# Patent

## Title
Oxazoline compounds as open-time extenders for latex paints

## Abstract

An aqueous coating composition containing a compound of formula (I)




wherein R1 is a C2-C20 hydrocarbyl group; and R2 and R3 independently are C1-C10 alkyl or HO(CH2CH2O)xCH2—, wherein x represents an integer from 0-5.

## Background
CROSS REFERENCE TO RELATED APPLICATIONS
This application claims priority to Indian Application 951/DEL/2014, filed Apr. 1, 2014, which is incorporated herein by reference.
BACKGROUND
This invention relates to an aqueous coating composition comprising oxazoline compounds.
U.S. Pub. No. 2012/0165428 discloses use of acrylic polymers containing polymerized hydrophilic monomer units as open-time extenders for latex paints. However, this reference does not disclose the compounds described in the present application or their use in latex paints as open-time extenders.
SUMMARY OF THE INVENTION
An aqueous coating composition comprising a compound of formula (I)




wherein R1 is a C2-C20 aliphatic hydrocarbyl group; and R2 and R3 independently are C1-C10 alkyl or HO(CH2CH2O)xCH2—, wherein x represents an integer from 0-5.


DETAILED DESCRIPTION
All temperatures are in ° C. and all percentages are weight percentages (wt %), unless specified otherwise. All operations are carried out at room temperature (20-25° C.) and normal atmospheric pressure (ca. 101 kPa) unless specified otherwise.
A hydrocarbyl group is a substituent group derived by removing a hydrogen atom from a hydrocarbon. Preferably a hydrocarbyl group is acyclic. Examples of aliphatic hydrocarbyl groups include alkyl, alkenyl and alkynyl groups, where the alkenyl and alkynyl groups may have more than one carbon-carbon multiple bond. Acyclic aliphatic hydrocarbyl groups may be straight or branched.
Preferably, R1 is a C5-C20 aliphatic hydrocarbyl group, preferably C7-C20, preferably C9-C19, preferably C11-C19, preferably C11-C17, preferably C13-C17, preferably C15-C17. Preferably, R1 is alkyl or alkenyl, preferably alkenyl. Preferably, R1 is a C7-C20 alkenyl group, preferably C9-C19, preferably C11-C17, preferably C13-C17, preferably C15-C17.
Preferably, when R1 is alkenyl it has one to three carbon-carbon double bonds, preferably one or two, preferably one; preferably the double bonds are in the cis configuration. Preferably, R2 and R3 independently are C1-C6 alkyl or HO(CH2CH2O)xCH2—, preferably C1-C4 alkyl or HO(CH2CH2O)xCH2—, preferably C1-C2 alkyl, or HO(CH2CH2O)xCH2—. Preferably, x is an integer from 0 to 4, preferably from 0 to 3, preferably from 0 to 2, preferably 0 or 1. Preferably R2 and R3 are both hydroxymethyl (HO(CH2CH2O)xCH2—, with x=0). Preferably R2 and R3 are both methyl or ethyl, preferably methyl. Preferably R2 is hydroxymethyl and R3 is methyl or ethyl. Preferably R2 and R3 are both HO(CH2CH2O)xCH2—, preferably with x from 0 to 4, preferably from 0 to 3, preferably from 0 to 2, preferably 0 or 1.
Especially preferred compounds of formula (I) include, e.g., the following




