IP Library Granted Patent US 9,988,533
Granted Patent B2
US 9,988,533 · App. 14/127,239 · Granted Jun 5, 2018

Aqueous binder compositions

Inventors: Johann Billiani (Graz, AT); Philippe Deligny (Waterloo, BE); Gerhard Reidlinger (Graz, AT); Anton Arzt (Neu-Tillmitsch, AT); Florian Lunzer (Graz, AT)
Assignees: ALLNEX BELGIUM S.A.; ALLNEX AUSTRIA GMBH
C08L75/14C08G18/0823C08G18/0866C08G18/348C08G18/4018C08G18/6517C08G18/6622C08G18/68C08G18/758C08G18/7621C08G18/7642C08L33/06C09D175/14
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Quick Facts
Patent No.
US 9,988,533
App. No.
14/127,239
Granted
Jun 5, 2018
Kind
B2
Abstract

The invention relates to mixtures of at least one acrylic resin dispersion A and a second dispersion B which is at least one of a polyurethane dispersion B1 which comprises, in its polymer, moieties derived from grafted fatty acids, and a mixture B2 of a polyurethane dispersion B21 and an aqueously dispersed alkyd resin B22, and to a method of use thereof for coating of porous substrates.

Claims (31)

1. A process for the preparation of mixtures of at least one acrylic resin dispersion A and a second dispersion B, where B is at least one of dispersion B1 and dispersion B2, where said dispersion B1 is a polyurethane dispersion comprising, in its polymer, moieties derived from grafted fatty acids which grafted fatty acids have at least 1.1 acid groups per molecule, and said dispersion B2 is a mixture of a polyurethane dispersion B21 and an aqueously dispersed alkyd resin B22,

the process comprising the following steps:

preparing at least one of said dispersion B1 and said dispersion B2,

wherein the dispersion B1 is prepared in a multi-step reaction where

in a first step, a fatty acid having at least one olefinic unsaturation is grafted with a mixture of olefinically unsaturated monomers which mixture comprises at least one acid-functional olefinically unsaturated monomer, to provide a grafted fatty acid having on average at least 1.1 acid groups per molecule,

in a second step, a compound which is hydroxy-functional is made by reacting with the grafted fatty acid at least one polyhydric alcohol having at least two hydroxyl groups, and at least one fatty acid, and

in a third step, a polyurethane is made by reacting the hydroxy functional compound with a polyfunctional isocyanate wherein the ratio n(—NCO)/n(—OH) of the amount of substance n(—NCO) of isocyanate groups in the polyfunctional isocyanate to the sum of the amounts of substance n(—OH) of hydroxyl groups in the hydroxyfunctional compounds employed in the third step is at least 1.05 mol/mol, and

in a further step, the product of the third step is reacted with at least one chain extender having at least two functional groups that react with isocyanate groups, and

wherein the dispersion B21 is prepared in a multi-step reaction where

in a first step, a fatty acid having at least one olefinic unsaturation is grafted with a mixture of olefinically unsaturated monomers which mixture comprises at least one acid-functional olefinically unsaturated monomer, to provide a grafted fatty acid having on average at least 1.1 acid groups per molecule,

in a second step, a compound which is hydroxy-functional is made by reacting with the grafted fatty acid at least one polyhydric alcohol having at least two hydroxyl groups, at least one fatty acid, and optionally, at least one polyfunctional acid having at least two acid groups, and/or an anhydride thereof, and

in a third step, a polyurethane is made by reacting the hydroxy functional compound with a polyfunctional isocyanate wherein the ratio n(—NCO)/n(—OH) of the amount of substance n(—NCO) of isocyanate groups in the polyfunctional isocyanate to the sum of the amounts of substance n(—OH) of hydroxyl groups in the hydroxyfunctional compounds employed in the third step has to be at least 1.05 mol/mol, and

in a further step, the product of the third step is reacted with at least one chain extender having at least two functional groups that react with isocyanate groups to yield polyurethane dispersion B21 which has a mass fraction of solids of from 30% to 65%, a hydroxyl number of from 20 mg/g to 200 mg/g, a specific content of chemically incorporated anionic groups of from 0 mmol/hg to 200 mmol/hg, and a mass fraction of ethylene oxide units of from 0% to 25% which are incorporated within terminal or lateral polyether chains within the polyurethane,

preparing a mixture of the dispersion B21 and the aqueously dispersed alkyd resin B22 to obtain the dispersion B2, and

mixing the at least one acrylic resin dispersion A and at least one of the second dispersions B1 and B2 to obtain a mixture.

2. The process of claim 1 wherein the mixtures comprise mass fractions of from 20% to 70% of acrylic resins present in the at least one acrylic resin dispersion A, and 80% to 30% of the polymer of the second dispersion B, where masses are always the mass of the solid resin present in the dispersion.

3. The process of claim 1 wherein the polymer of the second dispersion B is the polymer of the polyurethane dispersion B1 which comprises a mass fraction of moieties derived from grafted fatty acids in the polyurethane of from 12% to 40%, where masses are always the mass of the solid resin present in the dispersion.

4. The process of claim 1 wherein the polymer of the second dispersion B is a mixture of the polymers present in dispersion B2 which is a mixture of the polyurethane resin present in the polyurethane dispersion B21 and of the alkyd resin present in the aqueously dispersed alkyd resin B22, and wherein the mass fraction of the alkyd resin in the sum of the mass of alkyd resin and polyurethane resin is from 30% to 80%.

