Reactive hydroxylated and carboxylated polymers for use as adhesion promoters

Abstract

A polymer complex is disclosed which is the reaction product of one or more polymers having a terminal or pendant hydroxyl group, or a terminal or pendent carboxyl group, or combinations thereof, with at least one metal complex and one alkyl phosphate. This polymer complex acts as an adhesion promotion agent as well as a viscosity stabilizer when formulated in a printing ink or coating.

Claims

1. A polymer complex comprising the reaction product of: one or more polyacrylates having: a) a terminal or pendent carboxyl group, or a terminal or pendent hydroxyl group; or b) a combination of a terminal or pendent carboxyl group and a terminal or pendent hydroxyl group; with at least one metal orthoester and at least one alkyl phosphate.

2. The polymer complex of claim 1, wherein said metal orthoester has the formula metal(OR).sub.4, wherein each of the four R groups is independently an alkyl group.

3. The polymer complex of claim 2, wherein said alkyl group is a C.sub.1 to C.sub.8 alkyl group.

4. The polymer complex of claim 2, wherein said alkyl group is a C.sub.3 to C.sub.4 alkyl group.

5. The polymer complex of claim 1, wherein said metal orthoester is tetraisopropyltitanate.

6. The polymer complex of claim 1, wherein said alkyl phosphate is a monoalkyl phosphate having the formula (R.sub.1O)PO(OH).sub.2 or a dialkylphosphate having the formula (R.sub.2O)(R.sub.3O)PO(OH), wherein each of R.sub.1, R.sub.2 and R.sub.3 is independently an alkyl.

7. The polymer complex of claim 6, wherein said alkyl group is a C.sub.1 to C.sub.10 alkyl group.

8. The polymer complex of claim 6, wherein said alkyl group is a C.sub.1 to C.sub.5 alkyl group.

9. The polymer complex of claim 1, wherein said alkyl phosphate is amyl acid phosphate.

10. An ink or coating composition containing an adhesion promoting agent comprising the reaction product of: one or more polyacrylates having a) a terminal or pendent hydroxyl group; or b) a combination of a terminal or pendent carboxyl group and a terminal or pendent hydroxyl group; with at least one metal orthoester and at least one alkyl phosphate.

11. The composition of claim 10, wherein said metal orthoester has the formula metal(OR).sub.4, wherein each of the four R groups is independently an alkyl group.

12. The composition of claim 11, wherein said alkyl group is a C.sub.1 to C.sub.8 alkyl group.

13. The composition of claim 11, wherein said alkyl group is a C.sub.3 to C.sub.4 alkyl group.

14. The composition of claim 10, wherein said metal orthoester is tetraisopropyltitanate.

15. The composition of claim 10, wherein said alkyl phosphate is a monoalkyl phosphate having the formula (R.sub.1O)PO(OH).sub.2 or a dialkylphosphate having the formula (R.sub.2O)(R.sub.3O)PO(OH), wherein each of R.sub.1, R.sub.2 and R.sub.3 is independently an alkyl.

16. The composition of claim 15, wherein said alkyl group is a C.sub.1 to C.sub.10 alkyl group.

17. The composition of claim 15, wherein said alkyl group is a C.sub.1 to C.sub.5 alkyl group.

18. The composition of claim 10, wherein said alkyl phosphate is amyl acid phosphate.

19. A method of improving the adhesion performance of an ink or coating composition comprising adding to said composition an agent comprising the reaction product of one or more polyacrylates having a terminal or pendent hydroxyl group, or a combination of a terminal or pendent carboxyl group and a terminal or pendent hydroxyl group, and at least one metal orthoester and at least one alkyl phosphate.

20. The method of claim 19 wherein the viscosity stability of an ink or coating composition is also enhanced.

21. The method of claim 19, wherein said metal orthoester has the formula metal(OR).sub.4, wherein each of the four R groups is independently an alkyl group.

22. The method of claim 21, wherein said alkyl group is a C.sub.1 to C.sub.8 alkyl group.

23. The method of claim 21, wherein said alkyl group is a C.sub.3 to C.sub.4 alkyl group.

24. The method of claim 19, wherein said metal orthoester is tetraisopropyltitanate.

25. The method of claim 19, wherein said alkyl phosphate is a monoalkyl phosphate having the formula (R.sub.1O)PO(OH).sub.2 or a dialkylphosphate having the formula (R.sub.2O)(R.sub.3O)PO(OH), wherein each of R.sub.1 R.sub.2 and R.sub.3 is independently an alkyl.

