polymer.
Sufficient monoethylenically unsaturated acid to give an acid number of as well as a hydroxyl number of up to 100, -40 to +
Glass transition temperature of 25 ° C. and 500,000 to 3,000
Sufficient hydroxyalkyl acrylate or hydroxyalkyl methacrylate to give a weight average molecular weight of 0000, wherein the acid groups of the polymer are reacted with ammonia or amine, b. 10-40% by weight, based on the weight of the binder,
Consisting essentially of a blend of dispersed acrylic silane polymer and dispersed polyurethane of dispersed polyurethane selected from the group consisting of polyester urethane, polyether urethane or polyacrylourethane,
And a substrate formed from a coating composition wherein the composition comprises pigment in a pigment to binder weight ratio of 1: 100 to 200: 100. 9. A method for producing a substrate coated with a colored coat layer and a transparent coat layer adhered to the colored coat layer, comprising applying the colored coat layer to the substrate, At least partially drying, and then applying a clear coat layer, and curing both the color coat and the clear coat layer, wherein the color coat layer is dispersed in an aqueous carrier. A water-based coating composition comprising 30% by weight of a film-forming binder and having a pH of 7-10, the binder comprising: a. 60-90% by weight, based on the weight of the binder,
Acrylic silane polymers consisting essentially of polymerized monomers of alkyl methacrylates, alkyl acrylates or mixtures thereof, 1-10% by weight of silane-containing alkyl acrylates or methacrylates, based on the weight of the acrylic silane polymer, 2-100% of the polymer.
Sufficient monoethylenically unsaturated acid to give an acid number of as well as a hydroxyl number of up to 100, -40 to +
Glass transition temperature of 25 ° C. and 500,000 to 3,000
Sufficient hydroxyalkyl acrylate or hydroxyalkyl methacrylate to give a weight average molecular weight of 0000, wherein the acid groups of the polymer are reacted with ammonia or amine, b. 10-40% by weight, based on the weight of the binder,
Consisting essentially of a blend of dispersed acrylic silane polymer and dispersed polyurethane of dispersed polyurethane selected from the group consisting of polyester urethane, polyether urethane or polyacrylourethane,
And the coating composition is 1: 100 to 200: 10.
A method produced from a coating composition comprising a pigment in a pigment to binder weight ratio of 0.