Tin-Free, High-Melting Reaction Products of Carbonyl-Hydrogenated Ketone Aldehyde Resins, Hydrogenated Ketone Resins, and Carbonyl-Hydrogenated and Core-Hydrogenated Ketone Aldehyde Resins Based on Aromatic Ketones and Polyisocynates

Abstract

The invention relates to tin-free reaction products of hydroxyl-containing hydrogenated ketone resins, carbonyl-hydrogenated ketone-aldehyde resins, and carbonyl-hydrogenated and ring-hydrogenated ketone-aldehyde resins based on aromatic ketones and polyisocyanates, to a process for their preparation and to the use thereof, in particular as a main component, base component or additive component in coating materials, adhesives, inks, polishes, glazes, stains, pigment pastes, filling compounds, cosmetics articles, sealants and/or insulants.

Description

EXAMPLE 1

For the Preparation of a Reaction Product

The synthesis takes place by reacting 400 g of a carbonyl-hydrogenated resin formed from acetophenone and formaldehyde (OHN=240 mg KOH/g (acetic anhydride method), M_n˜1000 g/mol (GPC against polystyrene standard), melting range 114-120° C.) with 99.3 g of H₁₂MDI (Vestanat EP H₁₂MDI, Degussa AG) in the presence of 0.15% of Coscat 83 (based on resin, Caschem Catalysts) in 50% dilution with ethyl acetate in a three-necked flask equipped with stirrer, reflux condenser and temperature sensor under nitrogen at 55° C. until an NCO number of less than 0.1 has been reached.

This gives a pale, clear solution having a dynamic viscosity of 2.6 Pa·s. The Gardner color number of the solution is 0.4. After storage at 60° C. for 14 days the Gardner color number is 0.5, which within the bounds of the accuracy of the method can be considered unchanged and suggests high yellowing stability of the resin solution. After the solvent has been separated off a colorless powder is obtained which possesses a melting range of between 163 and 166° C.

	Coating material	A	I
	Nitrocellulose E 510 (65% in isopropanol)	19.3	13.5
	Ethyl acetate	23.2	19.5
	n-Butanol	5.0	5.0
	Methoxypropanol	2.5	2.5
	Vestinol AH	2.5	2.5
	Resin from example 1	—	7.5
	Total	52.5	50.5

Resin solutions A and I were applied using a doctor blade to a glass plate and also to various plastic plates and metal. The wet film thickness was 100 μm. After 14 days under standard conditions (23° C., 50% relative humidity), the gloss and adhesion of the films were measured.

Film Properties:

		Gloss
Coating	FT	60° angle
material	[μ]	(substrate: pine)
A	22-26	69
I	26-33	92

Blade Scratch Adhesion to Various Substrates:

Coating
material	Glass	ABS	PE	PVC	PC	Metal
A	0	0	10	10	10	2
I	0	0	08	5	2	0
0 = very good adhesion; 10 = no adhesion

Abbreviations

• ABS: Acrylonitrile-butadiene-styrene copolymer
• PC: Polycarbonate
• PE: Polyethylene
• PVC: Polyvinyl chloride
• FT: Film thickness

Claims

1. A tin-free high-melting reaction product essentially comprising the product of reaction, with a melting range of above 140° C., of A) at least one carbonyl-hydrogenated ketone-aldehyde resin and/or hydrogenated ketone resin and/or carbonyl-hydrogenated and ring-hydrogenated ketone-aldehyde resin based on aromatic ketoneswithB) at least one aromatic, aliphatic and/or cycloaliphatic diisocyanate or polyisocyanate.

2. A tin-free high-melting reaction product essentially comprising the product of reaction, with a melting range of above 140° C., of A) at least one carbonyl-hydrogenated ketone-aldehyde resin and/or hydrogenated ketone resin and/or carbonyl-hydrogenated and ring-hydrogenated ketone-aldehyde resin based on aromatic ketoneswithB) at least one aromatic, aliphatic and/or cycloaliphatic diisocyanate or polyisocyanateandC) at least one further, hydroxy-functionalized polymer.

