Use of fluorescent polymers in marking compositions for the diagnostic determination of cleaning performance

1. A fluorescent marking composition comprising:

a water-dispersible fluorescent polymer derived from polymerization of one or more polymerizable fluorescent monomer units and one or more polymerizable non-fluorescent monomer units;

the fluorescent monomer unit selected from the group of:

(1) derivatives of a substituted or non-substituted naphthalic anhydride;

(2) derivatives of a benzoxanthene dicarboxylic anhydride or a sulfonated benzoxanthene dicarboxylic anhydride;

(3) quinine;

(4) quinidine;

(5) pyranine derivatives; and

(6) mixtures and derivatives thereof;

wherein the polymer

has a weight average molecular weight of 2 to 2000 kDa, and

has a light absorption spectrum in the range of about 310 to about 400 nm and a light emission spectrum in the range of about 400 to about 750 nm.

2. The composition of claim 1 wherein the fluorescent monomer unit has structure (I), (II) or (III):

wherein:

n is an integer from 1 to 10;

A is alkyl, alkoxyalkyl, alkylamidoalkyl, aryl, or is absent; with the proviso that when A is absent, B is nitrogen and B is bonded directly to the imide nitrogen;

B is sulfur or nitrogen with the proviso that when B is sulfur, only one of R 10 or R 11 is present;

D is oxygen, nitrogen, sulfur or is absent, with the proviso that when D is absent, (CH 2 ) n is bonded directly to a carbon on the ring;

R 3 and R 4 are each independently sulfonic acid or a salt thereof, carboxylic acid or a salt thereof, allyloxy or vinylbenzyloxy, with the proviso that when one of R 3 or R 4 is sulfonic acid or a salt thereof or carboxylic acid or a salt thereof, the other must be allyloxy or vinylbenzyloxy;

R 5 is alkyl, alkylamino, hydroxyalkyl or allyl;

R 6 and R 7 are each independently alkyl;

R 8 is allyl, alkyl, vinylbenzyl or 2-hydroxy-3-allyloxypropyl;

R 9 is hydrogen, alkyl, alkoxy, halogen, sulfonic acid or a salt thereof, phosphonic acid or a salt thereof, dialkylamino, allyloxy or vinylbenzyloxy;

R 10 and R 11 are each independently alkyl;

R 12 is allyl, 2-hydroxy-3-allyloxypropyl, vinylbenzyl, 3-methacrylamidopropyl, 3-acrylamidopropyl, 2-acryloxyethyl or 2-methacryloxyethyl; and

X − is an anion.

3. The composition of claim 2 , wherein

the fluorescent monomer unit has the structure (I) and is 4-methoxy-N-(3-N′,N′-dimethylaminopropyl)naphthalimide vinyl benzyl chloride quaternary salt, 4-methoxy-N-(3-N′,N′-dimethylaminopropyl)naphthalimide 2-hydroxy-3-allyloxypropyl chloride quaternary salt, or 4-methoxy-N-(3-N′,N′-dimethylaminopropyl)naphthalimide allyl chloride quaternary salt;

the fluorescent monomer unit has the structure (II) and is N-allyl-4-(2-N′,N′-dimethylaminoethoxy)naphthalimide methyl sulfate quaternary salt; or

the fluorescent monomer unit has the structure (III) and is 5-allyloxy-4′-carboxy-1,8-naphthoylene-1′,2′-benzimidazole or 6-vinylbenzyloxy-4′-carboxy-1,8-naphthoylene-1′,2′-benzimidazole.

4. The composition of claim 2 , wherein the polymer is a random polymer of a fluorescent monomer unit and polymerizable monomer units (Q), (W), and optionally (S), wherein the polymer has a formula G a Q j W t , G a Q v W f S c , or a combination thereof wherein:

G is the fluorescent monomer unit;

Q is acrylic acid or a salt thereof, methacrylic acid or a salt thereof, maleic acid or a salt thereof, crotonic acid or a salt thereof, maleic anhydride, acrylamide, or acrylamidomethylpropane sulfonic acid or a salt thereof;

S is N-sulfomethacrylamide or N-sulfoethylacrylamide;

