Process for preparing aqueous copolymer dispersions
The invention relates to a process for preparing a cross-linkable aqueous copolymer dispersion, wherein the process includes (1) polymerizing 5 to 64% by weight of a reaction product of at least one fatty acid having at least one ethylenic double bond and one hydroxyl group in the molecule with a polyalcohol having a hydroxyl functionality of 2 to 8, preferably the triglyceride of ricinoleic acid with 36 to 95% by weight of additional unsaturated monomers, wherein additional unsaturated monomer are polymerized in presence of at least 20% by weight of the total amount of the reaction product as polymerization medium. Aqueous coating compositions containing the aforedescribed aqueous copolymer dispersions show very good drying results compared to known aqueous coating compositions of prior art. In addition coatings therefrom show improved hardness and scratch resistance as well as improved gloss and recoat adhesion.
1. Process for preparing a cross-linkable aqueous copolymer dispersion of a water-dilutable copolymer A, comprising the steps:
1. polymerizing by radical copolymerization
a. 5 to 64% by weight of a reaction product of at least one fatty acid having at least one ethylenic double bond and one hydroxyl group in the molecule with a polyalcohol having a hydroxyl functionality of 2 to 8 and
b. 36 to 95% by weight of at least one additional unsaturated monomer b), wherein the at least one additional unsaturated monomer b) contains hydrophilic ionic groups and wherein the % by weight of monomers a) and b) are adding up to 100%,
2. neutralizing the hydrophilic ionic groups of the copolymer A before and/or during dispersing or dissolving the copolymer A in an aqueous carrier,
3. dispersing or dissolving the neutralized copolymer A in an aqueous carrier,
wherein the at least one additional unsaturated monomer b) is polymerized in presence of at least 20% by weight of the total amount of the reaction product a), thereby forming a copolymer A) having an acid number of at least 10 mg KOH/g solids.
2. The process of claim 1 , wherein the copolymer A) comprises 10 to 50% by weight of the reaction product of at least one fatty acid having at least one ethylenic double bond and one hydroxyl group in the molecule with a polyalcohol having a hydroxyl functionality of 2 to 8, and 50 to 90% by weight of the at least one additional unsaturated monomer b), wherein the % by weight are adding up to 100%.
3. The process of claim 1 or 2 , wherein copolymer A) has an acid number of 15-80 mg KOH/g solids.
4. The process of claim 3 , wherein copolymer A) has a hydroxyl number of 50 to 250 mg KOH/g solids and a number average molecular weight Mn of 800 to 8000.
5. The process of claim 3 , wherein copolymer A) comprises
a) 5 to 64% by weight of the reaction product of at least one fatty acid having at least one ethylenic double bond and one hydroxyl group in the molecule with a polyalcohol having a hydroxyl functionality of 2 to 8 and
b) 36 to 95% by weight of unsaturated monomers comprising:
b1) at least one hydroxyl-functional unsaturated monomer,
b2) at least one acid-functional unsaturated monomer and
b3) optionally at least one other polymerizable unsaturated monomer different from monomers b1) and b2), wherein the % by weight of a) and b) are adding up to 100%.
6. The process of claim 3 , wherein copolymer A) comprises
a) 5 to 64% by weight of the reaction product of at least one fatty acid having at least one ethylenic double bond and one hydroxyl group in the molecule with a polyalcohol having a hydroxyl functionality of 2 to 8,
b1) 0 to 60% by weight of at least one hydroxyalkyl ester with at least one primary or secondary hydroxyl group derived from alpha, beta-ethylenically unsaturated monocarboxylic acids.
b2) 2 to 40% by weight of at least one an unsaturated acid functional monomer,
b3.1) 0 to 50% by weight of at least one ester of (meth)acrylic acid with aliphatic monohydric branched or linear as well as cyclic alcohols with 1 to 20 C atoms and
b3.2) 0 to 50% by weight of at least one unsaturated vinyl aromatic monomer, wherein the % by weight of reaction product a) and monomers b1) to b3.2) are adding up to 100%.
