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

Patent metadata

Field	Value
Publication number	US-10994041-B2
Application number	US-202016927437-A
Country	US
Kind code	B2
Filing date	Jul 13, 2020
Priority date	Jul 1, 2014
Publication date	May 4, 2021
Grant date	May 4, 2021

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.

First claim

What is claimed is:

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′-dimethylami

Assignees

• Ecolab Usa Inc

Inventors

• Wegner Joseph
• Brown Erin
• Atkins Jeffery
• Zinn Paul
• Walicki Robert
• Hu Lanhua

Classifications

• C09K11/025 Primary

  non-luminescent particle coatings or suspension media · CPC title

• C09K2211/1466

  containing nitrogen as the only heteroatom · CPC title

• C09B69/10

  Polymeric dyes; Reaction products of dyes with monomers or with macromolecular compounds · CPC title

• C09K2211/1433

  bridged by heteroatoms, e.g. N, P, Si or B · CPC title

• C09K11/06

  containing organic luminescent materials · CPC title