GB1565807A - Creation of Inventions and Patents with Artificial Intelligence

GB1565807A – Process and compositions for cleaning fabrics
– Google Patents

GB1565807A – Process and compositions for cleaning fabrics
– Google Patents
Process and compositions for cleaning fabrics

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Publication number
GB1565807A

GB1565807A
GB51859/75A
GB5185975A
GB1565807A
GB 1565807 A
GB1565807 A
GB 1565807A
GB 51859/75 A
GB51859/75 A
GB 51859/75A
GB 5185975 A
GB5185975 A
GB 5185975A
GB 1565807 A
GB1565807 A
GB 1565807A
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GB
United Kingdom
Prior art keywords
ferric ion
salt
complex
chelate complex
ion chelate
Prior art date
1975-12-18
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)

Expired

Application number
GB51859/75A
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)

UILEVER Ltd

Original Assignee
UILEVER Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
1975-12-18
Filing date
1975-12-18
Publication date
1980-04-23

1975-12-18
Application filed by UILEVER Ltd
filed
Critical
UILEVER Ltd

1975-12-18
Priority to GB51859/75A
priority
Critical
patent/GB1565807A/en

1976-12-13
Priority to IT69958/76A
priority
patent/IT1108151B/en

1976-12-13
Priority to NZ182870A
priority
patent/NZ182870A/en

1976-12-13
Priority to FI763578A
priority
patent/FI61714C/en

1976-12-14
Priority to AT923776A
priority
patent/AT362034B/en

1976-12-14
Priority to ES454217A
priority
patent/ES454217A1/en

1976-12-15
Priority to CH1578776A
priority
patent/CH624709A5/de

1976-12-15
Priority to US05/750,787
priority
patent/US4119557A/en

1976-12-16
Priority to DE19762657043
priority
patent/DE2657043A1/en

1976-12-16
Priority to BR7608454A
priority
patent/BR7608454A/en

1976-12-16
Priority to NO764273A
priority
patent/NO146244C/en

1976-12-17
Priority to PT65982A
priority
patent/PT65982B/en

1976-12-17
Priority to CA268,140A
priority
patent/CA1079007A/en

1976-12-17
Priority to ZA00767500A
priority
patent/ZA767500B/en

1976-12-17
Priority to FR7638181A
priority
patent/FR2335593A1/en

1976-12-17
Priority to NLAANVRAGE7614001,A
priority
patent/NL184483C/en

1976-12-17
Priority to BE173382A
priority
patent/BE849540A/en

1976-12-17
Priority to SE7614253A
priority
patent/SE425319B/en

1976-12-17
Priority to JP51151857A
priority
patent/JPS5276281A/en

1976-12-17
Priority to DK571876A
priority
patent/DK571876A/en

1980-04-23
Publication of GB1565807A
publication
Critical
patent/GB1565807A/en

Status
Expired
legal-status
Critical
Current

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Classifications

C—CHEMISTRY; METALLURGY

C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES

C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL

C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00

C11D3/39—Organic or inorganic per-compounds

C11D3/3902—Organic or inorganic per-compounds combined with specific additives

C11D3/3905—Bleach activators or bleach catalysts

C11D3/3932—Inorganic compounds or complexes

D—TEXTILES; PAPER

D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR

D06L—DRY-CLEANING, WASHING OR BLEACHING FIBRES, FILAMENTS, THREADS, YARNS, FABRICS, FEATHERS OR MADE-UP FIBROUS GOODS; BLEACHING LEATHER OR FURS

D06L4/00—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs

D06L4/10—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs using agents which develop oxygen

D06L4/12—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs using agents which develop oxygen combined with specific additives

