COATING COMPOSITIONS CONTAINING REACTIVE DILUENTS AND METHODS

Abstract

The present invention provides coating compositions that include reactive diluents and have high performance, low VOC levels, and low irritation levels. Certain embodiments of the present invention include water and water-dispersible polymers and other embodiments do not include water.

Claims

1-78. (canceled)

79. A method of coating a substrate, the method comprising: providing a coating composition comprising: a water-dispersible polymer; a reactive diluent comprising a compound having a molecular weight of at least 350 grams/mole, wherein the reactive diluent is substantially free of ethylene oxide and propylene oxide moieties and has an OH-functionality of no more than 30 milliequivalents KOH/gram; and water; applying the coating composition to a substrate; and allowing the coating composition on the substrate to harden.

80. The method of claim 79 wherein the water-dispersible polymer is selected from the group consisting of polyurethanes, epoxies, polyamides, chlorinated polyolefins, acrylics, polyesters, and mixtures or copolymers thereof.

81. The method of claim 80 wherein the water-dispersible polymer is a water-dispersible polyurethane.

82. The method of claim 79 wherein the reactive diluent comprises a (meth)acrylate, a vinyl ether, a (meth)allyl ether, or mixtures or copolymers thereof.

83. The method of claim 79 wherein the coating composition further comprises a free-radical initiator.

84. The method of claim 79 wherein the reactive diluent is present in an amount of 5 wt-% to 40 wt-%, based on the total weight of the reactive diluent and the water-dispersible polymer.

85. The method of claim 79 comprising no more than 7 wt-% volatile organic compounds.

86. A method of coating a substrate, the method comprising: providing a coating composition comprising: an oil-modified water-dispersible polymer; a reactive diluent comprising a compound having a molecular weight of at least 350 grams/mole, wherein the reactive diluent is substantially free of ethylene oxide and propylene oxide moieties and has an OH-functionality of no more than 30 milliequivalents KOH/gram; and water; applying the coating composition to a substrate; and allowing the coating composition on the substrate to harden.

87. The method of claim 86 wherein the reactive diluent is present in an amount of 5 wt-% to 40 wt-%, based on the total weight of the reactive diluent and the oil-modified water-dispersible polymer.

88. The method of claim 86 wherein the oil-modified water-dispersible polymer is an oil-modified water-dispersible polyurethane.

89. The method of claim 86 comprising no more than 7 wt-% volatile organic compounds.

90. The method of claim 86 wherein the reactive diluent comprises a (meth)acrylate, a vinyl ether, a (meth)allyl ether, or mixtures or copolymers thereof.

91. The method of claim 86 wherein the coating composition further comprises a free-radical initiator.

92. A method of coating a substrate, the method comprising: providing a coating composition comprising: an oil-modified polymer; and a reactive diluent comprising a compound having a molecular weight of at least 350 grams/mole, wherein the reactive diluent is substantially free of ethylene oxide and propylene oxide moieties and has an OH-functionality of no more than 30 milliequivalents KOH/gram; and water; applying the coating composition to a substrate; and allowing the coating composition on the substrate to harden.

93. The method of claim 92 wherein the oil-modified polymer is selected from the group consisting of an alkyd, an oil-modified polyurethane, an oil-modified epoxy, an oil-modified polyamide, an oil-modified acrylic, and mixtures or copolymers thereof

94. The method of claim 93 wherein the oil-modified polymer is an alkyd.

95. The method of claim 92 wherein the reactive diluent is present in an amount of 5 wt-% to 40 wt-%, based on the total weight of the reactive diluent and the oil-modified polymer.

96. The method of claim 92 comprising no more than 7 wt-% volatile organic compounds.

97. The method of claim 92 wherein the reactive diluent comprises a (meth)acrylate, a vinyl ether, a (meth)allyl ether, or mixtures or copolymers thereof.

98. The method of claim 92 wherein the coating composition further comprises a free-radical initiator.

Description

EXAMPLES

[0071] Objects and advantages of this invention are further illustrated by the following examples, but the particular materials and amounts thereof recited in these examples, as well as other conditions and details, should not be construed to unduly limit this invention.