3. A reaction product as claimed in claim 1, wherein C—H-acetic ketones are used in component A).

4. A reaction product as claimed in claim 1, wherein the carbonyl-hydrogenated ketone-aldehyde resins of component A) is ketones selected from acetone, acetophenone, ring-substituted acetophenone derivatives, 4-tert-butyl methyl ketone, methyl ethyl ketone, heptan-2-one, pentan-3-one, methyl isobutyl ketone, propiophenone, methyl naphthyl ketone, cyclopentanone, cyclododecanone, mixtures of 2,2,4- and 2,4,4-trunethylcyclopentanone, cycloheptanone and cyclooctanone, cyclohexanone and all alkyl-substituted cyclohexanones having one or more alkyl radicals, which contain in total from 1 to 8 carbon atoms, individually or in a mixture.

5. A reaction product as claimed in claim 1, wherein the carbonyl-hydrogenated ketone-aldehyde resins of component A) is an alkyl-substituted cyclohexanones having one or more alkyl radicals containing in total from 1 to 8 carbon atoms, individually or in a mixture, as starting compounds.

6. A reaction product as claimed in claim 5, wherein 4-tert-amylcyclohexanone, 2-sec-butylcyclohexanone, 2-tert-butylcyclohexanone, 4-tert-butylcyclohexanone, 2-methylcyclohexanone and/or 3,3,5-trimethylcyclohexanone are used.

7. A reaction product as claimed in claim 1, wherein the aldehyde component of the carbonyl-hydrogenated ketone-aldehyde resins in component A) is formaldehyde, acetaldehyde, n-butyraldehyde and/or isobutyraldehyde, valeraldehyde or dodecanal, alone or in mixtures.

8. A reaction product as claimed in claim 7, wherein formaldehyde and/or para-formaldehyde and/or trioxane are used.

9. A reaction product as claimed in claim 1, wherein carbonyl hydrogenation products of the resins formed from acetophenone, 4-tert-butyl methyl ketone, cyclohexanone, 4-tert-butylcyclohexanone, 3,3,5-trimethylcyclohexanone or heptanone, alone or in a mixture, and formaldehyde are used as component A).

10. A reaction product as claimed in claim 1, wherein the hydrogenated ketone resins of component A) comprise ketones selected from acetone, 4-tert-butyl methyl ketone, methyl ethyl ketone, heptan-2-one, pentan-3-one, methyl isobutyl ketone, propiophenone, cyclopentanone, cyclododecanone, mixtures of 2,2,4- and 2,4,4-trimethylcyclopentanone, cycloheptanone and cyclooctanone, cyclohexanone and all alkyl-substituted cyclohexanones having one or more alkyl radicals, which contain in total from 1 to 8 carbon atoms, individually or in a mixture.

11. A reaction product as claimed in claim 10, wherein cyclohexanone, 4-tertamylcyclohexanone, 2-sec-butylcyclohexanone, 2-tert-butylcyclohexanone, 4-tertbutylcyclohexanone, 2-methylcyclohexanone and/or 3,3,5-trimethylcyclohexanone are used.

12. A reaction product as claimed in claim 1, wherein aryl alkyl ketones are used in the carbonyl-hydrogenated and ring-hydrogenated ketone-aldehyde resins of component A).

13. A reaction product as claimed in claim 1, wherein the carbonyl-hydrogenated and ring-hydrogenated ketone-aldehyde resins of component A) comprise ketones selected from acetophenone, ring-substituted acetophenone derivatives, and methyl naphthyl ketone.

14. A reaction product as claimed in claim 1, wherein formaldehyde, acetaldehyde, n-butyraldehyde and/or isobutyraldehyde, valeraldehyde or dodecanal, alone or in mixtures, are used in the aldehyde component of the carbonyl-hydrogenated and ring-hydrogenated ketone-aldehyde resins of component A).

15. A reaction product as claimed in claim 1, wherein the component B) is diisocyanates selected from cyclohexane diisocyanate, methylcyclohexane diisocyanate, ethylcyclohexane diisocyanate, phenylene diisocyanate, propylcyclohexane diisocyanate, methyldiethylcyclohexane diisocyanate, tolylene diisocyanate, bis(isocyanatophenyl)methane, propane diisocyanate, butane diisocyanate, pentane diisocyanate, hexane diisocyanate, heptane diisocyanate, octane diisocyanate, nonane diisocyanate, nonane triisocyanate, decane diisocyanate and triisocyanate, undecane diisocyanate and triisocyanate, dodecane diisocyanates and triisocyanates, isophorone diisocyanate (IPDI), bis(isocyanatomethylcyclohexyl)methane (H12MDI), isocyanatomethyl methylcyclohexyl isocyanate, 2,5(2,6)-bis(isocyanatomethyl)bicyclo[2.2.1]heptane (NBDI), 1,3-bis(isocyanatomethyl)cyclohexane (1,3-H6-XDI) or 1,4-bis(isocyanatomethyl)cyclohexane (1,4-H6-XDI), alone or in mixtures.

