TW527453B - A process for inhibiting the re-absorption of migrating dyes in the wash liquor, the compounds used in said process and the detergent composition comprising said compounds - Google Patents

Abstract

The present invention provides a process for inhibiting the re-absorption of migrating dyes in the wash liquor, comprising introducing into a wash liquor containing a peroxide-containing detergent, from 0.5 to 150, preferably from 1.5 to 75, especially from 7.5 to 40 mg, per litre of wash liquor, of one or more compounds having the formula: in which n is 1, 2 or 3; A is an anion; Y is -(CH2)m in which m is an integer ranging from 1 to 8; -(CH2)p-CH(R1)- in which p is an integer ranging from 1 to 7 and R1 is linear or branched C1-C4-alkyl, preferably methyl; -CX=CX- in which X is cyano, linear or branched C1-C8-alkyl or di(linear or branched C1-C8-alkyl)-amino; -(CH2)q-NR1-(CH2)q- in which R1 has its previous significance and q is 1, 2, 3 or 4; or a 1,2-cyclohexylene residue having the formula: and R is cyano; halogen; hydroxy; OR1 in which R1 has its previous significance; CO2R2 in which R2 is hydrogen or linear or branched C1-C4-alkyl; nitro; linear or branched C1-C8-alkyl; di-(C1-C12alkyl)amino; NR3R4 in which R3 and R4 are the same or different and each is linear or branched C1-C12-alkyl; or -N⊕R1R3R4 in which R1, R3 and R4 have their previous significance.

Description

527453 Α7 Β7 Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the Invention (I) The present invention relates to a method for inhibiting the reabsorption of migration dyes in lotions. It is well known that a variety of different gold-contact compounds, such as manganese complexes, are used as catalysts in the oxidation of detergents with peroxy compounds, such as perborate or peroxy compounds. It is also known that certain other manganese compounds cause enhanced bleaching effects on dirt or dyes in lotions. What's more, these manganese composites do not deplete cotton, polyamide resin or polyester fibers at all, so the composites do not cause trouble of discoloration. One of the problems associated with assessing the use of a compound for inhibiting the reabsorption of migration dyes in lotions is the lack of adequate reliable and extensive screening techniques. This technique has been developed and used to quantify the potential of dye transfer inhibition effects. This screening step involves conducting different tests to make it possible to determine the usefulness / damage balance of any possible compound on a child-by-child basis. The selection of a compound is based on its specific effect, the range of use, compatibility with the most important system compounds, oxygen demand, and its potential for fiber and dye degradation. Moreover, the accuracy of these data can be Investigate the structure / effect relationship. When the manganese complex is applied to a new evaluation technique, it can be identified to show further manganese complexes, which are relatively low molecular weight as dye migration inhibitors and have excellent effects. When added horizontally, its effectiveness is substantially uniform. Therefore, the present invention provides a method for inhibiting the reabsorption of migration dyes in a lotion, which comprises introducing from 0.5 to 150, preferably from L5 to 75, per liter of lotion into a lotion containing a peroxide detergent. , Especially from 7.5 to 40 mg, one or more compounds of the following formula 5 (please read the precautions on the back first and then this IPT page)

, 1T

This paper size applies the Chinese National Standard (CNS) Λ4 specification (210X297 public power) 527453 A7 B7 V. Description of the invention (>)

(Please read the notes on the back before this page)

Where η is 1, 2 or 3; A is an anion;

R1 is a gas or Cl_C4 radical; Y is a linear or branched alkylene of the formula-[CO ^ KU, where m is an integer and the range is from 1 to 8, and each R1 has the meaning of the previous one; -CX = CX- where X is cyano, linear or branched C i -C8 alkyl or bis (linear or branched C 1 -C8 alkyl) amino;-(CHA-NUCH ^ wherein R i The meaning of one and Q is 1, 2, 3 or 4; or 1, 2, cyclohexene or phenylene residue with the following formula: printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs

6 This paper size applies the Chinese National Standard (CNS) Λ4 specification (210X 297 public bells) 527453 A 7 V. Description of the invention (printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economics where R7 is hydrogen, CH2OH or CH2NH2 or SOM, where M Is hydrogen, rhenium metal atom, ammonium or cation formed by amine, R and R > are cyano; halogen; hydroxyl; ORi or COORi where R i has the meaning of the previous one; nitro; partially or fully fluorinated Linear or branched C i-C 8 courtyard; NR3R4 where R3 and R4 are the same or different and are hydrogen or linear or branched (: i-C 1 2 alkyl; where R i, R3 and R4 have their The meaning of the former, or linear or branched C 1 -C8 alkylene-R2 where Rz is ORi, [(^ or NR3R4, Rs and R6 are hydrogen respectively; linear or branched ci -C4 alkyl; Substituted aryl or cyano, halogen, OL or COORi, nitro, linear or branched (: i-CS alkyl, NR3R4 substituted aryl, where R3 and R4 are the same or different and are hydrogen or Linear or branched C it -C 1 2 alkyl; β N + RiRsR4 where Ri, R3 and R4 have the same meaning as the previous one, or linear or branched C i-C8 alkylene-Rz where Rz is 0, C00R! Or NR3R4, but if R and R / are both C 1 -C4 alkyl, each η is 1. When Υ is 1, 2 · In the case of a cyclohexene residue, the residue may be in any of its cis / trans stereoisomer forms. Υ is preferably of the formula-[C (R8) 2] 2 where R8 is hydrogen or methyl, and -CX di ^ Where X is a fluoro group,-(CH2) q-NR ^ (CH2) q- which has the meaning of former ~ Hungary and Q is 1, 2, 3 or 4; or U-cyclohexene dyeing with the formula Phenylene residue: or