W is acrylic acid or a salt thereof, methacrylic acid or a salt thereof, itaconic acid or a salt thereof, maleic acid or a salt thereof, maleic anhydride, crotonic acid or a salt thereof, acrylamide, methacrylamide, vinyl sulfonic acid, styrene sulfonate, N-tert-butylacrylamide, N-isopropylacrylamide, N-butoxymethylacrylamide, N,N-dimethylacrylamide, N,N-diethylacrylamide, dimethylaminoethyl acrylate methyl chloride quaternary salt, dimethylaminoethyl acrylate benzyl chloride quaternary salt, dimethylaminoethyl acrylate methyl sulfate quaternary salt, dimethylaminoethyl methacrylate methyl sulfate quaternary salt, dimethylaminoethyl acrylamide methyl sulfate quaternary salt, dimethylaminopropyl acrylamide methyl sulfate quaternary salt, dimethylaminopropyl methacrylamide methyl sulfate quaternary salt, diallyldimethylammonium chloride, N-vinylformamide, a dimethylaminoethyl methacrylate acid salt, dimethylaminoethyl methacrylate methyl chloride quaternary salt, dimethylaminoethyl methacrylate benzyl chloride quaternary salt, methacrylamidopropyl trimethylammonium chloride, acrylamidopropyl trimethylammonium chloride, N,N′-methylene bisacrylamide, triallylamine, an acid salt of triallylamine, ethylene glycol dimethacrylate, 2-(hydroxymethyl)acrylic acid, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, glycidyl methacrylate, 2-acrylamido2-methylpropane sulfonic acid or a salt thereof, vinyl alcohol, vinyl acetate, or N-vinylpyrrolidone, with the proviso that Q and W cannot both be the same;

a is from about 0.001 to about 10 mole percent;

c is from about 1 to about 40 mole percent;

f is from about 1 to about 97.999 mole percent;

j is from 0 to about 99.999 mole percent;

t is from 0 to about 99.999 mole percent;

v is from 0 to about 97.999 mole percent;

the sum of a, j and t equals 100 mole percent; and

the sum of a, v, f and c equals 100 mole percent.

5. The composition of claim 4 , wherein the polymer has the formula G a Q j W t or G a Q v W f S c and wherein Q is acrylic acid; the polymer has the formula G a Q j W t and wherein Q is acrylic acid and W is acrylamide; the polymer has the formula G a Q j W t and wherein Q is acrylic acid and W is 2-acrylamido-2-methylpropane sulfonic acid; or the polymer has the formula the G a Q v W f S c and wherein Q is acrylic acid, W is acrylamide, and S is N-sulfomethylacrylamide.

6. The composition of claim 1 , wherein the fluorescent monomer unit has structure (IV) or (V):

wherein:

A is alkyl, alkoxyalkyl, alkylamidoalkyl, aryl, or is absent; with the proviso that when A is absent, E is nitrogen and E is bonded directly to the imide nitrogen;

E is sulfur or nitrogen with the proviso that when E is sulfur, only one of R 1 or R 2 is present;

D is alkyl, alkoxyalkyl, alkoxy, alkylamidoalkyl, alkylamino, NH, aryl or is absent;

R is independently hydrogen or alkyl;

R 1 and R 2 are each independently alkyl;

R 3 is allyl, 2-hydroxy-3-allyoxypropyl, vinyl benzyl, 3-methacrylamidopropyl, 3-acrylamidopropyl, 2-acryloxyethyl or 2-methacryloxyethyl;

R 4 is allyl, acryl, methacryl, 2-hydroxy-3-allyloxypropyl, vinyl benzyl, 2-acryloxyethyl and 2-methacryloxyethyl;

each R 5 is independently hydrogen, halogen, —NO 2 , —C(O)OH or a salt thereof, —PO(OH) 2 or a salt thereof, —SO 2 (OH) or a salt thereof, or —SO 2 (NR 2 );

X − is an anion; and

Z is —CH 2 —, —C(O)—, —CR 2 —, —NR—, —NR 2 + —, —N(OH)—, —O—, —S—, —S(O)—, or —SO 2 -.