26. The method of claim 25, wherein said alkyl group is a C.sub.1 to C.sub.10 alkyl group.

27. The method of claim 25, wherein said alkyl group is a C.sub.1 to C.sub.5 alkyl group.

28. The method of claim 19, wherein said alkyl phosphate is amyl acid phosphate.

29. The method of claim 19 which also promotes stabilizing the viscosity of the ink or coating composition.

30. The method of claim 29, wherein said metal orthoester has the formula metal(OR).sub.4, wherein each of the four R groups is independently an alkyl group.

31. The method of claim 30, wherein said alkyl group is a C.sub.1 to C.sub.8 alkyl group.

32. The method of claim 30, wherein said alkyl group is a C.sub.3 to C.sub.4 alkyl group.

33. The method of claim 29, wherein said metal orthoester is tetraisopropyltitanate.

34. The method of claim 29, wherein said alkyl phosphate is a monoalkyl phosphate having the formula (R.sub.1O)PO(OH).sub.2 or a dialkylphosphate having the formula (R.sub.2O)(R.sub.3O)PO(OH), wherein each of R.sub.1 R.sub.2 and R.sub.3 is independently an alkyl.

35. The method of claim 34, wherein said alkyl group is a C.sub.1 to C.sub.10 alkyl group.

36. The method of claim 34, wherein said alkyl group is a C.sub.1 to C.sub.5 alkyl group.

37. The method of claim 29, wherein said alkyl phosphate is amyl acid phosphate.

Description

DETAILED DESCRIPTION OF THE INVENTION

(1) It has now been surprisingly found that the adhesion promoting performance of hydroxylated and carboxylated polymers in a printing Ink or coating can be enhanced by incorporating additional reactive functional sites on the polymeric backbone of the polymer thereby developing a new class of reactive polymers.

(2) This new class of reactive polymers is the reaction product of at least one polymer containing terminal and/or pendant hydroxyl and/or terminal and/or pendant carboxyl groups, or combinations thereof, and at least one metal complex and at least one alkyl phosphate. The new polymer demonstrates unexpected levels of adhesion at lower levels of metal complex when compared to polymeric systems where the hydroxylated or carboxylated polymer and organometallic or metal containing compounds are added individually to, for example, a surface coating formulation. Specifically, two distinct beneficial effects have been recognized when these new reactive polymers are used in an ink or coating formulation.

(3) As compared to the individual use of metal complexes alone, the viscosity stability in Inks and coatings (especially pigmented systems) is enhanced

(4) As compared to the use of the hydroxylated or carboxylated polymers alone, the adhesion performance is enhanced and more rapidly achieved in surface coatings, especially under lower temperature drying conditions. In lamination applications improved performance is demonstrated by superior lamination bond strength.

(5) Metal Complex

(6) Preferably, the metal complex is metal orthoester which also preferably has the general formula (metal)(OR).sub.4 in which R represents an alkyl group which usually contains up to 8 carbon atoms. However, more preferably the alkyl group has 3 or 4 carbon atoms. It is of course possible that mixed alkyl orthometallics may be used such as mixed isopropyl butyl compounds. Most preferably, the metal containing compound is tetraisopropyltitanate.

(7) Polymer Backbone

(8) Generally speaking, the hydroxylated or carboxylated polymer used to prepare the reactive hydroxylated polymer can be any polymer having terminal and/or pendant hydroxyl or carboxyl groups. These can be either natural or synthetic resins, including (but not limited to) polyurethanes, polyurethane-ureas, polyamides, polyesters, polyacrylates, ketone-formaldehyde copolymers, nitrocellulose. These can be polymers suitable for both solvent based and water based coatings.

(9) Alkyl Phosphate

(10) The alkyl phosphate is used in the reaction to stabilize the polymer complex. Preferably, monoalkyl or dialkyl phosphates are used. The monoalkyl phosphate used will have the general formula (R.sub.1O)PO(OH).sub.2 and the dialkyl phosphate will have the general formula (R.sub.2O)(R.sub.3O)PO(OH), wherein R.sub.1, R.sub.2 and R.sub.3 each independently represents an alkyl group which can contain up to 10 carbon atoms but preferably contains no more than 5 carbon atoms. Also, preferably R.sub.1, R.sub.2 and R.sub.3 are identical when mixed monoalkyl and dialkyl phosphates are to be used but this need not necessarily be so. Naturally, if desired, the dialkyl phosphate can include different alkyl groups. Most preferably, the alkyl phosphate used is amyl acid phosphate.