Description

PATENT SPECIFICATION ( 11) 1 565 807
( 21) Application No 51859/75 ( 22) Filed 18 Dec 1975 ( 19) q ( 23) Complete Specification Filed 17 Dec 1976 -//s ( 44) Complete Specification Published 23 Apr 1980 ( 51) INT CL 3 DO 6 L 3/02 ( 52) Index at Acceptance -‘ Di P 1113 1303 FH ( 72) Inventor: DENNIS POSTLETHWAITE ( 54) PROCESS AND COMPOSITIONS FOR CLEANING FABRICS ( 71) We, UNILEVER LIMITED, a company organised under the laws of Great Britain, of Unilever House, Blackfriars, London E/C 4, England, do hereby declare the invention for which we pray that a patent may be granted to us and the method by which it is to be
performed, to be particularly described in and by the following statement:-
This invention relates to bleaching compositions and a process for cleaning fabrics 5 Fabric washing compositions comprising at least one surface-active compound of the anionic, nonionic or zwitterionic type and a percompound bleaching agent, such as sodium perborate, sodium persilicate, sodium percarbonate and sodium perphosphate, are known.
The amount of percompound bleaching agent used in such composition is normally about 5-35 % by weight of the total composition 10 It is known that many heavy metal ions catalyse the decomposition of H 202 and H 202-producing percompounds, such as sodium perborate It has also been suggested, to use heavy metal salts together with a chelating agent, for improving the bleaching activity of percompound bleaches.
Not all heavy metals nor all chelating agents on combination appeared to be suitable for 15 improving the bleaching performance of H 202-producing percompound bleaches Many combinations indeed show no effect or even a worsening effect on the bleaching performance; no proper rule seems, however, to exist by which the effect of metal ion/chelating agent combinations on the bleaching performance of percompound bleaches can be predicted 20 Many attempts have been made to select the most suitable metal/chelating agent combination for said purpose and to correlate bleach-catalysing effect with some physical constants of the combination, so far without much success U S patent no 3, 156,654 suggested particularly cobalt and copper salts in conjunction with pyridine-2-carboxylic acid or pyridine-2,6-dicarboxylic acid, preferably as a preformed complex as being a suitable 25 combination Further British patents nos 984,459 and 1,192,524 suggested the use of a copper salt in combination with other specific chelating agents, such as methylaminodiacetic acid, aminotriacetic acid, hydroxyethylaminodiacetic acid, ethylene diamine tetraacetic acid, and diethylene triamine pentaacetic acid.
Typical is that previous investigators have focussed their efforts practically towards the 30 use of non-ferrous metals such as Cobalt and Copper salts This is probably understandable from the fact, that all these metals including Cobalt and Copper-ions are known as very powerful H 202-decomposition catalysts.
It has now been found that, quite surprisingly, certain pre-formed ferric ion chelate complexes have a pronounced activating effect, which is at least equal to or even much 35 better than many of the hitherto known specific metal ion/chelating agent combinations on the bleaching performance of hydrogen peroxide and persalts, which effect, unlike that of some other metal ion/chelate systems, is reproducible and consistent.
The effect is quite surprising since not much attention has hitherto been paid to iron as a heavy metal catalyst for bleaching, possibly due to opined inferiority to other metals The 40 effect is furthermore surprising since the effect observed is specific to ferric ion in combination with specific chelating agents.
The term “persalt” is used here to mean a salt which releases hydrogen peroxide in aqueous solution, such as e g the alkali metal perborates, percarbonates, persilicates and perphosphates 45 – 1 565 807 The invention also provides a bleaching composition for fabrics comprising a persalt and a pre-formed ferric ion chelate complex, as defined hereunder.
Accordingly the invention provides a process for cleaning fabrics by contact with an aqueous solution of hydrogen peroxide or a persalt and a pre-formed ferric ion chelate complex as defined hereunder 5 The pre-formed ferric ion chelate complex used in the present invention is formed with a particular group of polycarboxyamine type chelating agents The polycarboxyamine type chelating agents used in conjunction with the ferric ion according to the invention are ethylenediaminetetraacetic acid (EDTA), nitrilotriacetic acid (NTA), diethylene triamine pentaacetic acid (DTPA) and hydroxyethyl ethylene diamine triacetic acid (HEEDTA) 10 For practical reasons a complex of ferric ion with ethylenediaminetetraacetic acid is preferred, particularly the one comprising ethylene diamine tetraacetic acid ferric mono sodium salt.
The complex of the invention can be readily prepared by the simple addition of a water-soluble ferric salt, e g ferric sulphate, to a warm to hot solution of the chelating 15 agent, from which the complex is isolated either by precipitation or crystallisation or by any other known separation technique.
The above-mentioned EDTA-ferric mono sodium salt can be prepared by the addition of a water-soluble ferric salt, e g ferric sulphate, to a hot solution of EDTA (tetra or disodium salt) The pale yellow complex crystallises out of solution and is a stable 20 non-hygroscopic solid, which on analysis appears to have the general formula lFe EDTA.n H 2 Ol- Na+ in which N = 0-2 It has a stability constant of 25 1 at 25 C.
As the persalt bleaching agent which is used in the present invention can be mentioned e.g sodium perborate tetrahydrate, the best known and most used percompound, as well as other persalts known in the art, such as sodium perborate monohydrate, sodium 25 percarbonate, sodium persilicate and sodium perphospates.
The range within which the ferric ion chelate complex in solution shows enhancement of the bleaching performance of hydrogen peroxide and persalts begins already at levels as low as 1 ppm and extends further to about 70 ppm On observation of a curve plotted for a 15 minute isothermal wash at 90 C, the main characteristics thereof are a rapid and 30 pronounced bleach activation on introduction of the complex of the invention into the system, followed by a gradual decline of the activation performance on further increase of the complex level over the concentration range studied The optimum p H for the best bleaching with the ferric ion chelate complex is between 8 5 and 10 5, preferably between 9 and 10 35 A major advantage of the present invention is that iron is used here, which unlike other heavy metals, such as copper, chromium, nickel and cobalt, is quite a harmless and non-sensitising metal, making the invention attractive for use in all sorts of applications where there is possible skin contact.
The practical value of the present invention is that at the same persalt level in the product 40 an increased bleaching action is achieved, and consequently a certain bleaching level can be achieved by using a lower proportion of the persalt in the composition at the expense of adding only very minor proportions of a complex as hereinbefore described.
According to the invention the optimum feasible concentration range for the ferric ion chelate complex in the wash-solution is of the order of 2 5-50 ppm, preferably 5-40 ppm, or 45 expressed in more desirable molar terms, from about 5-135 Rmoles/litre, preferably 10-120 ltmoles/litre.