7. The composition of claim 6 , wherein

the fluorescent monomer unit has the structure (IV) and is sulfonated-N-(3-N′,N′-dimethylaminopropyl)benzo (k,l) xanthene-3,4-dicarboxylic imide 2-hydroxy-3-allyloxypropyl quaternary salt, sulfonated-N-(3-N′,N′-dimethylaminopropyl)benzo (k,l) xanthene-3,4-dicarboxylic imide vinyl benzyl chloride quaternary salt, or sulfonated-N-(3-N′,N′-dimethylaminopropyl)benzo (k,l) xanthene-3,4-dicarboxylic imide allyl chloride quaternary salt; or

the fluorescent monomer unit has structure (V) and is N-(3-N′,N′-dimethylaminopropyl)benzo (k,l) xanthene-3,4-dicarboxylic imide allyl chloride quaternary salt.

8. The composition of claim 1 , wherein the fluorescent monomer has structure (VI) or (VII):

9. The composition of claim 1 , wherein the fluorescent monomer unit has structure (VIII) or (IX):

wherein:

M is hydrogen, sodium, potassium, cesium, rubidium, lithium or ammonium; and

n is an integer 1, 2, 3, 4, 6, or 9.

10. The composition of claim 9 , wherein

the fluorescent monomer unit has structure (VIII) and is 8-(allyloxy)-1,3,6-pyrene trisulfonic acid or a sodium, potassium, cesium, rubidium, lithium or ammonium salt thereof; or

the fluorescent monomer unit has structure (IX) and is 8-(3-vinylbenzyloxy)-1,3,6-pyrene trisulfonic acid, 8-(4-vinylbenzyloxy)-1,3,6-pyrene trisulfonic acid, or a sodium, potassium, cesium, rubidium, lithium or ammonium salt thereof.

11. The composition of claim 9 , wherein the polymer is a random polymer of a fluorescent monomer unit and polymerizable monomer units (B), (C), and (D), wherein the polymer has a formula G x B y , G x B j C k , G x B m D q , G x B r C s D t , or a combination thereof wherein:

B is an acrylic acid or a salt thereof, methacrylic acid or a salt thereof, maleic acid or a salt thereof, maleic anhydride, acrylamide, crotonic acid or a salt thereof, or a combination thereof,

C is methacrylic acid or a salt thereof, maleic acid or a salt thereof, maleic anhydride, crotonic acid or a salt thereof, itaconic acid or a salt thereof, acrylamide, methacrylamide, 2-acrylamido-2-methylpropanesulfonic acid or a salt thereof, polyethylene glycol monomethacrylate, vinyl phosphonic acid or a salt thereof, styrene sulfonic acid or a salt thereof, vinyl sulfonic acid or a salt thereof, 3-allyloxy-2-hydroxypropane sulfonic acid or a salt thereof, N-alkyl (meth)acrylamide, t-butyl (meth)acrylate, N-alkyl (meth)acrylate, N-alkanol-N-alkyl(meth)acrylate, vinyl acetate, 2-hydroxy N-alkyl(meth)acrylate, alkyl vinyl ether, alkoxyethyl acrylate, N-alkanol (meth)acrylamide, N,N-dialkyl(meth)acrylamide, 1-vinyl-2-pyrrolidinone, or a combination thereof,

D is sulfomethylacrylamide or sulfoethylacrylamide;

G is the fluorescent monomer unit;

j is from about 1 to about 98 mol %;

k is from about 1.999 to about 98 mol %;

m is from about 1 to about 95 mol %;

q is from about 4.999 to about 40 mol %;

r is from about 1 to about 89.999 mol %;

s is from about 1 to about 89.999 mol %;

t is from about 5 to about 40 mol %;

x is from about 0.001 to about 1 mol %;

y is from about 99.000 to about 99.999 mol %;

the sum of x and y equals 100 mol %;

the sum of x, j and k equals 100 mol %;

the sum of x, m and q equals 100 mol %; and

the sum of x, r, s and t equals 100 mol %.

