US4255273A
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US
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Fabric bleaching and stain removal compositions
Assignee: Procter and Gamble Co
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Filing: 1979-01-10
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Granted: 1981-03-10
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Expires: 1999-01-10
Abstract
Abstract Improved fabric bleaching and stain removal are achieved by use of a composition comprising a photoactivator and a cationic substance. The photoactivator is a porphine or a mono-, di-, tri-, or tetra-aza porphine, solubilized with anionic, nonionic and/or cationic substitutent groups, and metal free or metallated with Zn(II), Ca(II), Cd(II), Mg(II), Sc(III), Al(III) or Sn(IV). The cationic substance is preferably one that, in a laundry bath, itself performs a desired function such as acting as fabric softener, electrostatic control agent, surfactant, or germicide.
Inventors
- 👤 Nabil Y. Sakkab
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-10-28 20:34
CPC Classifications
C; C09; C09B; C09B47/00; C09B47/04; C09B47/045; C11; C11D; C11D3/00; C11D3/0005; C11D3/0063
Claims Analysis
Total Claims: 47
Claim 1
Independent Claim
202 words
A bleach composition consisting essentially of: (a) from about 0.5% to about 50% by weight of the composition of a cationic substance; (b) from 0.001% to 0.5% by weight of the composition of a water soluble photoactivator having the formula ##STR86## wherein each X is (═N--) or (═CY--), and the total number of (═N--) groups is 0, 1, 2, 3 or 4; wherein each Y, independently, is hydrogen or meso substituted alkyl, cycloalkyl, aralkyl, aryl, alkaryl or heteroaryl; wherein each R, independently, is hydrogen or pyrrole substituted alkyl, cycloalkyl, aralkyl, aryl, alkaryl or heteroraryl, or wherein adjacent pairs of R's are joined together with ortho-arylene groups to form pyrrole substituted alicyclic or heterocyclic rings; wherein A is 2(H) atoms bonded to diagonally opposite nitrogen atoms, or Zn(II), Cd(II), Mg(II), Sc(III), or Sn(IV); wherein B is an anionic, nonionic or cationic solubilizing group substituted into Y or R; wherein M is a counterion to the solubilizing groups; and wherein s is the number of solubilizing groups; and (c) balance selected from the group consisting of water, alcohols, glycols and glycol ethers, hydrotropes, clay, substrate, nonionic surfactants used in ratio to cationic substance between about 5:3 and about 200:1, insoluble aluminosilicate builder, and alkanolamine.
Claim 2
Dependent Claim
202 words
A bleach composition consisting essentially of: (a) from about 0.5% to about 50% by weight of the composition of a cationic substance; (b) from 0.001% to 0.5% by weight of the composition of a water soluble photoactivator having the formula ##STR86## wherein each X is (═N--) or (═CY--), and the total number of (═N--) groups is 0, 1, 2, 3 or 4; wherein each Y, independently, is hydrogen or meso substituted alkyl, cycloalkyl, aralkyl, aryl, alkaryl or heteroaryl; wherein each R, independently, is hydrogen or pyrrole substituted alkyl, cycloalkyl, aralkyl, aryl, alkaryl or heteroraryl, or wherein adjacent pairs of R's are joined together with ortho-arylene groups to form pyrrole substituted alicyclic or heterocyclic rings; wherein A is 2(H) atoms bonded to diagonally opposite nitrogen atoms, or Zn(II), Cd(II), Mg(II), Sc(III), or Sn(IV); wherein B is an anionic, nonionic or cationic solubilizing group substituted into Y or R; wherein M is a counterion to the solubilizing groups; and wherein s is the number of solubilizing groups; and (c) balance selected from the group consisting of water, alcohols, glycols and glycol ethers, hydrotropes, clay, substrate, nonionic surfactants used in ratio to cationic substance between about 5:3 and about 200:1, insoluble aluminosilicate builder, and alkanolamine.