(Please read the notes on the back first

2 ^ 1

This paper size is applicable to Chinese National Standard (CNS) Λ4 specification (210X 297 public momentum) 527453 Printed by Shelley Consumer Cooperative of Central Standards Bureau of Ministry of Economic Affairs A7 ____B7_ V. Description of invention (+) R or R > The preferred halogen atom is Gas, bromine and fluorine atoms. When η is 1, the R or R > group is at the 4-position of the individual benzene ring, but excluding the R or R > group when R or R > is nitro or C02R2 Is at the 5-position of the individual benzene ring. When η is 2, R or group is preferably at the 4,6-position of the individual benzene ring, but excluding when R or R > is nitro or CCbR2, R or R / group is preferably at the individual benzene ring 3,5_ position of the ring. When R or R — is a di (C i -C i 2 alkyl) amino group, the alkyl portion may be a linear- or branched alkyl portion, and it preferably contains from 1 to 8, more preferably from 1 To 4, especially 1 or 2 carbon atoms. Preferably, R and R / are dimethylamino, diethylamino, hydroxy, methoxy, ethoxy, chlorine or nitro. Anion A includes halides, especially chloride, perchlorate, sulfate, nitrate, hydroxide, BF4, PF /, carboxylate, especially acetate, trifluoromethanesulfonate or tosylate . Some of the compounds of formula (1) and the ligands derived therefrom are known compounds. For example, N, N-bis (4-dimethylaminosalicylidene) diimine is described in US Patent 5,281,578. Of vinyl ethylene; disclosed in EP-A-0 693 550 for the production of magnesium complexes of N, N · bis (4-diethylaminosalicylidene) diimidoethylene; and Bernado et al. Inorg * Chem. 35 (2) 387 (1996) discloses the production of N, N-bis (4-diethylaminosalicylidene) diimidecyclohexene and the production of N, N-bis (4 -Diethylaminosalicylidene) diimide ethylene magnesium complex. The novel compounds of formula (1) and the novel ligands derived from them are further examples of the present invention. What's more, the compound of formula (1), where A is an anion and a) Υ is (please read the precautions on the back before

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This paper size applies to China National Standard (CNS) A4 specification (210X 297 public #) 527453 A7 V. Description of the invention (<) -CH2CH2- and each R is a di- (C i-CZ alkyl) amino group; or b) Y is cyclohexene and each R is a di- (C i -Cz alkyl) amine group. The use as a dye transfer inhibitor has been widely pointed out in GB-A-2,296,015, but it is not specifically mentioned. On the other hand, compounds of formula (1), where A is an anion, Y is -CH2CH2- and each R is a hydroxyl group, are believed to be completely novel when used as dye transfer inhibitors. (Please read the notes on the back first

(This page)

， 1T Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 9 This paper size applies to the Chinese National Standard (CNS) Λ4 specification (210X 297 gong) 527453 A 7 B7 5. Description of the invention (Ip) is particularly useful in the application of the method of the present invention Interested in compounds of the formula: (c2h5) 2n