5. The process of claim 4 wherein the aqueously dispersed alkyd resin B22 comprises moieties derived from grafted fatty acids, and wherein the mass fraction of moieties derived from grafted fatty acids in the dispersion B2 is from 12% to 40%, where masses are always the mass of the solid resin present in the dispersion.

6. The process of claim 1 wherein the acrylic resin dispersion A has a minimum film forming temperature of less than 35° C., corresponding to a glass transition temperature of up to 30° C., a hydroxyl number of from 0 mg/g to 50 mg/g, and an acid number of from 2 mg/g to 25 mg/g, which are made by emulsion copolymerisation of at least two olefinically unsaturated monomers A1 and A2.

7. The process of claim 6 wherein the monomers A1 are selected from the group consisting of olefinically unsaturated monomers A1 selected from the group consisting

of esters A11 of olefinically unsaturated carboxylic acids with monohydroxy compounds such as aliphatic linear branched, or cyclic alcohols,

of olefinically unsaturated aromatic compounds A12 having at least one olefinically unsaturated aliphatic substituent on an aromatic residue derived from optionally substituted aromatic compounds by removal of a hydrogen atom bonded to an aromatic ring,

of olefinically unsaturated esters A13 of an unsaturated aliphatic alcohol and a saturated aliphatic carboxylic acid,

of ethers A14 of the formula R 1 —O—R 2 , wherein both R 1 and R 2 are linear or branched aliphatic radicals having from one to twenty carbon atoms, and at least one of R 1 and R 2 is olefinically unsaturated in which case the number of carbon atoms is at least two,

of unsaturated aliphatic ketones A15 of the formula R 3 —CO—R 4 , wherein both R 3 and R 4 are linear or branched or cyclic aliphatic radicals having from one to twenty carbon atoms, and at least one of R 3 and R 4 is olefinically unsaturated in which case the number of carbon atoms is at least two, and

of unsaturated aliphatic halogenides and nitriles A16 of the formula R 5 —X where X is F, Cl, Br, I, or CN, and R 5 is an unsaturated aliphatic radical having from two to twenty carbon atoms, where it is also possible that more than one hydrogen atom of the olefinically unsaturated aliphatic compound R 5 —H are substituted by the atoms or groups X.

8. The process of claim 6 wherein the monomers A2 have additional functionalities next to being olefinically unsaturated, which functionalities are selected from the group consisting of acid, hydroxyl, and acid amide, where the acid functionalities are carboxylic acid —COOH, sulphonic acid-SO 2 OH, sulphuric acid —O—SO 2 OH, phosphonic acid —PP(OH) 2 , phosphoric acid —O—PO(OH) 2 , and the acid amide functionalities are those of the corresponding amides.

9. The process of claim 1 wherein, in the dispersion B2 which is the mixture of the polyurethane dispersion B21 and the aqueously dispersed alkyd resin B22, the aqueous polyurethane dispersion B21 has a mass fraction of solids of from 30% to 65%, a hydroxyl number of from 20 mg/g to 200 mg/g, corresponding to an average hydroxy functionality a) of at least 1.8 in the polyurethane molecules, b) a mass fraction of —NH—CO— groups, calculated with a molar mass of from 43.02 g/mol, in the polyurethane of from 5% to 25%, c) a specific content of chemically incorporated anionic groups in the polyurethane of from 0 mmol/hg to 200 mmol/hg and d) a mass fraction of ethylene oxide units, calculated with a molar mass of from 44.05 g/mol, of from 0% to 25%, in the polyurethane, which are incorporated within terminal and/or lateral polyether chains within the polyurethane, wherein either the groups c) or the groups d), or both, are chemically bound within the polyurethane in an amount which is sufficient to maintain the polyurethane stably dispersed in water.

10. The process of claim 1 wherein a siccative is added to the mixture of the at least one acrylic resin dispersion A and the second dispersion B.

11. A method of use of the mixtures obtained by the process of claim 1 to prepare a coating composition by admixing a siccative, and at least one of pigments, defoamers, levelling agents, antisettling agents, antiskinning agents, and sag control agents, and applying the coating composition to a substrate selected from the group consisting of wood, leather, paper, cardboard, concrete, and plaster.

Assignments (5)
CORRECTIVE ASSIGNMENT TO CORRECT THE ASSIGNEE NAME PREVIOUSLY RECORDED AT REEL: 043934 FRAME: 0723. ASSIGNOR(S) HEREBY CONFIRMS THE ASSIGNMENT. Recorded Nov 17, 2017
From: DELIGNY, PHILIPPE
To: ALLNEX BELGIUM S.A.
Reel/Frame 044480/0927 →
CORRECTIVE ASSIGNMENT TO CORRECT THE ASSIGNEE NAME PREVIOUSLY RECORDED AT REEL: 031961 FRAME: 0094. ASSIGNOR(S) HEREBY CONFIRMS THE ASSIGNMENT. Recorded Sep 21, 2017
From: ALLNEX BELGIUM SA
To: ALLNEX BELGIUM S.A.
Reel/Frame 043934/0723 →
CHANGE OF ADDRESS OF ASSIGNEE Recorded Sep 21, 2017
From: ALLNEX BELGIUM S.A.
To: ALLNEX BELGIUM S.A.
Reel/Frame 044168/0952 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Jan 14, 2014
From: BILLIANI, JOHANN; REIDLINGER, GERHARD; ARZT, ANTON; LUNZER, FLORIAN
To: ALLNEX AUSTRIA GMBH
Reel/Frame 031961/0075 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Jan 14, 2014
From: DELIGNY, PHILIPPE
To: ALLNEX BELGIUM SA
Reel/Frame 031961/0094 →
Continuity (1)
Related Publication 20140135442A1 · May 15, 2014