Claim 3
Dependent Claim
203 words
A bleach composition consisting essentially of: (a) from about 0.5% to about 50% by weight of the composition of a cationic substance; (b) from 0.001% to 0.5% by weight of the composition of a water soluble photoactivator having the formula ##STR87## wherein each X is (═N--) or (═CY--), and the total number of (═N--) groups is 0, 1, 2, 3; wherein each Y, independently, is hydrogen or meso substituted alkyl, cycloalkyl, aralkyl, aryl, alkaryl or heteroaryl; wherein each R, independently, is hydrogen or pyrrole substituted alkyl, cycloalkyl, aralkyl, aryl, alkaryl or heteroraryl, or wherein adjacent pairs of R's are joined together with ortho-arylene groups to form pyrrole substituted alicyclic or heterocyclic rings; wherein A is 2(H) atoms bonded to diagonally opposite nitrogen atoms, or Zn(II), Ca(II), Cd(II), Mg(II) , Sc(III), Al(III ) or Sn(IV); wherein B is an anionic, nonionic or cationic solubilizing group substituted into Y or R; wherein M is a counterion to the solubilizing groups; and wherein s is the number of solubilizing groups (c) balance selected from the group consisting of water, alcohols, glycols and glycol ethers, hydrotropes, clay, substrate, nonionic surfactants used in ratio to cationic substance between about 5:3 and about 200:1, insoluble aluminosilicate builder, and alkanolamine.
Claim 4
Dependent Claim
203 words
A bleach composition consisting essentially of: (a) from about 0.5% to about 50% by weight of the composition of a cationic substance; (b) from 0.001% to 0.5% by weight of the composition of a water soluble photoactivator having the formula ##STR87## wherein each X is (═N--) or (═CY--), and the total number of (═N--) groups is 0, 1, 2, 3; wherein each Y, independently, is hydrogen or meso substituted alkyl, cycloalkyl, aralkyl, aryl, alkaryl or heteroaryl; wherein each R, independently, is hydrogen or pyrrole substituted alkyl, cycloalkyl, aralkyl, aryl, alkaryl or heteroraryl, or wherein adjacent pairs of R's are joined together with ortho-arylene groups to form pyrrole substituted alicyclic or heterocyclic rings; wherein A is 2(H) atoms bonded to diagonally opposite nitrogen atoms, or Zn(II), Ca(II), Cd(II), Mg(II) , Sc(III), Al(III ) or Sn(IV); wherein B is an anionic, nonionic or cationic solubilizing group substituted into Y or R; wherein M is a counterion to the solubilizing groups; and wherein s is the number of solubilizing groups (c) balance selected from the group consisting of water, alcohols, glycols and glycol ethers, hydrotropes, clay, substrate, nonionic surfactants used in ratio to cationic substance between about 5:3 and about 200:1, insoluble aluminosilicate builder, and alkanolamine.
Claim 5
Dependent Claim
115 words
The composition of claims 1 or 2 wherein, when B is cationic, M is an anion and s is from 1 to about 8; when B is nonionic, B is polyethoxylate, M is zero, s is from 1 to about 8, and the number of condensed ethylene oxide molecules per porphine molecule is from about 8 to about 50; when B is anionic and proximate, M is cationic and s is from 3 to about 8; when B is anionic and remote, M is cationic and s is from 2 to about 8; and when B is sulfonate the number of sulfonate groups is no greater than the number of aromatic and heteracylic substitutent groups.
Claim 6
Dependent Claim
25 words
The composition of claim 3 wherein B is quaternary pyridinium, quaternary ammonium, polyethoxylate, carboxylate, polyethoxy carboxylate, sulfate, polyethoxy sulfate, phosphate, polyethoxy sulfonate, or mixtures thereof.
Claim 7
Dependent Claim
38 words
The composition of claims 1 or 2 wherein the cationic substance comprises from about 0.5% to about 50% by weight of the composition, and the ratio of cationic substances to photoactivator is from about 1/1 to about 50,000/1.
Claim 8
Dependent Claim
49 words
The composition of claim 5 wherein the photoactivator comprises from 0.005% to about 0.1% by weight of the composition, the cationic substance comprises from about 2% to about 30% by weight of the composition, and the ratio of cationic substance to photoactivator is from about 20/1 to about 5,000/1.
Claim 9
Dependent Claim
35 words
The composition of claim 1 or 2 wherein the cationic substance is ##STR88## (8) mixtures thereof, L is a number from 1 to 10, Z is an anion in a number to give electrical neutrality.
