US2765239A - Process for the improvement of organic material - Google Patents

Description

wnnew Oct. 2, 1956 A. E. SIEGRIST 2,7652239 PROCESS FOR THE IMPROVEMENT OF ORGANIC MATERIAL Filed May 18, 1953 Textile Mnierial Optically Brightened With Ox-Diozole Compound.

INVENTOR ADOLF E SIEGRIST ATTORNEYS United States Patent PROCESS FOR THE IJVIPROVEMENT OF ORGANIC MATERIAL Adolf Emil Siegrist, Basel, Switzerland, assignor to Ciba Limited, Basel, Switzerland, a Swiss firm Application May 18, 1953, Serial No. 355,841 Claims priority, application Switzerland May 21, 1952 14 Claims. (Cl. 117-335) in which R and R1 stand for any organic residues, compounds with two 1:3:4-ox-diazole rings correspond to the general formula in which R, R1 and R: represent any organic residues and the index n stands for nought or 1. In compounds, which are to be used according to the invention and which correspond to either of the mentioned formulae or analogous formulae (if more than two ox-diazole rings are present), none of the residues R and R1, or R, R1 and R2, respectively, should contain any grouping imparting dyestuif character to the molecule and at least one of the mentioned residues should contain a system of conjugated double bonds which stands in conjugation with the double bonds of at least one ox-diazole ring. Such compounds have thus no dyestufl character in the narrow sense, but possess according to their constitution a more or less pronounced affinity to the most varying substrata. Owing to the fact that the compounds to be used according to the invention absorb a part of the ultra-violet rays of ordinary daylight, they cause the treated material to be less penetrable or quite unpenetrable for these rays. Therefore in cases in which ultra-violet rays have a damaging efiect on materials, the latter are protected. The treatment of human skin can also be taken into consideration in this connection. The protection of material, for instance of foodstufis, is also possible by treating the packing material or covers.

The improvement of organic material according to the invention not only aims at making the material unpenetrable for ultra-violet rays but especially at brightening such material. Not all compounds containing one or several 1:3:4-ox-diazole rings fluorescing green-blue to violet in ultra-violet light are suitable as brightening agents. For this purpose only those compounds can be used which have a strong fluorescence. -Data on the constitution of compounds which can be used as brightening agents are given hereinafter.

Fluorescent compounds, including those which serve only for improvement without brightening as well as those which brighten, can be applied by steeping the material to be improved with solutions, especially aqueous solutionsor dispersions of the compounds, and drying after centrifuging and squeezing out. Basic compounds containing no acid groups can be advantageously used as aqueous solutions of their salts formed with acids. lroducts containing acid groups are advantageously used in the form of the aqueous solutions of their metal salts. Apart from the mentioned aqueous solutions there can also be used solutions in organic solvents for improvement according to the invention. Further it is possible to treat materials with the compounds in dispersed form, for instance with dispersions obtained with dispersing agents such as soaps, soap-like materials, polyglycolethers of fatty alcohols, sulphite waste liquor or condensation products of naphthalene sulphonic acids which may be alkylated with formaldehyde.

The compounds to be used according to the present process, especially those suitable as brightening agents, can also be used in the course of the manufacturing process of the materials to be improved by adding the compounds for instance to a paper pulp or a viscose solution intended for the manufacture of films or filaments, or in other spinning compositions, for instance in a spinning composition containing a linear synthetic polyarnide or a solution of acetyl cellulose intended for spinning.

The compounds serving as brightening agents to be used according to the present process can also be used as follows:

(a) in admixture with dyestufis or as adjuvant to dyebaths, printing, discharge or resist pastes. Further for after-treatment of dyeings, printings or discharge printmgs.

(b) in admixture with chemical bleaching agents or as an a van to ga e mg s, r instance ogether ninmhrmchlmts- (c) In admixture with dressing agents, such as starch or synthetically prepared dressings. The products according to the invention can for instance be added to crease-proofing liquors.