Based on the normal dosage of use of 5 g/litre of bleaching, or bleaching and detergent compositions, said range will correspond to about 0 05 %-1 0 % by weight, preferably from about 0 1 % to about 0 8 % by weight of the total composition In admixture with a persalt 50 bleaching agent the ferric ion chelate complex will be present in an amount of about 0.25-5 %, by weight of the persalt.
Thus the bleaching, or H bleaching and detergent composition of the invention comprises from 0 % to about 50 % by weight of an organic surface-active agent selected from the group consisting of anionic, nonionic, zwitterionic, cationic detergents, and mixtures thereof; 55 from 5 % to 80 % by weight of builder salts; from 5 % to 35 % by weight of a persalt bleaching agent; and from 0 05 % to 1 0 % by weight of a pre-formed ferric ion chelate complex of ethylene diamine tetraacetic acid, nitrilotriacetic acid, diethylene triamine pentaacetic acid or hydroxyethyl ethylene diamine triacetic acid.
Preferred are detergent and bleaching compositions which contain from about 5 % to 60 about 35 % by weight of an organic surface-active agent selected from the group consisting of anionic and nonionic detergents, and mixtures thereof; from about 10 % to about 60 % by weight of water-soluble builder salts, preferably sodium tripolyphosphate; from about 10 % to about 25 % by weight of a persalt bleaching agent, preferably selected from the group consisting of alkali metal perborates, alkali metal percarbonates, and mixtures thereof; and 65 1 565 807 from about 0 1 % to about 0 8 % by weight of the pre-formed ferric ion chelate complex.
The p H of the composition of the invention (measured from a 0 5 % solution) should preferably lie within the range of about 85-10 5, more preferably between 9-10.
In addition thereto, inert salts, such as sodium sulphate, and any of the conventional adjuncts used in bleaching and detergent compositions, such as fluorescent agents, soil 5 suspending agents, e g sodium carboxymethyl cellulose; alkaline agents including enzymes may be present in the composition of the invention.
Typical anonionic detergents are the alkylbenzene sulphonates having from 8-16 carbon atoms in the alkyl group, e g sodium dodecylbenzene sulphonate; the olefin sulphonates having from 10-20 carbon atoms, obtained by reacting an alpha olefin with gaseous diluted 10 sulphur trioxide and hydrolysing the resulting product; alkyl sulphates such as tallow alcohol sulphate; and alkali metal salts of long chain fatty acids, such as stearic acid and/or palmitic acid.
Typical water-soluble nonionic detergents are the condensation products of alkyl phenols with ethylene oxide e g the reaction product of nonylphenol with 6-30 ethylene oxide units; 15 condensation products of higher fatty alcohols, such as tridecyl alcohol and secondarz C 10-C 15 alcohols with ethylene oxide, known under the trade name of “Tergitols” A supplied by Union Carbide; condensation products of tallow alcohol with ethylene oxide; condensation products of fatty amide with 8-15 ethylene oxide units and the condensation 20) products of polypropylene glycol with ethylene oxide Zwitterionic detergents include 20 derivatives of aliphatic quaternary ammonium, phosphonium and sulphonium compounds in which the aliphatic moieties can be straight chain or branched, and wherein one of the aliphatic substituents contains from 8 to 18 carbon atoms and one contains an anionic water-solubilizing group.
Cationic detergents include the quaternary ammonium compounds, e g cetyl trimethyl 25 ammonium bromide or chloride; and the fatty alkyl amines.
It is an important feature of the present invention that the ferric ion chelate complex is preformed before it is incorporated in the bleaching, or bleaching and detergent composition, or before addition to the bleaching bath, since only then there will be a maximum benefit achievable 30 The compositions of the invention may be presented in any of the known solid forms of bleaching or bleaching and detergent compositions, e g as a powder, which term includes also hollow beads such as obtained from spray-drying a slurry, coarse particles, and fine powders; as flakes, as granulates and as tablets.
A preferred form of the composition is a powder which is obtained by the conventional 35 spray-drying technique, wherein the basic detergent ingredients including the pre-formed ferric ion chelate complex is formed into a slurry which is then fed to a spray-drying tower to form a dry free-flowing powder which is collected at the bottom of the tower Any heat-sensitive ingredients can be dry mixed with the spray-dried powder Alternatively the pre-formed ferric ion chelate complex may be incorporated by postaddition as a separate 40 ingredient to the spray-dried base powder.
As explained above, the composition of the invention on dissolving in water will produce effective concentrations of the ferric ion chelate complex in the bleaching bath to catalyse the bleaching action of the persalt e g sodium perborate, to a satisfactory extent.
Accordingly in one aspect, the invention pertains to a process for cleaning fabrics by 45 contacting said fabrics with an aqueous solution comprising hydrogen peroxide or a hydrogen peroxide liberating persalts and 1-70 ppm, preferably from 2 550 ppm, of a pre-formed ferric ion chelate complex of ethylene diamine tetraacetic acid nitrilotriacetic acid, diethylene triamine pentaacetic acid, or hydroxyethyl ethylene diamine triacetic acid.
In one more specific embodiment of the invention the process comprises the use of a 50 solution comprising a persalt and 2 5-50 ppm of a ferric ion chelate complex selected from the group of Fe ‘/EDTA, Fe 3 +/NTA, Fe 3 +/DTPA Fe 32 +/HEEDTA and mixtures thereof, and having a p H of about 8 5-10 5 A preferable range of complex level is 5-40 ppm; a preferable p H range is from about 9-10.
It should be appreciated as indicated before that the invention is applicable with any of 55 the known percompound bleaching agents, including hydrogen peroxide and percompounds which liberate hydrogen peroxide in aqueous solution, such as the alkali metal perborates, percarbonates, persilicates, perphosphates, etc.
The invention can be applied to bleaching and cleaning baths such as are used for treating textiles, to wash liquors such as are used in commercial and domestic launderings, and to 60 solid bleaching compositions.
In practising the invention the man in the art is of course free to choose any level of the pre-formed complex within the range as defined hereinbefore, as he would think desirable for serving his purpose, but for economic reasons in the majority of cases the lowest level that still brings about the highest activation will be selected for use 65 A -‘S 1 565 807 The advantages of the invention are shown in the following illustrative examples.
Example I
The effect of various Fe 3 + systems on perborate bleaching using two detergent bases was 5 investigated.
Bleach tests were conducted in clean systems on tea-stained cotton test pieces using deionised water.
The results for given additives are shown in Table I in which bleaching scores are expressed in terms of conventional reflectance increase values (AR 460) 10 Bleach/washing conditions:
min isothermal wash at 90 C.
0.375 % detergent base solution + 0 125 % sodium perborate.
Fe 3 + level = 1 ppm (= 6 5 ppm pre-formed Fe 3 +/EDTA complex, when present) 15 EDTA level = 0 1 % and 0 2 % (when added separately) 15 TABLE I