EXAMPLE 1

Preparation of Reactive Polymers

(11) A. Adhesion-Modified Hydroxyl Functional Polyol Resin

(12) In a clean, dry reactor under nitrogen, n-propyl acetate (20.93 grams) was charged along with Degussa Synthetic Resin SK (20.94 grams). The resulting reaction slurry was stirred and heated to 50-60 C. until all of the resin was dissolved. The reactor temperature was then cooled to 25-35 C. Tetraisopropyltitanate (33.91 grams) was added over 15 minutes and the mixture stirred for 15 minutes. The formation of the intermediate reaction product was followed by monitoring changes in the infrared absorbance of the hydroxyl group at 3400 wavenumbers, where the signal intensity decreased to 11% of the initial signal upon completion of the reaction. Amyl acid phosphate (24.22 grams) was then added over 20 minutes while the reaction temperature was maintained below 60 C. When the addition was complete, the temperature was held at 60 C. for 1 hour. Thereafter, the resulting polymer was discharged at a temperature of 25-35 C. through a 25 micron filter bag and was observed to have the properties shown below in Table 1.

(13) TABLE-US-00001 TABLE 1 Property: Value: Notes on measurements Appearance Clear, yellow liquid Gardener Color 3-5 Brookfield Viscosity 50-150 centipoise 25 C., #3 spindle @ 60 rpm Percent Solids 58.0-62.0% 100 C. for 15 minutes using a forced air oven
B. Adhesion-Modified Acid Functional Polyurethane-Urea

(14) In a clean, dry reactor under nitrogen, a solution of an acid functional polyurethane-urea in n-propanol and n-propyl acetate (1,000 grams) were charged. The material was stirred at 25-35 C. Tetraisopropyltitanate (3 grams) was added over 15 minutes and the mixture stirred for 15 minutes. The formation of the Intermediate reaction product was followed by monitoring changes in the infrared absorbance of the acid carbonyl group at 3400 wavenumbers, where the signal Intensity decreased to 62% of the initial signal upon completion of the reaction. Butyl phosphate (2 grams) was then added over 20 minutes while the reaction temperature was maintained below 60 C. When this addition was complete, the temperature was held at 60 C. for 1 hour. Thereafter, the resulting polymer was discharged at a temperature of 25-35 C. through a 25 micron filter bag.

(15) C. Adhesion-Modified Acid Functional Polyamide Resin

(16) In a clean, dry reactor under nitrogen, n-propanol (350 grams) was charged, along with Cognis Versamid 972 (an acid functional polyamide resin) (150 grams). The resulting reaction slurry was stirred and heated to 50-60 C. until all of the resin dissolved. The reactor temperature was then cooled to 25-35 C. Tetraisopropyltitanate (3 grams) was then added over 15 minutes and the mixture stirred for 15 minutes. The formation of the intermediate reaction product was followed by monitoring changes in the infrared absorbance of the acid carbonyl group at the appropriate wavenumbers, where the signal intensity/abosorption decreased by a percentage upon completion of the reaction. Amyl acid phosphate (2 grams) was then added over 20 minutes while the reaction temperature was maintained below 60 C. When this addition was complete, the temperature was held at 60 C. for 1 hour. Thereafter, the resulting polymer was discharged at a temperature of 25-35 C. through a 25 micron filter bag.

(17) D. Adhesion-Modified Hydroxyl Functional Polyester Resin

(18) In a clean, dry reactor under nitrogen, a solution of a hydroxyl functional branched polyester in n-propanol and n-propyl acetate (1,000 grams) were charged. The material was stirred at 25-35 C. Tetraisopropyltitanate (0.6 grams) was then added over 15 minutes and the mixture stirred for 15 minutes. The formation of the intermediate reaction product was followed by monitoring changes in the infrared absorbance of the hydroxyl group at 3400 wavenumbers, where the signal Intensity decreased to 50% of the initial signal upon completion of the reaction. Butyl phosphate (0.4 grams) was then added over 20 minutes while the reaction temperature was maintained below 60 C. When this addition was complete, the temperature was held at 60 C. for 1 hour. Thereafter, the resulting polymer was discharged at a temperature of 25-35 C. through a 25 micron filter bag.

EXAMPLE 2

Preparation of Printing Inks and Testing

(19) A printing ink having the composition detailed in Table 2 was prepared using IA10 adhesion (titanium chelate) promoting agent the synthesis of which is detailed in U.S. Pat. No. 4,659,848, herein incorporated by reference. Additional printing inks were prepared using no adhesion promoting agent, synthetic resin SK, combination of IA10 and SK or the reaction product of the present invention as described in Example 1.