The brightening agents containing at least one 113:4- ox-diazole ring, those which are water-soluble as well as the water-insoluble, can be used together with washing agents. The washing agent and the brightening agent may be added separately to the washing liquor. However, it is of advantage to use a washing agent which is admixed with a brightening agent of the invention. Suitable washing agents are, for example, soaps, salts of sulphonated washing agents such, for example, as salts of sulphonated benzimidazoles containing as a substituent at the Z-carbon atom a higher alkyl radical, and also salts of monocarboxylic acid esters of 4-sulphophthalic acid with higher fatty alcohols, salts of fatty alcohol sulphonates, of alkylaryl sulfonic acids or of condensation products of higher fatty acids with aliphatic oxyor amino-sulphonic acids. There may also be used washing agents free from ions, for example, polyglycol ethers, which are derived from ethylene oxide and higher fatty alcohols, alkylphenols or fatty amines.

The washing agents containing the brightening agents of the invention may also contain the additions cus- A small proportion of the ox-diazole compound in relation to the washing agent generally suffices. There may be used, for example, a proportion of the ox-diazole compound within the range of 0.1-5 percent on the weight of the washing agent. However, there may be used smaller proportions, for example, 0.01 percent orless. The brightening agents of this invention may also be used in admixture with known brightening agents.

The washing agents of this invention can be used in the ordinary washing processes. In this manner the materials to be cleaned can be washed and brightened simultaneously.

Among the materials which may be improved in accordance with the invention, i. e. which accordinng to the fluorescent compounds used may only be made impenetrable to ultraviolet rays or may also be brightened there may be mentioned the following:

(a) Textile materials generally, which may be present in any form, for instance as fibres, filaments, yarns, woven or knitted materials or as felt and all finished products made of these materials; these textile materials may consist of: natural materials of animal origin, such as wool and silk, or of vegetable origin such as cellulose materials of cotton, hemp, flax, linen, jute and ramie, further of semi-synthetic materials, such as regenerated cellulose, for instance, artificial silk, viscoses including staple fibres or synthetic materials produced by polymerisation or mixed polymerisation or those obtained by polycondensation such as polyesters, especially polyamides such as nylon.

(b) Fibres of another kind which are not textile mamaterials, which may be of animal origin, such as feathers, hair, also furs and skins and leather obtained from the latter by natural or chemical tanning, as well as finished products thereof; also fibres of vegetable origin, such as straw, wood, wood-pulp or fibre materials consisting of compressed fibres, such as paper, cardboard or pressed wood as well as products manufactured from the latter.

-(c) Plastics in general which may be present in any form, for instance as powder, film, lacquer, resin or pressed articles, also natural or synthetic colloids, such as gelatine or starch, natural or synthetic rubber, synthetically manufactured glasses or photographic emulsions, as well as films or papers manufactured from the latter, other materials of natural or artificial, organic or inorganic origin, such as oils, fats as well as carbohydrates intended for use as foodstuffs, for instance flour, sugar, etc., also inorganic pigments, such as plaster of Paris, whitewash, or finally cosmetic preparations, such as agents for the care of teeth or hair.

It goes without saying that not all compounds fluorescing green-blue to violet with at least one 1:3:4-oxdiazole ring are equally suitable for the various uses given above. The possibility of using the various compounds is subject to the affinity depending on the constitution of the compounds to the different materials and 5 to the degree of the fluorescence. The expert can however easily select the compound suit-able for use in a given case.

As already mentioned, the main object of the present invention is optical brightening. For this purpose compounds insoluble in Water may be used. It is especially advantageous however, to use compounds containing groups imparting solubility in water, such as free or neutralized sulfonic acid and/or oarboxylic groups, quaternary ammonium groups or polyglycol residues. When the compounds possess groups capable of forming salts, such as sulfonic acid or carboxylic groups or amino groups, which may be alkyl-ated or aralkylated, such as monoethyl-amino, diethylamino, dimethylamino, hydroxyet-hylamino, dioxyethylamino, or benzylethylamino groups, it is advantageous to use the water-soluble salts thereof.

In order that the compounds fluorescing green-blue to violet in ultra-violet light and containing at least one 1:3z4-ox-diazole ring may be used as brightening agents, they should have a certain intensity. of fluorescence. The

4 latter depends on the number of double bonds in conjugated relation with the double bonds of the ox-diazole ring and on the presence or absence of atom groups in creasing fluorescence. For compounds having groups capable of forming salts it was found that the following conditions should be fulfilled to make them useful as optical brightening agents.