2 Additive Detergent Base A Detergent Base B 20 2 AR AR None 14 8 13 1 Fe 3 + + EDTA 15 9 16 8 Fe 3 + 2 EDTA 14 4 25 Fe 3 + / EDTA 17 6 20 1 complex 30Compositions of detergent bases A B 30 Sodium dodecylbenzene sulphonate 20 6 30 6 Coconut ethanolamide 3 9 4 6 Sodium toluene sulphonate 2 6 Sodium tripolyphosphate 45 2 53 6 Alkaline silicate 14 2 35 Sodium sulphate 13 7 9 2 Sodium carboxymethylcellulose 1 5 The results show that there is a definite advantage in the use of the preformed Fe 3 +/EDTA complex over the Fe 3 + and EDTA added separately 40 Example II
This example illustrates the effect of Fe 3 +/EDTA complex level on the bleaching performance of sodium perborate.
Bleach tests were conducted in clean systems on tea-stained cotton test pieces using 45 deionised water.
The results are shown in Table II, in which bleaching scores are expressed in terms as used in Example I.
Bleach/washing conditions: 50 min isothermal wash at 90 C; heat-up from 20-95 C.
0.375 % detergent base solution + 0 125 % sodium perborate.
A TABLE II
Complex ppm in soln.
level wt% in product Detergent Base A Heat-up 20-95 C AR 0 1 3 2.6 3.9 5.2 6.5 13 1 19.5 26.0 32.5 0 0.03 0.05 0.08 0.10 0.13 0.26 0.40 0.52 0.65 16.6 22.0 21.0 20.6 20.6 20.1 Detergent Base B min isothermal wash at 90 C A R 16.1 18.1 19.6 19.7 19.7 20.7 21.0 20.1 19.4 19.3 Example III
This example illustrates the effect of Fe 3 +/NTA complex, Cu 2 +/EDTA complex and Co 2 +/EDTA complex on the bleaching performance of sodium perborate.
Bleach tests were conducted in clean systems on tea-stained cotton test pieces using deionised water.
Bleach/washing conditions:
0.375 % detergent base A+ 0 125 % sodium perborate min isothermal washes at 75 C and 90 C.
The results are shown in Table III.
TABLE III
Complex Fe 3 +/NTA Cu 2 +/EDTA Co 2 +/EDTA Level ppm in soln.
0 4.4 8.7 21.8 43.6 C AR 6.9 7.9 9.1 9.6 8.2 0 6.2 12.4 31.1 62.2 0 6.7 13.3 33.3 66.6 7.7 7.8 8.5 8.1 8.6 C AR 13.9 15.8 17.0 15.1 12.3 14.5 13.5 11.6 13.3 15.0 14.7 14.4 14.4 11.5 10.7 note: 4 4 ppm Fe 3 +/NTA = 6 2 ppm Cu 2 +/EDTA = 6 7 ppm Co 2 +/EDTA = 1 ppm metal ion equivalent.
These results clearly show the non-effectiveness of copper/EDTA and cobalt/EDTA complexes to catalyse bleaching by sodium perborate, in contrast to the positive effects observed with a ferric ion chelate complex of the invention.
Example IV
This Example illustrates the effect of Fe 3 +/EDTA complex on commercial products containing sodium perborate.
Three commercial perborated detergent powders were obtained and their perborate levels were determined by iodometric titration The following perborate levels were found:
1 565 807 1 565 807 Product I 22 3 % Product II 22 8 % Product III 18 8 % Bleach tests (heat-up wash cycle 20 -95 C) conducted with these powders at 0 5 % product concentration and at different Fe 3 +/EDTA levels on tea-stained cotton test cloths using deionised water gave results as shown in Table IV below.
TABLE IV
Complex level ppm soln.
Complex level ppm soln.
6.5 13.1 19.5 26.0 32 8 Product I AR Product II AR 19.9 UK Surf AR 24.5 22.5 22.8 21.8 21.4 17.8 Bio OMO AR 22.3 21.7 21.1 20.5 20.7 Product III AR 15.6 Tide AR 19.4 18.6 19.0 18.2 18.3 The results again demonstrate a pronounced activating effect for systems concerning Fe 3 +/EDTA complex of the invention.
Example V
In order to assess perborate savings which may be realised with Fe 3 + /EDTA catalysed bleaching, experiments were performed at different perborate levels Two series of experiments were conducted The first series of experiments directly compared the effect of a constant level of Fe 3 +/EDTA complex at decreasing perborate levels with the performance of perborate alone.
First series of experiments min isothermal washes at 90 C 0.375 % detergent base A + sodium perborate 6 5 ppm Fe 3-/EDTA complex (= 1 ppm Fe 3 + on solution = 0 13 % powder) The results are given in the following Table V 1 complex on base TABLE V 1
Perborate level AR % on product 13 16 19 22 25 11.7 12.7 14.2 15.5 16.4 15.1 Control experiment without complex.
These results when plotted graphically will show that the 25 % perborate product without complex is equivalent to one containing about 21 % perborate + 0 13 % ferric ion/EDTA complex This suggests that use of the complex may save approximately 4 % of sodium perborate.
A second series of experiments was conducted, comparing a system outside the invention with the system of the invention using the following bleach/washing conditions:
15 min isothermal washes at 90 C using deionised water.
7 1 565 807 7 0.375 % detergent base A Fe 3 +/EDTA = 1 ppm EDTA = 5 5 ppm.
Fe 3 +/EDTA complex = 6 5 ppm The results are given in the following Table V 2 below.
5 TABLE V 2
Additive Perborate levels 10 % 15 % 20 % 25 % 10 A R A R A R 104 R None 9 2 10 2 12 5 15 0 Fe 3 +/EDTA 8 4 10 1 13 5 15 9 Fe 3 +/EDTA 9 4 11 8 15 2 17 6 complex These results again confirm the superiority of the pre-formed Fe 3 +/EDTA complex over its separate components 20 Graphical treatment of the data shows that a product containing 19 5 % perborate + 0.13 % complex is equivalent to a 25 % perborate only product, giving a potential perborate saving in this instance of approximately 5 5 %.
Example VI 25
The following Example gives a further illustration of the effectiveness of the use of pre-formed ferric ion chelate complexes according to the invention for activating the bleach performance of H 202 at 90 C Figures are also given for some cobalt and copper complexes, for comparison.
Bleach tests were conducted using an isothermal wash at 90 C for 15 minutes, as the 30 standard conditions The complexes assessed were prepared by simple aqueous mixing in stoichiometric ratio of metal ion and chelating agent, followed by isolation, either by precipitation or crystallisation.
All evaluations were conducted in solutions of an EDTA-free detergent base A of Example I and a standard complex level such that its level of metal ion in solution was 1 35 ppm, was adopted.
To 250 ml of base solution ( 0 375 %), thermostatted at 90 C, were added 1 0 ml of standard metal ion complex solution, four tea-stained test pieces ( 5 x 5 cm), and finally sodium perborate ( 0 313 g) in that order After 15 minutes the test pieces were withdrawn and subsequently, after rinsing and drying, assessed reflectometrically at R 460 Control 40 runs were conducted in the absence of metal ion complex.
The results are summarised in the following Table VI.
TABLE VI
45 Complex Bleach Activation Complex increment’) Ratio 2) Equivalent A(AR) A R Level 3) Fe 350 /NTA C E L (%) 5 5 Fe 3 +/NTA + 2 9 1 19 21 Fe 3 +/DTPA + 2 4 1 16 22 Fe 3 +/HEEDTA + 2 3 1 15 22 Fe 3 +/EDTA + 2 7 1 14 22 Cu 2 +/NTA + 2 8 1 15 22 55 Cu 2 +/DTPA 0 3 0 98 26 Cu 2 +/EDTA 1 0 0 93 27 Co 2 +/EDTA 0 3 0 98 26 Co 2 +/DPA 4) O 5 0 92 27 Co 2 +/p A 5) -10 0 0 47 53 60 Bleach increment A(AAR): The reflectance difference between clothes bleached in the presence and absence of complex, i e.
A (AR) = AR,: ARP Q 0 1 565 807 where ARC = Reflectance increase from perborate + complex A Rp = Reflectance increase from perborate alone.
2) Activation ratio (A R): The ratio of reflectance increase in the presence of complex to that in its absence, i e.
A.R = A Rc / A Rp 3) Complex equivalent level (C E L): Level of perborate required in a system with the complex for its performance to match that of 25 % perborate alone; i e O C.E L = 25/A R.
154) Pyridine-2,6-dicarboxylic acid is 1 5) Pyridine-2-carboxylic acid.
The above results show that under the conditions tested all the Fe 3 + complexes examined increased the bleach performance; the Cu 2 + complexes and Co 2 + complexes tested generally deactivated bleach performance, except for Cu 2 +/NTA Apparently they act 20 principally as efficient H 202 decomposition catalysts.