(20) TABLE-US-00002 TABLE 2 INK #1 INK #2 INK #3 INK #4 INK #5 IA10 only SK only Experimental IA10 and SK Control (Comparative) (Comparative) (Example 1 A) (Comparative) (Comparative) Pigment Red 48:2 52.8 52.8 52.8 52.8 52.8 SS nitrocellulose 20.2 20.2 20.2 20.2 20.2 isopropyl acetate 15.4 15.4 15.4 15.4 15.4 denatured ethanol 133.6 133.6 133.6 133.6 133.6 n-propyl acetate 18.0 18.0 18.0 18.0 18.0 Total 240.0 240.0 240.0 240.0 240.0 Disperse and add: denatured ethanol 62.6 62.6 62.6 62.6 64.5 n-propyl acetate 19.8 19.8 19.8 20.8 20.4 isopropyl alcohol 15.4 15.4 15.4 15.4 15.8 RS nitrocellulose 15.4 15.4 15.4 15.4 15.8 polyurethane 30.9 30.9 30.9 30.9 31.8 Citric acid 0.8 0.8 0.8 0.8 0.9 wax compound 3.1 3.1 3.1 3.1 3.2 slip compound 7.3 7.3 7.3 7.3 7.5 IA10 (titanium 4.8 2.8 chelate) Synthetic Resin 4.8 1.0 SK Example 1 (492- 4.8 753) 400.0 400.0 400.0 400.0 400.0
Viscosity Stability

(21) Ink samples were tested using a #3 Zahn dip-type efflux viscosity cup. Table 3 illustrates the results.

(22) TABLE-US-00003 TABLE 3 Aged Viscosity Ink # Initial Viscosity (16 hours @ 48 C.) 1 30 seconds 24 seconds 2 25 seconds 20 seconds 3 30 seconds 20 seconds 4 25 seconds 22 seconds 5 25 seconds 52 seconds
Adhesion

(23) Test inks 1-5 were reduced to print viscosity (25 seconds @ 25 C. in a #2 Zahn dip-type efflux viscosity cup) and were printed on treated polypropylene using a flexographic handproofer. One Bump indicates one application of ink. Two Bumps indicates two applications of the same ink, one over the other. The results are illustrated in Table 4.

(24) TABLE-US-00004 TABLE 4 Air dried Oven dried (no heat applied) (10 seconds @ 80 C. Ink # One Bump Two Bumps One Bump Two Bumps 1 2 5 1 1 2 2 5 1 2 3 1 4 1 1 4 5 4 1 1 5 5 5 1 4 *1 = Best, 5 = Worst

(25) From the above data, the inks of the present invention show superior viscosity stabilization and tape adhesion properties than commercial and prior art inks.

EXAMPLE 3

(26) Laminating Inks#6 and 7 were prepared as detailed in Table 5 using IA10 (titanium chelate) adhesion promoting agent and the reactive polymer product described in Example 1.

(27) TABLE-US-00005 TABLE 5 Percent by weight Ink #6 Ink #7 Component: Comparative Experimental Titanium dioxide 44.1 44.1 SS nitrocellulose solution 2.9 2.9 polyurethane 31.4 31.4 n-propyl acetate 14.7 14.7 n-propyl alcohol 4.9 4.9 IA10 titanium chelate 2 0 Product of Example 1 A 0 2
Viscosity Stability

(28) The inks were tested using a #3 Zahn dip-type efflux viscosity cup. The results are illustrated in Table 6.

(29) TABLE-US-00006 TABLE 6 Aged viscosity Ink # Initial viscosity (16 hours @ 48 C.) 6 30 seconds 60 seconds 7 30 seconds 42 seconds
Adhesion

(30) Inks 6 and 7 were reduced to print viscosity (25 seconds @ 25 C. in a #2 Zahn dip-type efflux viscosity cup) and were printed on treated polypropylene using a flexographic handproofer. One Bump indicates one application of ink. Two Bumps indicates two applications of the same ink, one over the other. The results are illustrated in Table 7.

(31) TABLE-US-00007 TABLE 7 Ink # Oven dried (10 seconds @ 80 C.) 6 1 7 1 1 = Best; 5 = worst

(32) From the above data, the Inks of the present invention show superior, viscosity stabilizing than inks containing the adhesion promoter IA10.

(33) Lamination Bond Strength

(34) The lamination bond strength of a standard, conventional ink formulated from a commercial urethane/urea polymer was evaluated against an ink made with the reactive polymer described in Example 1. These results are shown in Table 8.

(35) TABLE-US-00008 TABLE 8 Lamination Bond Lamination Bond Strength of Strength of Ink formulated with reactive Substrate Commercial Ink polymer from Example 1 A. 48 LBT 49 538 Emblem 1500 Nylon 434 572 50 M30 317 685 SP 65 70 186

(36) From Table 8, it can be seen that the inks formulated with the reactive polymer from Example 1 have superior lamination bond strength than commercial Inks made with urea/urethane resins.

(37) The invention has been described in terms of preferred embodiments thereof, but is more broadly applicable as will be understood by those skilled in the art. The scope of the invention is only limited by the following claims.