In compounds with one lz3-z4'ox-diazole ring corresponding to the formula N-N all LR.

the radicals R and R1, when they have no substituents which enhance fluorescence other than sulfonic acid and/or carboxylic acid groups, should each contain at least 4 double bonds which are in conjugated relation with the double bonds oi the ox-diazole ring. When the residues R and R1 contain aromatically bound amino groups, which may be alkylated or aralkylated, the number of. conjugated double bonds may be reducedby one, in other 'words, it is suflicient if each of the residues contains 3 conjugated double bonds and an aromatically bound amino group, or if the residue R contains 3, conjugated double bonds and an aromatically bound amino group and the residue R1 at least 4 conjugated double bonds. A similar regularity was observed in compounds with two ox-diazole rings. These compounds correspond to the general formula N -N N'-N R--ii -(Rzh-Q! iii-31 in which the index n represents nought or 1. In these compounds also the conditions given above for compounds having one ox-diazole ring apply to the residues R and Ri. In the case when n represents 1 the residue R2 should have at least one double bond which is in conjugated relation with the double bonds of both oxdiazole rings. The residues R, R1 and R2 may be of an aromatic, aliphatic, aralipha-tic or heterocyclic character and may, if desired, have substituents not imparting dyestutf character to the molecule, such as halogen atoms, alkyl or alkoxy groups. Summing up, it may be-said that those compounds are suitable forum as optical brightening agents which are colorless or almost colorless, fluoresce -green-blue to violetxin ultra-violet light and are watersoluble in the form of salt and-correspond to=the general formula I. o J..-

in which the index m stands for-nought or a small numher and the index n for nought or 1 and R, R1 and R2 represent aromatic, aliphatic, araliphatic or heterocyclic residues-which, if desired, may-have substituents not imparting dyestufi character to the molecule, on condition that the residues R and R1 possess groups capable of forming salts and that if these residues-are free from aromatically bound amino groups and-possess sulfonic acid or carboxylic acid groups as. salt-forminggroups, the mentioned residues R1 and R2, should each-have .at least 4 doublebonds which are-in. conjugated: relation with the ox-diazole double-bonds and with the further condition that if there is an aromatically bound amino group present in one of the residues R1 and R2 or in both, the residue carrying such an amino group may have. a conjugated double :bond less, and. the third condition that residue-Rzshould contain at least one double bondpin conjugated relation with the ox-diazole double bonds.-

It. is of.advantage touse the compounds of the. last mentioned formula in.which.the index. In. stands for nought or 1. As examples of compounds which may be used for the invention there may be mentioned:

(1) 2:5-bis-(sulpho-styryl)-1:3:4-ox-diazole of the formula HOJS (2) 2:5-bis-(sulpho-2'-chloro-styry1)-l :3 :4-ox-diazole of the formula (3) 2:5-bis-(sulpho-4'-chloro-styryl)-l 3 :4-ox-diazole of the formula 801K 801B -(4) 2 :S-bissulpho-4'-methy-l-styryl) 41 :3 :4-ox-diazole of the formula N--N on or an-l i z-cn=on HI BOrH son;

(5) S-sulpho styryl 2 [5' sulphostyryl l:3':4'- ox-diazolyl-(2')]-1:3:4-ox-diazole of the formula amma t -(6) 1 [5' sulpho styryl 1':3':4' ox diazolyl- (2')] 4 [5" sulpho styryl 1":3":4" ox diazolyl- (2")]-benzene of the formula Bos "(7) ,5 bis [5 sulpho styryl 1:3:4 ox diazolyl(2) J-ethylene of the formula the formula azole of the formula (10) 2 sulphostyryl 5 sulpho diphenyl (4')- 1:3 :4-ox-diazole of the formula hots BOIH 5 (8) 2:5-bistsulpho-diphenyl-(4')14:3:4-ox-diazole of N i-0nd:

(9) Sulfonated 2:5-bis-[naphthy1-(1')]-1:3:4-ox-di- 503E Q k/30C? a note (11) 2:5-bis-[4"-carboxy-diphenyl-(4') 1-1 :3 :4-ox-diazole of the formula nooc-O-O 0 -C -Oco on (12) 2:5 bis [4' dimethylamino phenyl (1')]- 1 :3 :4-ox-diazole of the formula on, N-N on,