Claim 10
Dependent Claim
19 words
The composition of claim 7 wherein, in the cationic substance, L is equal to 1 and Y is ##STR89##
Claim 11
Dependent Claim
33 words
The composition of claim 8 wherein, in the cationic substance, m is equal to 1, X is equal to 3, R 1 is C 10 -C 20 alkyl, and R 2 is methyl.
Claim 12
Dependent Claim
33 words
The composition of claim 8 wherein, in the cationic substance, m is equal to 2, X is equal to 2, R 1 is C 10 -C 20 alkyl, and R 2 is methyl.
Claim 13
Dependent Claim
33 words
The composition of claim 8 wherein, in the cationic substance, m is equal to 3, X is equal to 1, R 1 is C 8 -C 11 alkyl, and R 2 is methyl.
Claim 14
Dependent Claim
299 words
The composition of claim 1 wherein the cationic substance is selected from the group consisting of (a) quaternary ammonium salts having the following structure ##STR90## where R 1 has from about 9 to about 26 carbon atoms and is a hydrophobic group which is alkyl, aryl, alkaryl, aralkyl or alkyl heterocyclic; saturated or unsaturated; the alkyl chain of which is straight or branched; unsubstituted or substituted with halogen, hydroxy, amino, ester, or ether groups; where R 2 , R 3 and R 4 each have from 1 to about 9 carbon atoms, and are the same or different, and have combined a total of from 3 to about 15 carbon atoms in groups which are alkyl, aryl, alkaryl, aralkyl or heterocyclic; saturated or unsaturated; the alkyl chains of which are straight or branched; unsubstituted or substituted with halogen, hydroxy, nitro, amino, sulfonamide, ester or ether groups; and where X is an anionic solubilizing group; (b) Quaternary salts having the structure ##STR91## where R 1 and X are the same as defined immediately hereinbefore in paragraph (a) and U is an unsaturated heterocyclic group, unsubstituted or substituted with a short chain alkyl group; (c) Quaternary salts having the structure ##STR92## where R, R 2 and X are the same as defined hereinbefore in paragraph (a); and S is a saturated heterocyclic group, unsubstituted or substituted with a short chain alkyl group; and (d) polyamido quaternized biurets ##STR93## wherein R is an aliphatic hydrocarbyl group (saturated or unsaturated), a substituted aliphatic hydrocarbyl group, or an alkoxylated aliphatic hydrocarbyl group having from about 10 to 30 carbon atoms; A is a vicinal dihydroxy alkyl group containing at least 3 carbon atoms, m is 1 to about 8, and X is an anion selected from the halogen, acetate, phosphate, nitrate and methylsulfate radicals.
Claim 15
Dependent Claim
58 words
The composition of claim 12 wherein the cationic substance has the structure ##STR94## where R 1 has from about 12 to about 20 carbon atoms and is straight chained; where R 2 and R 3 are, independently, methyl or ethyl; where R 4 is methyl, ethyl, benzyl or chlorobenzyl; and where X is an organic or inorganic anion.
Claim 16
Dependent Claim
47 words
The composition of claim 12 wherein the cationic substance has the structure ##STR95## R 1 has from about 10 to about 20 carbon atoms and is straight chained and where the heterocyclic group is pyridine, picoline, quioline, quinalidine, thioazole, pyrrole, imidazole, pyrazole, oxacole, pyrazine, pyridiazine, or pyrimidine.
Claim 17
Dependent Claim
42 words
The composition of claim 12 wherein the cationic substance has the structure ##STR96## R 1 has from about 10 to about 20 carbon atoms and is straight chained and where the heterocyclic group is piperidine, piperazine, pyrrolidine, indoline, imidazolidine, pyrazolidine, or morpholine.
Claim 18
Dependent Claim
39 words
The composition of claim 12 wherein the cationic substance has the structure ##STR97## where R has from about 12 to about 22 carbon atoms, A has from 3 to about 8 carbon atoms, and m is 2 or 3.
Claim 19
Dependent Claim
67 words
The composition of claim 7 additionally containing a nonionic surfactant comprising an alkyl polyethoxylate having the formula R(OCH 2 CH 2 ) n OH where R is a primary or secondary alkyl chain having from about 8 to about 22 carbon atoms, and the average value of n is from about 2 to about 9, said nonionic surfactant having an HLB from about 5 to about 17.