In the formulas shown above the indicated carbon-carbon double bond has the cis (Z) configuration.
Preferably, the 1-octanol/water partition coefficient, log Poct/wat (Moriguchi model), of the compound is from 1 to 5; preferably at least 1.5, preferably at least 2; preferably no more than 4.5, preferably no more than 4.3. The compound of formula (II) has log (Poct/wat) of 4.15, the compound of formula (III) has log (Poct/wat) of 2.4, the compound of formula (IV) has log(Poct/wat) of 3.13, the compound of formula (V) has log(Poct/wat) of 3.93 and the compound of formula (VI) has log(Poct/wat) of 4.77.
Preferably, the aqueous coating composition is a latex paint. Preferably, the latex paint comprises an acrylic binder (acrylic emulsion polymer), titanium dioxide and/or other pigments/opacifiers and other typical ingredients of a latex paint, e.g., biocide, low-VOC solvent, defoamer, wetting agent and thickener. Preferably, the aqueous coating composition comprises from 30 to 60 wt % water (preferably 36 to 52 wt %), from 15 to 40 wt % acrylic binder on a solids basis (preferably 18 to 32 wt %) and from 15 to 35 wt % opacifying minerals (e.g., titanium dioxide, calcium carbonate) (preferably 18 to 32 wt %). Preferably, the pH of the aqueous coating composition is from 7 to 10, preferably from 8 to 9.5.
Preferably, the compound of formula (I) is present in the aqueous coating composition in an amount from 0.1 to 10 wt %, based on the weight of the entire composition; preferably at least 0.3 wt %, preferably at least 0.5 wt %, preferably at least 0.7 wt %; preferably no more than 7 wt %, preferably no more than 5 wt %, preferably no more than 4 wt %, preferably no more than 3 wt %, preferably no more than 2.5 wt %, preferably no more than 2 wt %, preferably no more than 1.5 wt %. More than one compound of formula (I) may be present in the aqueous coating composition. Amounts of the compound of formula (I) apply to the total of all compounds of formula (I).
The present invention is also directed to a method for increasing the open time of an aqueous coating composition (preferably a latex paint) by adding to the composition at least one compound of formula (I) in the amounts described herein. The compounds may be added to the initial acrylic polymer dispersion or to the final formulated coating composition containing pigments and other ingredients. The compounds may be added in combination with other organic or inorganic bases, e.g., sodium hydroxide, amines, etc. The compounds may be dispersed in solvents or carriers, including, e.g., oil, water, glycols, surfactants. It is believed that many of the compounds described herein will have the additional advantage of being low-VOC additives, especially compounds which are hydroxy substituted and/or which have longer hydrocarbon substituents. Many of these compounds could further impart other properties in the paint such as Freeze-Thaw, neutralization and biocidal efficacy.
EXAMPLES
Example 1
Paint Formulation: Paint samples based on the following paint formulations are used














Paint
Paint
Paint



Sample A
Sample B
Sample C


Ingredient
(% by wt)
(% by wt)
(% by wt)


















Water
3.00
3.00
3.00


TRITON CF 10 wetting agent
0.30
0.30
0.30


BYK 024 defoamer
0.05
0.05
0.05


OROTAN 731 dispersant
1.00
1.00
1.00


KATHON LXE biocide
0.20
0.20
0.20


ROCIMA 350 biocide
0.35
0.35
0.35


Catcite 2 microns
5.00
5.00
5.00


TIONA 595 TiO2
20.00
20.00
20.00


Water
3.50
3.50
3.50


TEXANOL coalescent
2.5
2.5
2.5


ALKATERGE TM E additive
0.0
1.0
0.0


ALKATERGE TM T-IV additive
0.0
0.0
1.0


NOPCO NDW defoamer
0.20
0.20
0.20


PRIMAL HG-91 acrylic binder
40.00
40.00
40.00


ROPAQUE ULTRA E acrylic binder
8.00
8.00
8.00


TT- 935 high shear rheology modifier
0.20
0.20
0.20


RM2020 low shear rheology modifier
2.50
2.50
2.50


Water
13.2
12.2
12.2


Total
100
100
100


pH
8.9
8.9
8.9









The schematic of the structure of ALKATERGETM E is as follows,




The schematic of the structure of ALKATERGETM T-IV is as follows,




    
    
        1. Paint drawdowns of 75 μm thickness are 5 done on a glass sheet.
        2. Equispaced “X” marks are drawn on the drawdown.
        3. Paint is applied perpendicular to the drawdown, brushing the “X” mark across the initial drawdown.
        4. Perpendicular sections are repeated at 5, 6, 7, 8, 9, 10, 11 and 12 minutes after the making of the “X” marks.
        5. Open time of the paint is taken to be the time elapsed when the “X” marks become visible.
    