) OK $0 on. o \CHI 1 3 2:5 -bis-[4'-diethylamino-phenyl-( 1 ]-1 :3 :4-ox-diazole of the formula ('14) 2:5 bis [4' sulphomethylamino phenyl- 20 (l')]-1:3:4-ox-diazole of the formula N--N non-om-NHOP: gO-Nn-om-sona panic;

The following examples illustrate the invention, the parts and percentages being by weight unless otherwise 40 stated and the relationship of parts by weight to parts by volume being the same as that of the kilogram to the litre:

Example 1 Bleached cotton material is treated on a foulard with a solution which contains, per litre, 0.4 gram of the disodium salt of 2:5-bis-(sulphostyry1)-1z3z4-ox-diazole of the formula The treated cotton material has a whiter appearance than 65 the untreated material.

Example 2 Undyed cotton yarn is treated at a goods-toliq'uor ratio of 1:30 for about hour at room temperature in a bath 7() which contains, per litre, 0.04 gram of the disodium salt of 2:5-bis- [sulpho-dipheny-l-(4'-) J-l 3 :4-ox-diazole of the formula- 0 H mi m 7 After rinsing anddrying the yarn has ahigher content of white than the corresponding untreated material.

Example 3 Cotton is washed at a goods-to-liquor ratio of 1:40 boiling in a bath which contains 10 grams of a washing agent of the following composition:

soap

calcined soda sodium pyrophosphate sodium perborate magnesium silicate of the ox-diazole derivative mentioned hereinafter 31.6% water The material is then rinsed and dried. The cotton thus treated possesses a whiter appearance than cotton which has been washed with the same washing agent but without the addition of the ox-diazole derivative. The optical brightening agent used in this example is the disodium salt of the 1-[5-sulpho-styryl-l':3':4'ox-diazoly1- (2')] 4 [5" sulpho styryl 1":3":4": ox diazolyl-(2")l-benzene of the formula Ifil--N N HOlS Example 4 The sodium salt of Z-heptadecyl- -benzyl-benzimidazyl-disulphonic acid is mixed with 0.05-0.5% of the optical brightening agent used in Example 3. Undyed cotton which was washed in the usual way with the mixture thus obtained has a brighter appearance than the cotton which was washed with the above mentioned sodium salt of Z-heptadecyl-N-benzyl-benzimidazyI-disulphonic acid alone.

Example 0.1-0.5 gram per litre of the disodium salt ofthe 2:5 bis-(sulpho-2-chloro-styryl)-1:3z4-ox-diazole of the formula SOaH Gotham-( i -CH=CH nos 0 is added to a sodium hypocblorite bath containing 2 grams of active chlorine per litre. The cellulose material treated in the bath appears brighter than the material treated without the addition of the above mentioned oxdiazole.

Example 6 A washing agent is prepared which dissolves in water with a weakly acid reaction by mixing 5 parts of the 7 sodium salt of 2-heptadecyl-N-benzyl-beuzimidazole-disulfonic acid, 1 part of primary sodium phosphate and 0.2-1 part of the disodium salt of 2:5-bis-(sulpho-styryl)-l:3z4- ox-diazole of the formula Undyed textile material of synthetic polyamide fibres, for instance nylon or Perlon, which was washed for 16 hour at 50 C. and a goods-to-liquor ratio of 1:40 in a bath containing 10 grams per litre of the washing agent de: scribed above has a brighter appearance than material which was washed with the same washing agent but without the. addition of the ox-diazole derivative.

SOgH

NN uasi twang Boss 0 After dosing and drying the material has a higher content of white than the corresponding untreated material.

Example 8 Undyed textile material or synthetic polyamide fibres, for instance nylon or Perlon, is treated at a goods-toliquor ratio of 1:40 for an homat C. in a bath containing, per litre, 0.4 gram formic acid, 0.2 gram of the optical brightening agent mentioned in Example 7 and 0.008 gram of the dyestufi of the formula CHg-CH;

BOIH

After rinsing and drying the dyed textile material has a much cleaner appearance than the correspondence material dyed with the dyestuif only.

Example 9 Wool is treated at a goods-to-liquor ratio of 1:40 for A to 55 hour at 45 -50 C. in a bath containing per litre, 0.025 gram of 2:5-bis-[4-dimethylamino-phenyl-(1)]- 1:3 :4-ox-diazole of the formula N-N CH:

Q C \O/ CHz dissolved in 1215 parts of sulphuric acid of 10% strength. The material is then rinsed and dried. The wool thus treated has a higher content of white than the corresponding untreated material.