Claims (12)

WHAT WE CLAIM IS:-

1 A process for cleaning fabrics by contacting the fabrics with an aqueous solution comprising hydrogen peroxide or a hydrogen peroxide liberating per-salt and 1-70 ppm of a pre-formed ferric ion chelate complex of ethylene diamine tetraacetic acid, nitrilotriacetic acid, diethylene triamine pentaacetic acid, or hydroxyethyl ethylene diamine triacetic acid.

2 A process according to claim 1, wherein the solution has a p H of 8 510 5 and the pre-formed ferric ion chelate complex is present in an amount of 2 5-50 ppm.

3 A process according to claim 2, wherein said pre-formed ferric ion chelate complex is 30 present in an amount of 5 40 ppm.

4 A process according to claim 2, wherein the p H of the solution is from 9-10.

A process for cleaning fabrics by contacting the fabrics with an aqueous solution comprising hydrogen peroxide or a hydrogen peroxide liberating per-salt and 1-70 ppm of a pre-formed ferric ion chelate complex, substantially as hereinbefore described in any one of 35 the Examples and Tables.

6 A bleaching composition suitable for use in a process according to claim 1 comprising, by weight, a) from 5 to 35 % of a per-salt b) from 5 to 80 % of a builder salt and (c) from 0 05 to 1 % of a pre-formed ferric ion chelate complex of ethylene diamine 40 tetraacetic acid, nitrilotriacetic acid, diethylene triamine pentaacetic acid or hydroxyethyl ethylene diamine triacetic acid.

7 A composition according to claim 6 additionally comprising up to 50 % by weight of an organic surface active agent.

8 A composition according to claim 7 comprising, by weight, (a) from 10 to 25 % of the per-salt b) from 10 to 60 % of the water-soluble builder salt c) from 0 1 to 0 8 % of the ferric ion chelate complex and (d) from 5 to 35 % of an anionic or nonionic surface active agent, or a mixture thereof.

9 A composition according to any one of the preceding claims, having a p H, measured 50 as a 0 5 % solution in distilled water of from 8 5 to

10 5 A composition according to claim 9 wherein the p H is from 9-10.

11 A composition according to any one of claims 6-10, wherein said ferric ion chelate complex is present in an amount of 0 25 5 % by weight of the per-salt.