16. A reaction product as claimed in claim 1, wherein polyisocyanates prepared by dimerization, trimerization, allophanatization, biuretization and/or urethanization of simple diisocyanates are used as component B).

17. A reaction product as claimed in claim 1, wherein isocyanates based on IPDI, TMDI, H12MDI and/or HDI are used as component B).

18. A reaction product as claimed in claim 1, wherein 1 mol of component A), based on Mn, and from 0.2 to 15 mol, of component B) are used.

19. A reaction product as claimed in claim 1, wherein the melting range of the reaction product of A) and B) is above 140° C.

20. A reaction product as claimed in claim 1, wherein polyesters, polyacrylates, nonhydrogenated ketone-aldehyde resins and/or nonhydrogenated and/or ring-hydrogenated phenyl-aldehyde resins are used as hydroxy-functionalized polymers C).

21. The reaction product as claimed in claim 1, where mixtures of the polymers C) and component A) are subjected to polymer-analogous reaction with component B).

22. A process for preparing a reaction product essentially comprising the product of reaction, with a melting range of above 140° C., of A) at least one carbonyl-hydrogenated ketone-aldehyde resin and/or hydrogenated ketone resin and/or carbonyl-hydrogenated and ring-hydrogenated ketone-aldehyde resin based on aromatic ketoneswithB) at least one aromatic, aliphatic and/or cycloaliphatic diisocyanate or polyisocyanateand if desired,C) at least one further, hydroxy-functionalized polymerby reacting A) and B) and, where used, C) at temperatures from 20 to 150° C. in the presence of a catalyst which contains no tin.

23. A process as claimed in claim 22, wherein the reactants are A) at least one carbonyl-hydrogenated ketone-aldehyde resin and/or hydrogenated ketone resin and/or carbonyl-hydrogenated and ring-hydrogenated ketone-aldehyde resin based on aromatic ketoneswithB) at least one aromatic, aliphatic and/or cycloaliphatic diisocyanate or polyisocyanateandC) at least one further, hydroxy-functionalized polymer.

24. A process as claimed in claim 23, wherein the catalysts are selected from the group comprising zirconium, iron, bismuth and/or aluminum.

25. A process as claimed in claim 24, wherein compounds comprising bismuth are used as catalyst.

26. A process as claimed in claim 22, wherein the catalyst is stabilized.

27. A process as claimed in claim 26, wherein the catalyst is stabilized with monocarboxylic and/or dicarboxylic acids.

28. A process as claimed in claim 22, wherein the catalysts are organic compounds.

29. A process as claimed in claim 28, wherein the catalysts are tertiary amines.

30. A process as claimed in claim 29, wherein the catalysts are selected from the group 1,4-diazabicyclo[2.2.2]octane (DABCO), 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU), N,N-dimethylcyclohexylamine (DMCA) and/or 1,5-diazabicyclo[2.3.0]non-5-ene (DBN).

31. A process as claimed in claim 22, wherein component B is added in the presence of the tin-free catalyst to the solution or melt of component A).

32. A process as claimed in claim 22, wherein component B is added in the presence of the tin-free catalyst to the solution or melt of component A) and the hydroxy-functional polymer C).

33. A process as claimed in claim 22, wherein reaction is carried out at temperatures between 30 and 150° C., preferably between 50 and 140° C.

34. The reaction product as claimed in claim 1 as a main component, base component or additive component in a coating material, adhesive, ink, polish, glaze, stain, pigment paste, filling compound, cosmetics article, sealant and/or insulant.

35. The reaction product as claimed in claim 1 as a main component, base component or additive component in a coating material, adhesive, ink, polish, glaze, stain, pigment paste, filling compound, cosmetics article, sealant and/or insulant for the purpose of improving the adhesion properties and hardness.