Example 10 Bleached cotton material is treated on a foulard at 50 C. with a finishing liquor consisting of 20 grams/ litre potato starch and 0.5 gram/litre of the ox-diazole compound used in Example 7. After drying, the cotton material thus finished has a whiter appearance than the cotton material finished with starch only.

Example 1] A film is prepared from a solution containing 10 percent of acetyl-cellulose and 0.0 1-0.05% of the 2:5-bis- [4'-diethylamino-phenyl-(l)]-1:3:4-ox-diazole of the formula 01H: NN CIHJ O a a \0/ ClHl in acetone. After drying, the film is unpenetrable for ultra-violet rays, whilst a film prepared without the oxdiazole compound is penetrated by the rays.

What is claimed is:

l. A process for the brightening of organic material which comprises treating the material with a substantially colorless compound which exhibits in solution or when applied to a substratum a green-blue to violet fluorescence '9 in ultra-violet light or in daylight and is water-soluble in the form of salts and corresponds to the general formula wherein n stands for at most 2 and m for a small number and R, R1 and R2 represent radicals selected from the group consisting of aromatic, aliphatic, araliphatic and heterocyclic radicals which are free from groups imparting dyestufl character to the molecule, the radicals R and R1 carrying groups capable of forming salts with the proviso that when these radicals are free from aromatically bound amino groups and possess acid groups as salt forming groups the mentioned radicals must each have at least 4 double bonds in conjugated relation with the ox-diazole double bonds, with the second proviso that when an aromatically bound amino group is present in the radicals R and R1, the radical carrying such an amino group may have one conjugated double bond less, and with the third proviso that the radical R2 must contain at least one double bond in conjugated relation with the ox-diazole double bonds.

2. A process for the brightening of organic material, which comprises treating the material with 2:5-bis-(sulfostyryl) -1 :3 :4-ox-diazole.

3. A process for the brightening of organic textile material which comprises treating the material with 2:5- bis-(sulfo-styryl -l 3 :4-ox-diazole.

4. A process for the brightening of organic material of synthetic polyamide fibres, which comprises treating the material with 2:5-bis'(sulfo-styryl)-l:3z4-ox-diazole.

5. A process for the brightening of organic material which comprises treating the material with 2:5-his-[4"- carboxydiphenyl-(4) ]-l :3 :4-ox-diazole.

6. A process for the brightening of organic material which comprises treating the material with 5-sulfo-styryl- 2- [5' sulfo-styryll':3:4'- ox-diazolyl- (2') 1:3:4- oxdiazole.

7.A process for the brightening of organic material which comprises treating the material with 1-[5'-sulfostyryl-1z3z4 ox-diazolyl (2')] 4 [5" sulfostyryl l": "-ox'diazolyl-(T)l-benzene.

8. A process for the brightening of organic material, which comprises treating the material with a:fl-bis-[5 sulfostyryl-l :3 :4-ox-diazolyl (2) l-ethylene.

9. Brightened organic material which has incorporated in it a substantially colorless compound which exhibits in solution or when applied to a substratum a green-blue to violet fluorescence in ultra-violet light or in daylight and is water-soluble in the form of salts and corresponds to the general formula wherein n stands for at most 2 and m for a small number and R, R1 and R2 represent radicals selected from the group consisting of aromatic, aliphatic, araliphatic and heterocyclic radicals which are free from groups imparting dyestufi character to the molecule, the radicals R and R1 carrying groups capable of forming salts with the proviso that when these radicals are free from aromatically bound amino groups and possess acid groups as salt forming groups the mentioned radicals must each have at least 4 double bonds in conjugated relation with the ox-diazole double bonds, with the second proviso that when an aromatically bound amino group is present in the radicals R and R1, the radical carrying such an amino group may have one conjugated double bond less, and with the third proviso that the radical R2 must contain at least one double bond in conjugated relation with the oxdiazole double bonds.

