Thiophene Azo Dyes and Laundry Care Compositions Containing the Same

Patent metadata

Field	Value
Publication number	US-2016194499-A1
Application number	US-201514714478-A
Country	US
Kind code	A1
Filing date	May 18, 2015
Priority date	Nov 12, 2010
Publication date	Jul 7, 2016
Grant date	—

Abstract

This application relates to thiophene azo dyes for use as hueing agents, laundry care compositions comprising such thiophene azo dyes, processes for making such thiophene azo dyes, and laundry care compositions and methods of using the same. The thiophene azo dyes contain a formally charged moiety and are generally comprised of at least two components: at least one chromophore component and at least one polymeric component. Suitable chromophore components generally fluoresce blue, red, violet, or purple color when exposed to ultraviolet light, or they may absorb light to reflect these same shades. These thiophene azo dyes are advantageous in providing a hueing effect, for example, a whitening effect to fabrics, while not building up over time and causing undesirable blue discoloration to the treated fabrics. The thiophene azo dyes are also generally stable to bleaching agents used in laundry care compositions.

First claim

We claim:

1 . A thiophene azo dye which contains a formally charged group and does not comprise a meta-bis(2-hydroxy-3-trimethylammoniumpropyl) amino tolyl group, and which is represented by formula (I):

wherein:
R 1 -R 3 are each independently selected from H, electron-withdrawing groups, and electron-donating groups, provided that at least one of R 1 -R 3 is an electron-withdrawing group; and
X is an organic group having a molecular weight of 65-4,855 daltons and is represented by formula (II) or (VII):

wherein:
R 4 is a group of any of the formulae (III), (V) and (VI)

wherein:
R 8 each independently is H, C 1-8 -alkyl optionally substituted with a hydroxy, or acetyl;
R 11 and R 12 each independently are H, C 1-8 -alkyl, aryl, acetyl or hydroxyl;
R 13 is aryl, arylalkyl, C 1-18 -alkyl or siloxane;
R 14 each independently is H, C 1-4 -alkyl;
Y is sulfonate, carboxylate, phosphonate or a quaternary ammonium species selected from imidazolium, pyridinium, morpholinium and piperidinium; or a group of the formula (IV)

wherein
R 9 is C 1-8 -alkyl optionally substituted with —OH,
R 10 is C 1-18 -alkyl optionally substituted with —OH, C 2-8 -alkyl substituted with sulfonate, or C 1-8 -alkyl substituted with carboxylate,
Z is a charge balancing counterion of unit charge c; and
b is 1 if R 10 is C 1-18 -alkyl optionally substituted with —OH and otherwise is 0;
m is an integer of 0-10;
n is an integer of 0-10;

R 5 is the same as R 4 or is C 1-12 -alkyl, aryl or arylalkyl;
R 6 each independently is C 1-6 -alkyl, C 1-4 -alkoxy, nitro, hydroxyl, halogen, or —NHC(O)R 22 [wherein R 22 is H, —NH 2 , C1-6-alkyl, phenyl, —(CH 2 ) s OR 23 (wherein s is 1 or 2 and R 23 is selected from methyl, phenyl, and —CO 2 CH 2 CN)], —NHSO 2 R 24 [wherein R 24 is C 1-4 -alkyl or phenyl];
said alkyl, alkoxy and acetamido groups may be optionally substituted with a formally charged group; and

a is an integer of 0-4;

wherein
R 4 and R 5 each independently are
(a) alkyl, aryl, arylalkyl,
(b) [(CH 2 CR′HO) x (CH 2 CR″HO) y R 15 ] or [CH 2 CH(OR 16 )CH 2 OR 17 ], wherein x+y≦20; y≧1; and z=0-10; and
R′ is selected from H, methyl, CH 2 O(CH 2 CH 2 O) z R 15 , and mixtures thereof;
R″ is selected from H, CH 2 O(CH 2 CH 2 O) z R 15 , and mixtures thereof;
R 15 each independently is H or —CH 2 CH(R 18 )—N + R 19 R 20 R 21 , wherein
R 18 is H or methyl;
R 19 and R 20 each independently are C 1-4 -alkyl optionally substituted with —OH; and
R 21 is C 1-12 -alkyl optionally substituted by —OH, or (CH 2 ) r O p Q [wherein r is an integer of 1-8; p is 0 or 1; and Q is —CO 2 − or —SO 3 − ];