7. The process of claim 3 , wherein the fatty acid in the reaction product of at least one fatty acid having at least one ethylenic double bond and one hydroxyl group in the molecule with a polyalcohol having a hydroxyl functionality of 2 to 8 is ricinoleic acid.
8. The process of claim 3 , wherein the reaction product of at least one fatty acid having at least one ethylenic double bond and one hydroxyl group in the molecule with a polyalcohol having a hydroxyl functionality of 2 to 8 is the triglyceride of ricinoleic acid.
9. The process of claim 3 , wherein the reaction product of at least one fatty acid having at least one ethylenic double bond and one hydroxyl group in the molecule with a polyalcohol having a hydroxyl functionality of 2 to 8 is castor oil.
10. The process of claim 3 , wherein the copolymer A) is a graft copolymer comprising:
8-92% by weight of the graft copolymer of a polymeric backbone of polymerized reaction product a) and unsaturated monomers b) and
92-8% by weight of the graft copolymer, of a macromonomer c) attached to said polymeric backbone at a single terminal point of said macromonomer, wherein the % by weight are adding up to 100%, said macromonomer having a number average molecular weight Mn of 500-8000 and comprising 10 to 100% by weight of the macromonomer of ethylenically unsaturated acid-functional and/or amine-functional monomers.
11. The process of claim 10 , wherein the copolymer A) is prepared by polymerizing unsaturated monomers b) in presence of a mixture of 20 to 80% by weight of the reaction product a) of at least one fatty acid having at least one ethylenic double bond and one hydroxyl group in the molecule with a polyol having a hydroxyl functionality of 2 to 8 and 20 to 80% by weight of macromonomer c), wherein the % by weight are adding up to 100%.
12. Aqueous copolymer dispersion prepared according to the process of claim 3 .
13. The aqueous copolymer dispersion of claim 12 further comprising a cross-linking agent.
14. Process for preparing a cross-linkable aqueous copolymer dispersion of a water-dilutable copolymer A, comprising the steps:
1. polymerizing by radical copolymerization
a. 5 to 64% by weight of the triglyceride of ricinoleic acid or castor oil and
b. 36 to 95% by weight of at least one additional unsaturated monomer b), wherein the at least one additional unsaturated monomer b) contains hydrophilic ionic groups and wherein the % by weight of monomers a) and b) are adding up to 100%,
2. neutralizing the hydrophilic ionic groups of the copolymer A before and/or during dispersing or dissolving the copolymer A in an aqueous carrier,
3. dispersing or dissolving the neutralized copolymer A in an aqueous carrier,
wherein the at least one additional unsaturated monomer b) is polymerized in presence of at least 20% by weight of the total amount of component a), thereby forming a copolymer A) having an acid number of at least 10 mg KOH/g solids.
15. Process for preparing a cross-linkable aqueous copolymer dispersion of a water-dilutable copolymer A, comprising the steps:
1. polymerizing by radical copolymerization
a. 5 to 64% by weight of a reaction product of at least one fatty acid having at least one ethylenic double bond and one hydroxyl group in the molecule with a polyalcohol having a hydroxyl functionality of 2 to 8 and
b. 36 to 95% by weight of at least one additional unsaturated monomer b), wherein the at least one additional unsaturated monomer b) contains hydrophilic ionic groups and wherein the % by weight of monomers a) and b) are adding up to 100%,
2. neutralizing the hydrophilic ionic groups of the copolymer A before and/or during dispersing or dissolving the copolymer A in an aqueous carrier,
3. dispersing or dissolving the neutralized copolymer A in an aqueous carrier,
wherein the at least one additional unsaturated monomer b) is polymerized in presence of 30 to 100% by weight of the total amount of the reaction product a), thereby forming a copolymer A) having an acid number of at least 10 mg KOH/g solids.