10. Brightened textile material which has incorporated in it a substantially colorless compound which exhibits in 10 solution or when applied to a substratum a green-blue to violet fluorescence in ultra-violet light or in daylight and is water-soluble in the form of salts and corresponds to the general formula NN B-E 8-3.1

wherein R and R1 represent sulfonated araliphatic radicals which are free from groups imparting dyestufi character to the molecule and have each at least 4 double gong: in conjugated relation with the ox-diazole double 11. Brightened textile material of synthetic polyamide fibres which has incorporated in it 2:5-bis-(sulfostyryl)- 1 :3 :4-ox-diazole.

12. A washing agent containing a substantially colorless compound which exhibits in solution or when applied to a substratum a green-blue to violet fluorescence in ultraviolet light or in daylight and is water-soluble in the form of salts and corresponds to the general formula wherein n stands for at most 2 and m for a small number and R, R1 and R2 represent radicals selected from the group consisting of aromatic, aliphatic, araliphatic and heterocyclic radicals which are free from groups imparting dyestufl character to the molecule, the radicals R and R1 carrying groups capable of forming salts with the proviso that when these radicals are free from aromatically bound amino groups and possess acid groups as salt forming groups the mentioned radicals must each have at least 4 double bonds in conjugated relation with the ox-diazole double bonds, with the second proviso that when an aromatically bound amino group is present in the radicals R and R1, the radical carrying such an amino group may have one conjugated double bond less, and with the third proviso that the radical R2 must contain at least one double bond in conjugated relation with the ox-diazole double bonds.

13. A dye preparation containing in addition to at least one dyestufi a substantially colorless compound which exhibits in solution or when applied to a substratum a green-blue to violet fluorescence in ultra-violet light or in daylight and is water-soluble in the form of salts and corresponds to the general formula wherein n stands for at most 2 and m for a small number and R, R1 and R: represent radicals selected from the group consisting of aromatic, aliphatic, araliphatic and heterocyclic radicals which are free from groups imparting dyestufi character to the molecule, the radicals R and R1 carrying groups capable of forming salts with the proviso that when these radicals are free from aromatically bound amino groups and possess acid groups as salt forming groups the mentioned radicals must each have at least 4 double bonds in conjugated relation with the ox-diazole double bonds, with the second proviso that when an aromatically bound amino group is present in the radicals R and R1, the radical carrying such an amino group may have one conjugated double bond less, and with the third proviso that the radical Ra must contain at least one double bond in conjugated relation with the ox-diazole double bonds.

14. An improved finishing preparation for textiles containing a substantially colorless compound which exhibits in solution or when applied to a substratum a green-blue to violet fluorescence in ultra-violet light or in daylight and is water-soluble in the form of salts and corresponds to the general formula g Rt wherein n stands for at most 2 and m for a small number and R, R1 and R2 represent radicals selected from the group consisting of aromatic, aliphatic, araliphatic and heterocyclic radicals which are free irom groups imparting dyestufi character to the molecule, the radicals R and R1 carrying groups capable of forming salts with the proviso that when these radicals are free from aromatically bound amino groups and possess acid groups as salt forming groups the mentioned radicals must each have at least 4 double bonds in conjugated relation with the ox-diazole double bonds, with the second proviso that when an aromatically bound amino group is present in the radicals 12 R and R1, the radical carrying such an amino group may have one conjugated double bond less, and with the third proviso that the radical R2 must contain at least one double bond in conjugated relation with the ox-diazo1e double bonds.

References Cited in the file of this patent UNITED SIATES PATENTS 2,191,810 Stevens Feb. 27, 1940 2,320,654 Reister June 1, 1943 2,338,782 Reister Jan. 11, 1944 2,476,525 Anish July 19, 1949 2,620,282 Fry et a1 Dec. 2, 1952 2,649,385 Kendall et a1 Aug. 18, 1953 FOREIGN PATENTS 425,609 Great Britain Mar. 21, 1935

Claims (1)

1. A PROCESS FOR THE BRIGHTENING OF ORGANIC METERIAL WHICH COMPRISES TREATING THE MATERIAL WITH A SUBSTANTIALLY COLORLESS COMPOUND WHICH EXHIBITS IN SOLUTION OR WHEN APPLIED TO A SUBSTRATUM A GREEN-BLUE TO VIOLET FLUORESCENCE IN ULTRA-VIOLET LIGHT OR IN DAYLIGHT AND IS WATER-SOLUBLE IN THE FORM OF SALTS AND CORRESPONDS TO THE GENERAL FORMULA

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