12. The composition of claim 11 , wherein the polymer has the formula G x B y wherein B is acrylic acid or a salt thereof; the polymer has the formula G x B j C k wherein B is acrylic acid or a salt thereof, and C is acrylamide; the polymer has the formula G x B m D q wherein B is acrylic acid or a salt thereof, and D is sulfomethylacrylamide; or the polymer has the formula G x B r C s D t wherein B is acrylic acid or a salt thereof, C is acrylamide, and D is sulfomethylacrylamide.

13. The composition of claim 1 , wherein the composition does not further comprise a fluorescent dye encapsulated by, coated with, or entrapped within a non-fluorescent polymer; or a fluorescent dye covalently linked to a non-fluorescent polymer in an amount sufficient to leave a mark on a surface to which the composition is applied after removal of the composition from the surface.

14. The composition of claim 1 , wherein the composition does not further comprise a fluorescent dye encapsulated by, coated with, or entrapped within a non-fluorescent polymer; or a fluorescent dye covalently linked to a non-fluorescent polymer.

15. The composition of claim 1 , wherein the composition further comprises a solvent selected from the group of water, an alcohol, an alkylene glycol alkyl ether, a dialkylene glycol alkyl ether, or a combination thereof.

16. The composition of claim 1 , wherein the composition further comprises a thickener selected from the group of xanthan gum, guar gum, modified guar, a polysaccharide, an alginate, a modified starch, hydroxypropyl cellulose, hydroxypropyl methyl cellulose, carboxymethyl cellulose, hydroxyethyl cellulose, hydrophobically modified hydroxyethyl cellulose, hydrophobically modified hydroxypropyl cellulose, a polyacrylate, a vinyl acetate/alcohol copolymer, casein, a urethane copolymer, dimethicone PEG-8 polyacrylate, poly (DL-lactic-co-glycolic acid), a polyethylene glycol, a polypropylene glycol, pectin, or a combination thereof.

17. The composition of claim 1 , wherein the composition further comprises a surfactant, and the surfactant comprises a nonionic surfactant, an anionic surfactant, a cationic surfactant, an amphoteric surfactant, or a combination thereof.

18. The composition of claim 17 , wherein the amphoteric surfactant comprises an alkyl amine oxide, an N-alkylamino propionic acid, an N-alkyl-β-imino dipropionic acid, an imidazoline carboxylate, an alkyl betaine, an alkyl amido amine, an alkyl amido betaine, an alkyl sultaine, an alkyl amphodiacetate, an alkyl amphoacetate, an alkyl sulfobetaine, a polymeric sulfobetaine, an amphohydroxypropylsulfonate, a phosphatidylcholine, a phosphatidylethanolamine, a phosphatidylserine, a sphingomyelin, an alkyl amidopropyl phosphatidyl PG-dimonium chloride, or a combination thereof, or the nonionic surfactant comprises a linear alkyl alkoxylate, a polyalkylene oxide an alkylphenol alkoxylate, a branched alcohol alkoxylate, a secondary alcohol alkoxylate, a castor oil alkoxylate, an alkylamine alkoxylate, a fatty acid alkoxylate, a sorbitol oleate alkoxylate, a fatty alkanolamide, an alkyldialkanolamide, a polyalkylene glycol alkylamide, or a combination thereof.

19. The composition of claim 1 , wherein the composition further comprises a preservative, a pH adjusting agent, or a combination thereof.

20. The composition of claim 1 , wherein the composition is a ready-to-use formulation comprising from about 1 to about 30 wt. % of the fluorescent polymer; from about 60 to about 99 wt. % of a solvent; and from about 0.05 to about 1 wt. % of a thickener.

21. The composition of claim 1 , wherein the composition is a ready-to-use formulation comprising from about 4 to about 25 wt. % of the fluorescent polymer; from about 50 to about 95 wt. % of a solvent, from about 0.1 to about 0.4 wt. % of a thickener, and from about 0.5 to about 10 wt. % of a surfactant.

22. The composition of claim 1 , wherein the composition comprises about 8 to about 16 wt. % of the fluorescent polymer; from about 1 to about 6 wt. % of an amphoteric surfactant; from about 0.1 to about 0.4 wt. % of a thickener; from about 0.1 to about 0.7 wt. % of a preservative; from about 67 to about 91 wt. % of a solvent; and an optional pH adjusting agent.