    


Paint Properties:
Paint properties such as the opacity and the color difference are measured for the paint samples. Drawdown of the paint samples is carried out using BYK Gardener applicator of 75 micrometer thickness. The opacity and color differences are measured using spectrophotometer of the make Gregtag Macbeth Color-Eye 2180. The color difference is calculated as,

ΔE=√{square root over ((ΔL)2+(Δa)2+(Δb)2)}

Here, ΔL, Δa and Δb are the differences between the CIE color space L, a, b values of the paint sample and the reference. Paint sample A is treated as the reference. Drawdowns of 100 micrometer thickness were carried out and the scrub resistance was measured in terms of the percentage loss after 800 scrub cycles.
Results: The table below lists the time elapsed when the X marks become visible for the different paint samples.














Paint Sample
Time (minutes)



















A (no additive)
7



B (ALKATERGE TM E)
10



C (ALKATERGE TM T-IV)
9










Opacity and the Color Difference:















Paint Sample A





(Reference)
Paint Sample B
Paint Sample C



















Opacity (%)
94.44
94.88
94.92


ΔL
0
0.38
0.52


Δa
0
0.05
0.03


Δb
0
−0.19
−0.28


ΔE
0
0.43
0.59









Scrub Resistance:














Paint Sample
% Loss after 800 cycles



















A (no additive)
3



B(ALKATERGE TM E)
2.5



C (ALKATERGE TM T-IV)
2










Conclusion: Open time of the paint samples B and C which contain at 1.0 wt % of ALKATERGETM E and ALKATERGETM T-IV, respectively, is more than that of the reference paint (sample A) by up to 45% (3 minutes). The other paint properties measured in this work showed equivalent performance.

## Claims

1. An aqueous coating composition comprising
0.1-10 wt %, based on the weight of the entire composition, of a compound of formula (I)




wherein R1 is a C2-C20 hydrocarbyl group; and R2 and R3 independently are C1-C10 alkyl or HO(CH2CH2O)xCH2, wherein x represents an integer from 0-5;
30 to 60 wt % water;
15 to 40 wt % acrylic binder on a solids basis; and
15 to 35 wt % opacifying minerals,
wherein the aqueous coating composition is a latex paint.

2. The aqueous coating composition of claim 1 in which R1 is a C7-C20 aliphatic hydrocarbyl group.

3. The aqueous coating composition of claim 1 in which R2 and R3 independently are C1-C6 alkyl or HO(CH2CH2O)xCH2, wherein x represents an integer from 0-5.

4. The aqueous coating composition of claim 1 in which x is from 0 to 3.

5. The aqueous coating composition of claim 1 in which R1 is an alkyl or alkenyl group.

6. The aqueous coating composition of claim 1 in which R1 is a C15-C17 alkyl or alkenyl group.

7. The aqueous coating composition of claim 1 in which x is 0 or 1.

8. The aqueous coating composition of claim 1 in which the composition has a pH from 7 to 10.

9. The aqueous coating composition of claim 1 in which the compound of formula (I) is present in the aqueous coating composition in an amount from 0.1 to 5 wt %, based on the weight of the entire composition.

10. The aqueous coating composition of claim 1 in which R1 is a C11-C19 aliphatic hydrocarbyl group.

11. The aqueous coating composition of claim 1 in which R1 is a C11-C17 alkyl or alkenyl group.

12. The aqueous coating composition of claim 11 in which the alkenyl group comprises one to three carbon-carbon double bonds.

13. The aqueous coating composition of claim 11 in which the alkenyl group comprises cis carbon-carbon double bonds.

14. The aqueous coating composition of claim 1 in which R2 and R3 independently are C1-C2 alkyl or HO(CH2CH2O)xCH2, wherein x represents an integer from 0-5.

15. The aqueous coating composition of claim 1 in which x is 0.

16. The aqueous coating composition of claim 1 in which the compound of formula (I) is selected from the group consisting of

17. The aqueous coating composition of claim 1 in which the composition comprises two or more compounds of formula (I).

18. The aqueous coating composition of claim 1 comprising 18-32 wt % opacifying minerals.

19. The aqueous coating composition of claim 1 wherein the opacifying minerals comprise titanium dioxide.