[0072] The following abbreviations have been used herein: [0073] DMPADimethylolpropionic acid (GEO, Allentown, PA) [0074] DiEMPTADi-trimethylolpropane tetraacrylate (Sartomer, Exton, Pa.) [0075] 4-HBA4-Hydroxy butylacrylate (Aldrich, Milwaukee, Wis.) [0076] TMPTrimethylol Propane (Aldrich) [0077] DESMOPHEN S-105-110Polyester diol (Bayer, Pittsburgh, Pa.) [0078] TEATriethyl Amine (Aldrich) [0079] DBTDLDibutyl Tin Dilanrate (Air Products, Allentown, Pa.)

Example 1

Preparation of (Meth)Acrylate Functional Polyurethane Dispersion (PUD) with DIEMPTA Reactive Diluent

[0080] A reactor was charged with 96.0 parts DiTMPTA, 48.0 parts 4-HBA, 91.4 parts DESMOPHEN S-105-110 polyester diol, 293 parts DMPA, 9.6 parts TMP, and 500 ppm of 2,6 di-tert-butyl-4-methylphenol. The reaction mixture was heated to 80 C. under an air sparge, where upon 250 ppm DBTDL was added and the reaction processed until the isocyanate level was below 9.2%. The urethane polymer was cooled to 65 C. and then neutralized with 22.1 parts TEA. The urethane polymer viscosity at 65 C. was 6,000 centipoise (cps) as measured by a Brookfield DV-I+ Viscometer and a Number 31 spindle at 1.5 revolutions per minute (RPM).

[0081] At a process temperature of 65 C., the (meth)acrylate urethane polymer formed above was then dispersed into 895.5 parts room temperature deionized water and subsequently chain extended with 51.1 parts hydrazine (35% in water). The dispersion was then adjusted to 35% solids with deionized water.

[0082] The physical properties of the chain extended (meth)acrylate functional polyurethane dispersion were as follows (NVM %=nonvolatile material by weight):

TABLE-US-00001 EXAMPLE 1 NVM % 35% % VOC 1.4% (TEA)

Example 2

UV Curable Coating Composition With DiTMPTA Containing (Meth)Acrylate Functional PUD

[0083] Under agitation to a stainless steel mixing vessel was added 85 parts of the dispersion from Example 1, 0.85 part, IRGACURE 500 from Ciba, 8.05 parts deionized water, 5.00 parts DOWANOL DPM from Dow Chemical, 1.00 part SUREYNOL 104PA from Air Products, and 0.10 part BYK 333 from BYK Chemie. A 3-mil thick (0.00762-cm) wet film was then applied to a Leneta Form 7B test chart and air dried for 15 minutes followed by force dry for 5 minutes at 65 C. The dried (meth)acrylate polymer film was then cured by mercury ultraviolet lamps. Total UV exposure was 1000 millijoules per square centimeter (mj/cm.sup.2).

[0084] Performance properties are outlined below. Gloss is reported in accordance with ASTM test specification, D-523. All other cured film properties are reported on a scale of 1-10, with 10 being no effect or best.

TABLE-US-00002 TEST RESULT Gloss 60 degree measurement 88-90 1 hour Exposure to mustard 9+ 1 hour exposure to 100 proof 9 vodka 100 MEK double rubs 9 80 degree flexibility 10 Fingernail mar 10

[0085] Gloss measurement was performed with a Micro-Gloss 60 from BYK Gardner in accordance with ASTM test method D-523.

[0086] 1-Hour spot test exposure to 100 proof vodka and to mustard were performed in accordance with ASTM test method D-1308.

[0087] MEK double rub testing was performed in accordance with ASTM test method D-5402.

[0088] 180-Degree flexibility was performed by bending the test chart 180 degrees around a inch (1.27 cm) diameter rod and visually looking for film cracking.

[0089] Fingernail mar was performed by rubbing the back of the fingernail softly across the cured coating and looking for surface mar.

[0090] The complete disclosures of the patents, patent documents, and publications cited herein are incorporated by reference in their entirety as if each were individually incorporated. Various modifications and alterations to this invention will become apparent to those skilled in the art without departing from the scope and spirit of this invention. It should be understood that this invention is not intended to be unduly limited by the illustrative embodiments and examples set forth herein and that such examples and embodiments are presented by way of example only with the scope of the invention intended to be limited only by the claims set forth herein as follows.