Claim 20
Dependent Claim
189 words
The composition of claim 4 wherein the cationic substance is R.sup.1.sub.m R.sup.2.sub.X Y.sub.L Z wherein each R 1 is an organic group containing a straight or branched alkyl or alkenyl group optionally substituted with up to 3 phenyl groups and optionally interrupted by up to 4 structures selected from the group consisting of ##STR98## and mixtures thereof, and which contains from about 8 to 22 carbon atoms, and which may additionally contain up to 20 ethoxy groups, m is a number from one to three, no more than one R 1 in a molecule can have more than 12 carbon atoms when m is 3, each R 2 is an alkyl or hydroxyalkyl group containing from 1 to 4 carbon atoms or a benzyl group with no more than one R 2 in a molecule being benzyl, x is a number from 0 to 3, the remainder of any carbon or nitrogen atom positions being filled by hydrogens, Y is selected from the group consisting of ##STR99## (8) mixtures thereof, L is a number of 1 to 10, Z is an anion in a number to give electrical neutrality.
Claim 21
Dependent Claim
19 words
The composition of claim 18 wherein, in the cationic substance, L is equal to 1 and Y is ##STR100##
Claim 22
Dependent Claim
299 words
The composition of claim 4 wherein the cationic substance is selected from the group consisting of (a) quaternary ammonium salts having the following structure ##STR101## where R 1 has from about 9 to about 26 carbon atoms and is a hydrophobic group which is alkyl, aryl, alkaryl, aralkyl or alkyl heterocyclic; saturated or unsaturated; the alkyl chain of which is straight or branched; unsubstituted or substituted with halogen, hydroxy, amino, ester, or ether groups; where R 2 , R 3 and R 4 each have from 1 to about 9 carbon atoms, and are the same or different, and have combined a total of from 3 to about 15 carbon atoms in groups which are alkyl, aryl, alkaryl, aralkyl or heterocyclic; saturated or unsaturated; the alkyl chains of which are straight or branched; unsubstituted or substituted with halogen, hydroxy, nitro, amino, sulfonamide, ester or ether groups; and where X is an anionic solubilizing group; (b) Quaternary salts having the structure ##STR102## where R 1 and X are the same as defined immediately hereinbefore in paragraph (a) and U is an unsaturated heterocyclic group, unsubstituted or substituted with a short chain alkyl group; (c) Quaternary salts having the structure ##STR103## where R, R 2 and X are the same as defined hereinbefore in paragraph (a); and S is a saturated heterocyclic group, unsubstituted or substituted with a short chain alkyl group; and (d) polyamido quaternized biurets ##STR104## wherein R is an aliphatic hydrocarbyl group (saturated or unsaturated), a substituted aliphatic hydrocarbyl group, or an alkoxylated aliphatic hydrocarbyl group having from about 10 to 30 carbon atoms; A is a vicinal dihydroxy alkyl group containing at least 3 carbon atoms, m is 1 to about 8, and X is an anion selected from the halogen, acetate, phosphate, nitrate and methylsulfate radicals.
Claim 23
Dependent Claim
71 words
The composition of claim 20 wherein the cationic substance has the structure ##STR105## where R 1 has from about 12 to about 20 carbon atoms and is straight chained; where R 2 and R 3 are, independently, methyl or ethyl; where R 4 is methyl, ethyl, benzyl or chlorobenzyl; and where X is halide, nitrate, sulfate, hydroxide, methyl sulfate, toluene sulfonate, and carbonate, phosphate, acetate, propionate, benzoate tartrate, citrate, and salicylate.
Claim 24
Dependent Claim
47 words
The composition of claim 20 wherein the cationic substance has the structure ##STR106## R 1 has from about 10 to about 20 carbon atoms and is straight chained and where the heterocyclic group is pyridine, picoline, quinoline, quinaldine, thiozole, pyrrole, imidazole, pyrazole, oxaxole, pyrazine pyridiazine, or pyrimidine.
Claim 25
Dependent Claim
42 words
The composition of claim 20 wherein the cationic substance has the structure ##STR107## R 1 has from about 10 to about 20 carbon atoms and is straight chained and where the heterocyclic group is pyridine, piperazine, pyrrolidine, indoline, imidazolidine, pyrazolidine, or morpholine.