R 16 is selected from H, (CH 2 CH 2 O) z R 15 , and mixtures thereof; and
R 17 is selected from C 1-16 -alkyl, C 6-10 -aryl, and mixtures thereof; or

(c) the amino addition product of styrene oxide, glycidyl methyl ether, isobutyl glycidyl ether, isopropylglycidyl ether, t-butyl glycidyl ether, 2-ethylhexylgycidyl ether, and glycidylhexadecyl ether, followed by the addition of 1-10 alkylene oxide units, wherein at least one such alkyleneoxide unit is substituted with a group R 15 that is not H;

R 6 each is as defined above;
Z is a charge balancing counterion of unit charge c; and
b is the number of groups R 15 not being H and not comprising a covalently bound charge balancing counterion;
with the proviso that the molecule contains at least one R 15 not being H.

2 . The thiophene azo dye of claim 1 , which has a maximum extinction coefficient of 1,000-1,000,000 l/mol/cm, in the wavelength range of 400-750 nm in methanol solution.

3 . The thiophene azo dye of claim 2 , which has, in the wavelength range of 560-610 nm, a maximum extinction coefficient of 20,000-250,000 l/mol/cm.

4 . The thiophene azo dye of claim 1 , which has a molecular weight of >300 daltons.

5 . The thiophene azo dye of claim 1 , which has an aqueous partition value of 10-100% and comprises a non-covalently bound charge balancing counterion.

6 . The thiophene azo dye of claim 1 , which has an aqueous partition value of 0-40% and comprises a covalently bound charge balancing counterion.

7 . The thiophene azo dye of claim 1 , wherein R 1 -R 3 each independently are H, C 1-4 -alkyl, C 3-10 -aryl, carboxylate, cyano, sulfonate, phosphonate, sulfate, acetate, nitro, C 1-4 -alkyl ester, halogen or amino.

8 . The thiophene azo dye of claim 1 , wherein X is a group of formula (II)

wherein:
R 4 is a group of any of the formulae (Ill), (V) and (VI)

wherein:
R 8 is H, C 1-4 -alkyl, or acetyl;
R 11 and R 12 each independently are H, C 1-4 -alkyl, or aryl;
R 13 is aryl, benzyl, or C 1-18 -alkyl;
R 14 each independently is H, C 1-4 -alkyl;
Y is imidazolium or a group of the formula (IV)

wherein
R 9 is C 1-2 -alkyl,
R 10 is C 1-8 -alkyl optionally substituted with —OH, C 2-4 -alkyl substituted with sulfonate, or C 1-4 -alkyl substituted with carboxylate,
Z is a charge balancing counterion of unit charge c; and
b is 1 if R 10 is C 1-8 -alkyl optionally substituted with —OH and otherwise is 0;

m is an integer of 0-10 in formula (III)
is an integer of 0-5 in formula (V)
is an integer of 0-10 in formula (VI)

n is an integer of 0-5;

R 5 is the same as R 4 or is C 1-6 -alkyl or benzyl;
R 6 each independently is methyl, methoxy or acetamido; and
a is an integer of 0-2.

9 . The thiophene azo dye of claim 8 , wherein R 1 -R 3 each independently are H, C 1-4 -alkyl, C 3-10 -aryl, carboxylate, cyano, sulfonate, phosphonate, sulfate, acetate, nitro, C 1-4 -alkyl ester, halogen or amino.

Assignees

• Milliken & Co

Inventors

• Torres Eduardo
• Hong Xiaoyong M
• Mahaffey Robert L
• Valenti Dominick J
• Miracle Gregory S

Classifications

• C09B44/04

  from coupling components containing amino as the only directing group · CPC title

• C09B44/08

  from coupling components containing heterocyclic rings · CPC title

• C09B69/106 Primary

  containing an azo dye · CPC title

• C11D3/42

  Brightening agents {; Blueing agents} · CPC title

• C09B29/3682 Primary

  containing only sulfur as heteroatom · CPC title