12 A bleaching composition comprising a per-salt, a builder salt and a pre-formed 55 ferric ion chelate complex substantially as hereinbefore described in any one of the Examples and Tables.
P.G MOLE, Agent for the Applicants.
Printed for Her Majesty’s Stationery Office, by Croydon Printing Company Limited, Croydon, Surrey, 1980.
Published by The Patent Office 25 Southampton Buildings, London, WC 2 A l AY,from which copies may be obtained.
o

GB51859/75A
1975-12-18
1975-12-18
Process and compositions for cleaning fabrics

Expired

GB1565807A
(en)

Priority Applications (20)

Application Number
Priority Date
Filing Date
Title

GB51859/75A

GB1565807A
(en)

1975-12-18
1975-12-18
Process and compositions for cleaning fabrics

IT69958/76A

IT1108151B
(en)

1975-12-18
1976-12-13

COMPOSITION AND PROCEDURE FOR CLEANING FABRICS

NZ182870A

NZ182870A
(en)

1975-12-18
1976-12-13
Bleaching composition comprising a per salt and a ferricion chelate comples

FI763578A

FI61714C
(en)

1975-12-18
1976-12-13

BLEKANDE DETERGENTKOMPOSITION SAERSKILT FOER RENGOERING AV TYGER SAMT FOERFARANDE FOER RENGOERING AV TYGER

AT923776A

AT362034B
(en)

1975-12-18
1976-12-14

Bleach or bleach / detergent

ES454217A

ES454217A1
(en)

1975-12-18
1976-12-14
Bleaching compositions and process for cleaning fabrics

CH1578776A

CH624709A5
(en)

1975-12-18
1976-12-15

US05/750,787

US4119557A
(en)

1975-12-18
1976-12-15
Bleaching compositions and process for cleaning fabrics

DE19762657043

DE2657043A1
(en)

1975-12-18
1976-12-16

BLEACH AND METHOD OF CLEANING FABRICS

BR7608454A

BR7608454A
(en)

1975-12-18
1976-12-16

PROCESS TO PREPARE A WHITE COMPOSITION AND PROCESS FOR CLEANING FABRICS

NO764273A

NO146244C
(en)

1975-12-18
1976-12-16

Bleach / detergent mixture for TOEY CLEANING

PT65982A

PT65982B
(en)

1975-12-18
1976-12-17
Compositions and process for cleaning fabrics

CA268,140A

CA1079007A
(en)

1975-12-18
1976-12-17
Compositions and process for cleaning fabrics

ZA00767500A

ZA767500B
(en)

1975-12-18
1976-12-17
Compositions and process for cleaning fabrics

FR7638181A

FR2335593A1
(en)

1975-12-18
1976-12-17

BLEACHING COMPOSITIONS AND METHOD FOR CLEANING CLOTH

NLAANVRAGE7614001,A

NL184483C
(en)

1975-12-18
1976-12-17

METHOD FOR PREPARING AN ANY WASHING ACTION BLEACH FOR TEXTILE

BE173382A

BE849540A
(en)

1975-12-18
1976-12-17

COMPOSITIONS AND METHOD FOR CLEANING CLOTH

SE7614253A

SE425319B
(en)

1975-12-18
1976-12-17

WHITING LAUNDRY COMPOSITION

JP51151857A

JPS5276281A
(en)

1975-12-18
1976-12-17
Bleaching agent compounds and method of cleaning clothes

DK571876A

DK571876A
(en)

1975-12-18
1976-12-17

BLEACH AND BLEACH AND DETERGENT PRODUCT

Applications Claiming Priority (1)

Application Number
Priority Date
Filing Date
Title

GB51859/75A

GB1565807A
(en)

1975-12-18
1975-12-18
Process and compositions for cleaning fabrics

Publications (1)

Publication Number
Publication Date

GB1565807A
true

GB1565807A
(en)

1980-04-23

Family
ID=10461670
Family Applications (1)

Application Number
Title
Priority Date
Filing Date

GB51859/75A
Expired

GB1565807A
(en)

1975-12-18
1975-12-18
Process and compositions for cleaning fabrics

Country Status (20)

Country
Link

US
(1)

US4119557A
(en)

JP
(1)

JPS5276281A
(en)

AT
(1)

AT362034B
(en)

BE
(1)

BE849540A
(en)

BR
(1)

BR7608454A
(en)

CA
(1)

CA1079007A
(en)

CH
(1)

CH624709A5
(en)

DE
(1)

DE2657043A1
(en)

DK
(1)

DK571876A
(en)

ES
(1)

ES454217A1
(en)

FI
(1)

FI61714C
(en)

FR
(1)

FR2335593A1
(en)

GB
(1)

GB1565807A
(en)

IT
(1)

IT1108151B
(en)

NL
(1)

NL184483C
(en)

NO
(1)

NO146244C
(en)

NZ
(1)

NZ182870A
(en)

PT
(1)

PT65982B
(en)

SE
(1)

SE425319B
(en)

ZA
(1)

ZA767500B
(en)

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* Cited by examiner, † Cited by third party

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Priority date
Publication date
Assignee
Title

EP0123489A2
(en)

1983-04-20
1984-10-31
The Procter & Gamble Company
Detergent compositions

EP0124341A2
(en)

1983-04-29
1984-11-07
The Procter & Gamble Company
Bleach auxiliaries, their manufacture and use in bleach and laundry compositions

US10426142B2
(en)

2015-05-12
2019-10-01
Zodiac Pool Care Europe
Pool cleaning apparatus with a filtration device that can be extracted via a lateral face

WO2023031026A1
(en)

2021-09-01
2023-03-09
Unilever Ip Holdings B.V.
Oral care composition

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Assignee
Title

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(en)

1979-01-22
1980-12-09
S. C. Johnson & Son, Inc.
Hydrogen peroxide bleach composition

JPS5598750A
(en)

1979-01-23
1980-07-28
Fuji Photo Film Co Ltd
Photographic bleaching composition

FR2503746A1
(en)

1981-04-09
1982-10-15
Air Liquide

ACTIVE BINDERING COMPOSITION USING PEROXIDE PRODUCTS

GR76237B
(en)

1981-08-08
1984-08-04
Procter & Gamble

US4481129A
(en)

1981-12-23
1984-11-06
Lever Brothers Company
Bleach compositions

US4400361A
(en)

1982-03-30
1983-08-23
Purtec Systems, Inc.
Method of removing H2 S from a gas stream utilizing boron-vanadium and iron complexes

US4488980A
(en)

1982-12-17
1984-12-18
Lever Brothers Company
Detergent compositions

US4478733A
(en)