Claim 26
Dependent Claim
39 words
The composition of claim 20 wherein the cationic substance has the structure ##STR108## where R has from about 12 to about 22 carbon atoms, A has from 3 to about 8 carbon atoms, and m is 2 or 3.
Claim 27
Dependent Claim
17 words
The composition according to any of claims 1 or 2 wherein B is imidazolinium or quaternary ammonium.
Claim 28
Dependent Claim
14 words
The composition according to any of claims 1 or 2 wherein B is polyethoxylate.
Claim 29
Dependent Claim
22 words
The composition according to any of claims 1 or 2 wherein B is carboxylate, polyethoxycarboxylate, sulfate, polyethoxysulfate, phosphate, sulfonate, or mixtures thereof.
Claim 30
Dependent Claim
21 words
The composition according to any of claims 1 or 2 wherein the photoactivator is zinc phthaloxyanine sulfonate, tri- or tetra-sulfonate salt.
Claim 31
Dependent Claim
18 words
The composition according to any of claims 1 or 2 wherein the composition is incorported into substrate articles.
Claim 32
Dependent Claim
35 words
A process for removing stains from textiles which comprises treating the textiles, in the presence of visible light and oxygen, with an aqueous solution of the bleach composition of any of claims 1 or 2.
Claim 33
Dependent Claim
30 words
The composition according to any of claims 1 or 2 wherein the composition is incorporated into substrate articles and wherein the photoactivator is zinc phthalocyanine sulfonate, tri- or tetra-sulfonate salt.
Claim 34
Dependent Claim
13 words
The composition according to claim 18 wherein B is imidazolinium or quaternary ammonium.
Claim 35
Dependent Claim
13 words
The composition according to claim 20 wherein B is imidazolinium or quaternary ammonium.
Claim 36
Dependent Claim
10 words
The composition according to claim 18 wherein B is polyethoxylate.
Claim 37
Dependent Claim
10 words
The composition according to claim 20 wherein B is polyethoxylate.
Claim 38
Dependent Claim
18 words
The composition according to claim 18 wherein B is carboxylate, polyethoxycarboxylate, sulfate, polyethoxysulfate, phosphate, sulfonate, or mixtures thereof.
Claim 39
Dependent Claim
18 words
The composition according to claim 20 wherein B is carboxylate, polyethoxycarboxylate, sulfate, polyethoxysulfate, phosphate, sulfonate, or mixtures thereof.
Claim 40
Dependent Claim
17 words
The composition according to claim 18 wherein the photoactivator is zinc phthalocyanine sulfonate, tri- or tetra-sulfonate salt.
Claim 41
Dependent Claim
17 words
The composition according to claim 20 wherein the photoactivator is zinc phthalocyanine sulfonate, tri- or tetra-sulfonate salt.
Claim 42
Dependent Claim
14 words
The composition according to claim 18 wherein the composition is incorporated into substrate articles.
Claim 43
Dependent Claim
14 words
The composition according to claim 20 wherein the composition is incorporated into substrate articles.
Claim 44
Dependent Claim
31 words
A process for removing stains from textiles which comprises treating the textiles, in the presence of visible light and oxygen, with an aqueous solution of the bleach composition of claim 18.
Claim 45
Dependent Claim
31 words
A process for removing stains from textiles which comprises treating the textiles, in the presence of visible light and oxygen, with an aqueous solution of the bleach composition of claim 20.
Claim 46
Dependent Claim
26 words
The composition according to claim 18 wherein the composition is incorporated into substrate articles and wherein the photoactivator is zinc phthalocyanine sulfonate, tri- or tetra-sulfonate salt.
Claim 47
Dependent Claim
26 words
The composition according to claim 20 wherein the composition is incorporated into substrate articles and wherein the photoactivator is zinc phthalocyanine sulfonate, tr- or tetra-sulfonate salt.
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USPTO Annuity & Maintenance Windows
| Annuity Stage | Window Opens | Payment Deadline | Surcharge Period Until | Estimated Fee | Status |
|---|---|---|---|---|---|
| 3.5 Years (Year 4) | 1984-03-09 | 1984-09-08 | 1985-03-10 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1988-03-09 | 1988-09-08 | 1989-03-10 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1992-03-09 | 1992-09-08 | 1993-03-10 | $7700.00 | Window Closed / Lapsed |