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

• US 9,624,423 B2
• Filed: 07/01/2014
• Issued: 04/18/2017
• Est. Priority Date: 07/01/2014
• Status: Active Grant

• Current Assignee: Ecolab USA Incorporated (Ecolab, Inc.)
• Original Assignee: Ecolab USA Incorporated (Ecolab, Inc.)
• Inventors: Wegner, Joseph, Brown, Erin, Atkins, Jeffery, Zinn, Paul, Walicki, Robert, Hu, Lanhua
• Primary Examiner(s): Porta, David
• Assistant Examiner(s): BOOSALIS, FANI POLYZOS
• Application Number:
  US14/320,881
• Publication Number:
  US 20160002525A1
• Time in Patent Office: 1,022 Days
• CPC Class Codes: A61L 2/18 Liquid substances or solutions comprising solids or dissolved gases
• CPC Class Codes: A61L 2/28 Devices for testing the effectiveness or completeness of sterilisation, e.g. indicators which change colour apparatus involving enzymes or microorganisms C12M1/34; methods involving enzymes or microorganisms C12Q1/00
• CPC Class Codes: C08F 220/06 Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
• CPC Class Codes: C09B 69/10 Polymeric dyes; Reaction products of dyes with monomers or with macromolecular compounds addition products of alkylene oxide to dyes, C09B69/00; dyeing with polymeric dyes D06P1/0056
• CPC Class Codes: C09K 11/025 non-luminescent particle coatings or suspension media
• CPC Class Codes: C09K 11/06 containing organic luminescent materials
• CPC Class Codes: C09K 2211/1416 Condensed systems
• CPC Class Codes: C09K 2211/1433 bridged by heteroatoms, e.g. N, P, Si or B
• CPC Class Codes: C09K 2211/1466 containing nitrogen as the only heteroatom
• CPC Class Codes: G01N 31/226 for investigating the degree of sterilisation

Abstract

The present invention generally relates to fluorescent marking compositions and their use to determine whether a surface has been cleaned. More particularly, the marking compositions comprise fluorescent polymers.

Claims

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;

a solvent; and

a thickener;

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 monomer unit has structure (I), (II) or (III):

3. The composition of claim 2, wherein the monomer unit has the structure (I) and is 4-methoxy-N-(3-N′

,N′

-dimethylaminopropyl)naphthalimide vinyl benzyl chloride quaternary salt, or 4-methoxy-N-(3-N′

,N′

-dimethylaminopropyl)naphthalimide 2-hydroxy-3-allyloxypropyl chloride quaternary salt;

4-methoxy-N-(3-N′

,N′

-dimethylaminopropyl)naphthalimide allyl chloride quaternary salt;

the monomer unit has the structure (II) and is N-allyl-4-(2-N′

,N′

-dimethylaminoethoxy)naphthalimide methyl sulfate quaternary salt;

or the 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_aQ_jW_t, G_aQ_vW_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_aQ_jW_t or G_aQ_vW_fS_c and wherein Q is acrylic acid;

the polymer has the formula G_aQ_jW_t and wherein Q is acrylic acid and W is acrylamide;

the polymer has the formula G_aQ_jW_t and wherein Q is acrylic acid and W is 2-acrylamido-2-methylpropane sulfonic acid;

or the polymer has the formula the G_aQ_vW_fS_c and wherein Q is acrylic acid, W is acrylamide, and S is N-sulfomethylacrylamide.

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

7. The composition of claim 6, wherein the 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 monomer unit (G) has structure (VI) or (VII):

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

10. The composition of claim 9, wherein the monomer unit having structure (VIII) is 8-(allyloxy)-1,3,6-pyrene trisulfonic acid or a sodium, potassium, cesium, rubidium, lithium or ammonium salt thereof;

or the monomer unit having structure (IX) 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_xB_y, G_xB_jC_k, G_xB_mD_q, G_xB_rC_sD_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_xB_y wherein B is acrylic acid or a salt thereof;

the polymer has the formula G_xB_jC_k wherein B is acrylic acid or a salt thereof, and C is acrylamide;

the polymer has the formula G_xB_mD_q wherein B is acrylic acid or a salt thereof, and D is sulfomethylacrylamide;

or the polymer has the formula G_xB_rC_sD_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 solvent comprises 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 thickener comprises 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. % solvent; and

from about 0.05 to about 1 wt. % of the 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. % solvent, from about 0.1 to about 0.4 wt. % of the thickener, and from about 0.5 to about 10 wt. % of the 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 the amphoteric surfactant;

from about 0.1 to about 0.4 wt. % of the thickener;

from about 0.1 to about 0.7 wt. % of the preservative;

from about 67 to about 91 wt. % of the solvent; and

an optional pH adjusting agent.

23. A method of determining whether a location has been cleaned, the method comprising applying the composition of claim 1 to a location on an environmental surface;

and determining if any of the fluorescent polymer remains on the location after one or more opportunities to clean the environmental surface.

24. A kit for determining whether a surface has been cleaned, the kit comprising:

the composition of claim 1; and

a dispenser for dispensing the composition or an applicator for applying the composition to a surface.

25. A fluorescent marking composition comprising a water-dispersible fluorescent polymer derived from polymerization of acrylic acid, 2-acrylamido-2-methylpropane sulfonic acid, and 4-methoxy-N-(3-N′

,N′

-dimethylaminopropyl)-naphthalimide 2-hydroxy-3-allyloxypropyl quaternary salt.

26. A method of determining whether a location has been cleaned, the method comprising:

applying a fluorescent marking composition comprising a solvent and a water-dispersible fluorescent polymer to a location on an environmental surface; and

determining if any of the fluorescent polymer remains on the location after one or more opportunities to clean the environmental surface, wherein the water-dispersible fluorescent polymer is derived from polymerization of one or more polymerizable fluorescent monomer units and one or more polymerizable non-fluorescent monomer units.