1982-12-17
1984-10-23
Lever Brothers Company
Detergent compositions

GB8312185D0
(en)

1983-05-04
1983-06-08
Unilever Plc
Bleaching and cleaning composition

GB8329762D0
(en)

1983-11-08
1983-12-14
Unilever Plc
Manganese adjuncts

GB8908416D0
(en)

1989-04-13
1989-06-01
Unilever Plc
Bleach activation

JPH06503251A
(en)

1990-12-19
1994-04-14
アラーガン、インコーポレイテッド

Compositions and methods for disinfecting contact lenses

WO1994004167A1
(en)

1991-02-26
1994-03-03
THE UNITED STATES OF AMERICA represented by THE SECRETARY, DEPARTEMENT OF HEALTH AND HUMAN SERVICES
Metal-based formulations with high microbicidal efficiency valuable for disinfection and sterilization

DE4216363A1
(en)

1992-05-18
1993-11-25
Henkel Kgaa

Process for color stabilization of surfactants

EP0588413A1
(en)

1992-09-15
1994-03-23
Unilever N.V.
Detergent composition

CA2187175A1
(en)

1994-04-07
1995-10-19
Stefano Scialla
Bleach compositions comprising metal-containing bleach catalysts and antioxidants

US5686014A
(en)

1994-04-07
1997-11-11
The Procter & Gamble Company
Bleach compositions comprising manganese-containing bleach catalysts

BR9507984A
(en)

1994-06-13
1997-11-18
Unilever Nv

Bleaching and oxidation catalyst and bleaching composition

GB2294268A
(en)

1994-07-07
1996-04-24
Procter & Gamble
Bleaching composition for dishwasher use

US5578136A
(en)

1994-08-31
1996-11-26
The Procter & Gamble Company
Automatic dishwashing compositions comprising quaternary substituted bleach activators

KR100350924B1
(en)

1994-12-06
2002-10-31
제일제당주식회사
Bleach-containing detergent composition having improved bleaching stability

EP0807159B1
(en)

1995-02-02
2000-05-24
The Procter & Gamble Company
Automatic dishwashing compositions comprising cobalt chelated catalysts

ES2163006T3
(en)

1995-02-02
2002-01-16
Procter & Gamble

METHOD FOR ELIMINATING TE STAINS IN AUTOMATIC DISHWASHERS USING COMPOSITIONS THAT INCLUDE COBALT CATALYSTS (III).

US5968881A
(en)

1995-02-02
1999-10-19
The Procter & Gamble Company
Phosphate built automatic dishwashing compositions comprising catalysts

CN1192774A
(en)

1995-06-16
1998-09-09
普罗格特-甘布尔公司
Automatic dishwashing compositions comprising cobalt catalysts

CA2224559A1
(en)

1995-06-16
1997-01-03
The Procter & Gamble Company
Bleach compositions comprising cobalt catalysts

US5703034A
(en)

1995-10-30
1997-12-30
The Procter & Gamble Company
Bleach catalyst particles

EP0778342A1
(en)

1995-12-06
1997-06-11
The Procter & Gamble Company
Detergent compositions

US5876625A
(en)

1996-07-22
1999-03-02
Carnegie Mellon University
Metal ligand containing bleaching compositions

US5904734A
(en)

1996-11-07
1999-05-18
S. C. Johnson & Son, Inc.
Method for bleaching a hard surface using tungsten activated peroxide

DE19721886A1
(en)

1997-05-26
1998-12-03
Henkel Kgaa

Bleaching system

AU1463799A
(en)

1997-11-21
1999-06-15
Procter & Gamble Company, The
Product applicator

WO2004069979A2
(en)

2003-02-03
2004-08-19
Unilever Plc
Laundry cleansing and conditioning compositions

KR100647976B1
(en)

2004-05-03
2006-11-23
애경산업(주)
Bleach and detergent compositions containing macrocyclic manganese complex

US7833423B2
(en)

2004-06-01
2010-11-16
Regenesis Bioremediation Products
Enhanced oxidation process for removal of water and soil contaminants

WO2007025244A2
(en)

2005-08-25
2007-03-01
Houle Philip R
Treatment systems for delivery of sensitizer solutions

US20070138674A1
(en)

2005-12-15
2007-06-21
Theodore James Anastasiou
Encapsulated active material with reduced formaldehyde potential

US20090001339A1
(en)

2007-06-29
2009-01-01
Tae Young Lee
Chemical Mechanical Polishing Slurry Composition for Polishing Phase-Change Memory Device and Method for Polishing Phase-Change Memory Device Using the Same

KR20090002506A
(en)

2007-06-29
2009-01-09
제일모직주식회사
Cmp slurry composition for the phase change memory materials and polishing method using the same

WO2013103630A1
(en)

2012-01-04
2013-07-11
The Procter & Gamble Company
Fibrous structures comprising particles and methods for making same

EP3075832B1
(en)

2015-03-30
2021-04-14
Dalli-Werke GmbH & Co. KG
Manganese-amino acid compounds in cleaning compositions

US10244762B1
(en)

2016-02-25
2019-04-02
Arch Chemicals, Inc.
Solid aquatic organism control composition and method of use

JP6790257B2
(en)

2016-11-01
2020-11-25
ザプロクターアンドギャンブルカンパニーＴｈｅＰｒｏｃｔｅｒ＆ＧａｍｂｌｅＣｏｍｐａｎｙ

Leuco colorants as bluish agents in laundry care compositions, their packaging, kits and methods

WO2018085300A1
(en)

2016-11-01
2018-05-11
The Procter & Gamble Company
Methods of using leuco colorants as bluing agents in laundry care compositions

JP6886045B2
(en)

2017-01-27
2021-06-16
ザプロクターアンドギャンブルカンパニーＴｈｅＰｒｏｃｔｅｒ＆ＧａｍｂｌｅＣｏｍｐａｎｙ

Activator-containing articles that exhibit consumer-acceptable article usage characteristics

US11697904B2
(en)

2017-01-27
2023-07-11
The Procter & Gamble Company
Active agent-containing articles that exhibit consumer acceptable article in-use properties

US11697905B2
(en)

2017-01-27
2023-07-11
The Procter & Gamble Company
Active agent-containing articles that exhibit consumer acceptable article in-use properties

US11697906B2
(en)

2017-01-27
2023-07-11
The Procter & Gamble Company
Active agent-containing articles and product-shipping assemblies for containing the same

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2017-08-18
2019-02-20
The Procter & Gamble Company
Cleaning agent

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(en)

2018-12-14
2020-06-18
The Procter & Gamble Company
Foaming Fibrous Structures Comprising Particles and Methods for Making Same

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2023-03-09
Unilever Ip Holdings B.V.
Bleach catalysts, bleach systems and cleaning compositions

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(en)

2021-09-01
2023-03-09
Unilever Ip Holdings B.V.
Bleach catalysts, bleach systems and cleaning compositions

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1961-06-19
1964-11-10
Shell Oil Co
Bleaching

GB1182143A
(en)

1966-03-01
1970-02-25
United States Borax Chem
Bleaching Compositions and Methods.

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1968-03-04
1970-01-06
Peter Strong & Co Inc
Denture cleansers

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(en)

1975-12-08
1977-06-07
Scott Paper Company
Metal plate treating solution

1975

1975-12-18
GB
GB51859/75A
patent/GB1565807A/en
not_active
Expired

1976

1976-12-13
IT
IT69958/76A
patent/IT1108151B/en
active

1976-12-13
NZ
NZ182870A
patent/NZ182870A/en
unknown

1976-12-13
FI
FI763578A
patent/FI61714C/en
not_active
IP Right Cessation

1976-12-14
AT
AT923776A
patent/AT362034B/en
not_active
IP Right Cessation

1976-12-14
ES
ES454217A
patent/ES454217A1/en
not_active
Expired

1976-12-15
US
US05/750,787
patent/US4119557A/en
not_active
Expired – Lifetime

1976-12-15
CH
CH1578776A
patent/CH624709A5/de
not_active
IP Right Cessation

1976-12-16
DE
DE19762657043
patent/DE2657043A1/en
active
Granted

1976-12-16
BR
BR7608454A
patent/BR7608454A/en
unknown

1976-12-16
NO
NO764273A
patent/NO146244C/en
unknown

1976-12-17
BE
BE173382A
patent/BE849540A/en
not_active
IP Right Cessation

1976-12-17
FR
FR7638181A
patent/FR2335593A1/en
active
Granted

1976-12-17
NL
NLAANVRAGE7614001,A
patent/NL184483C/en
not_active
IP Right Cessation

1976-12-17
DK
DK571876A
patent/DK571876A/en
not_active
Application Discontinuation

1976-12-17
SE
SE7614253A
patent/SE425319B/en
not_active
IP Right Cessation

1976-12-17
PT
PT65982A
patent/PT65982B/en
unknown

1976-12-17
CA
CA268,140A
patent/CA1079007A/en
not_active
Expired

1976-12-17
ZA
ZA00767500A
patent/ZA767500B/en
unknown

1976-12-17
JP
JP51151857A
patent/JPS5276281A/en
active
Granted

Cited By (7)

* Cited by examiner, † Cited by third party

Publication number
Priority date
Publication date
Assignee
Title

EP0123489A2
(en)

1983-04-20
1984-10-31
The Procter & Gamble Company
Detergent compositions

EP0123489A3
(en)

1983-04-20
1987-05-20
The Procter & Gamble Company
Detergent compositions

US4680131A
(en)

1983-04-20
1987-07-14
The Proctor & Gamble Company
Detergent compositions

EP0124341A2
(en)

1983-04-29
1984-11-07
The Procter & Gamble Company
Bleach auxiliaries, their manufacture and use in bleach and laundry compositions

EP0124341A3
(en)

1983-04-29
1988-09-07
The Procter & Gamble Company
Bleach auxiliaries, their manufacture and use in bleach and laundry compositions

US10426142B2
(en)

2015-05-12
2019-10-01
Zodiac Pool Care Europe
Pool cleaning apparatus with a filtration device that can be extracted via a lateral face

WO2023031026A1
(en)

2021-09-01
2023-03-09
Unilever Ip Holdings B.V.
Oral care composition

Also Published As

Publication number
Publication date

NO146244C
(en)

1982-08-25

NO764273L
(en)

1977-06-21

ZA767500B
(en)

1978-07-26

NL184483B
(en)

1989-03-01

DE2657043C2
(en)

1990-08-16

US4119557A
(en)

1978-10-10

JPS5520520B2
(en)

1980-06-03

FI61714B
(en)

1982-05-31

ATA923776A
(en)

1980-09-15

SE425319B
(en)

1982-09-20

PT65982B
(en)

1978-11-07

DK571876A
(en)

1977-06-19

NO146244B
(en)

1982-05-18

FI763578A
(en)

1977-06-19

FR2335593B1
(en)

1979-03-09

IT1108151B
(en)

1985-12-02

JPS5276281A
(en)

1977-06-27

NZ182870A
(en)

1978-06-20

CH624709A5
(en)

1981-08-14

BR7608454A
(en)

1977-12-13

FI61714C
(en)

1982-09-10

PT65982A
(en)

1977-01-01

NL7614001A
(en)

1977-06-21

DE2657043A1
(en)

1977-06-23

AT362034B
(en)

1981-04-27

ES454217A1
(en)

1978-03-01

NL184483C
(en)

1989-08-01

SE7614253L
(en)

1977-06-19

BE849540A
(en)

1977-06-17

CA1079007A
(en)

1980-06-10

FR2335593A1
(en)

1977-07-15

Contact information