j〇C (ch3) 2n

HO

J〇C

CH— CH2I I

CH = N N = CH

〇, v N (C2H5) 2 (1A) I Cl CH— CH2

N = CH XI

(1B) 0 ^ N (CH3) 2 I Cl CH— CH2

CH = N N = CH

(1C); and 〇, ^ '〇H i Cl (Please read the notes on the back first

, 1T Printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs (c2h5) 2n

I

n (c2h5) 2 (1D) · ^ Mn I Cl The paper size is applicable to Chinese National Standard (CNS) Λ4 specification (210X297 cm) 527453 A7 B7 V. Description of the invention (7) The present invention also provides a detergent composition, It contains i) 5.90%, preferably 5-70% of A) anionic surfactant and / or B) non-ionic surfactant; ii) 5-70%, preferably 5-50%, In particular, 5-40% of C) builders > iii) 0.1-30%, preferably 1-12% of D) peroxide; and iv) 0.005-2%, preferably 0,02 -1%, especially 0. 1-0. 5% E) Compounds of formula (1) or (2) as defined above, respectively based on the weight of the total weight of the detergent. The detergent can be formulated as a solid; or as a non-aqueous liquid monkey washing agent containing not more than 5, preferably 0_1% by weight of water, and based on a builder suspension in a non-ionic surfactant, For example, as described in GB-A-2158454, in the case of the powder, the detergent is in powder or granular form. The production of this powder or granular form by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs can be produced by spray drying. D) and E) all form an aqueous sludge to form a matrix powder first; then, by dry blending, add the composition D) and E) to the matrix powder. In a further method, the composition E) is added Into an aqueous slime containing the composition A), B) and C), and then spray-drying the slime before drying and blending the composition D) to the mixture. In yet another method, the composition B) does not exist, or is only partially present in the aqueous slime containing the compositions A) and c); the composition E) is pulverized to the composition B), and it is then added To spray-dried matrix powder; and finally composition D) is dry blended into the mixture. This paper size applies the Chinese National Standard (CNS) Λ4 specification (210X 297 gong) 527453 Printed by the Consumer Cooperatives of the Central Standardization Bureau of the Ministry of Economic Affairs A7 B7 V. Description of the invention (?) Anionic surfactant composition A) can be, for example, sulfuric acid Salt, sulfonate or carboxylate surfactant, or a mixture of the above. The preferred sulfate is an alkyl sulfate and has 12-22 carbon atoms in the alkyl group, optionally combined with an alkylethoxy group. Sulfate and has 10-20 carbon atoms in the alkyl group. Preferred sulfonates include alkylbenzene sulfonates and have 9 to 15 carbon atoms in the alkyl group. In each case, the cation is more rhenium metal, especially sodium. A preferred carboxylic acid salt is a sarcosinate of the formula R-CO-mR ^ -Ci ^ COOM1, where R is a fluorenyl or sulfonyl group and has 9.17 carbon atoms in the fluorenyl or sulfonyl group, R 1 is hydrogen or C i -C 4 alkyl and M 1 is a fluorene metal. The composition B) of the nonionic surfactant may be, for example, a condensate of ethylene oxide and a C9-Ci5-grade alcohol and has 3 to 8 moles of ethylene oxide per mole. The composition C) of the synergist can be a phosphonium metal phosphate, especially a tripolyphosphate; a carbonate or bicarbonate, especially its sodium salt; a silicate: an aluminosilicate; a polycarboxylic acid ester; Polycarboxylic acids; organic phosphonates; or aminoalkylene poly (phosphonates); or mixtures of the foregoing. The preferred citrate salt is crystalline layered sodium silicate of the formula NaHSim〇2m + l · ρΗ20 or Na2Sim〇2m + 1 · pH20 m, where m is a number from 1.9 to 4 and P is 0 to 20. Preferred aluminosilicates are commercial synthetic materials and are referred to as zeolites A, B, X, and HS, or mixtures thereof. Zeolite A is preferred. Preferred polycarboxylic acid esters include polycarboxylic acid hydroxyesters, especially citrates (please read the notes on the back first)

(This page)

、 1T This paper size applies Chinese National Standard (CNS) Λ4 specification (210 × 297). Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 527453 A7 B7 V. Description of the invention (9), polyacrylates and their and butadiene Copolymer of dianhydride. Preferred polycarboxylic acids include nitrilotriacetic acid and ethylenediaminetetraacetic acid. Ethylenediaminedisuccinic acid is in the racemic form and the enantiomer s, s-form. ◊ Preferred organic phosphonate or amine group Alkylene poly (phosphonic acid alkylene) is alkali gold ethyl 1-hydroxydiphosphonate, nitrilotrimethylenephosphonate, ethylenediamine tetramethylenephosphonate and diethylenetriamine Pentamethylene phosphonate. The composition of peroxide D) can be any organic or inorganic peroxide compound, which is mentioned in the literature or can be purchased from the market, which bleach textiles at the conventional washing temperature, for example, the temperature range is from 30 ° C to 90 ° C. In particular, the organic peroxide is, for example, a single peroxide or a polyperoxide and has an alkyl chain of at least 3, preferably 6 to 20 carbon atoms; Diperoxydicarboxylates of up to 12 carbon atoms, such as diperoxyperazelaate, diperoxypersebacate, diperoxyphthalate and / or diperoxy Peroxydodecanediates, especially their corresponding free acids. However, it is preferred to use highly reactive inorganic peroxides such as persulfate, perborate and / or percarbonate. It is of course also possible to use organic and / or inorganic peroxides. Peroxides can have different crystalline forms and / or different degrees of hydration. They can be used in combination with other organic or inorganic materials, thus improving their storage stability. Adding peroxide to the detergent can be achieved in particular by mixing the compounds, for example by means of a spinning metering system and / or a fluidized bed mixer. Detergents may contain one or more fluorescent whitening agents in addition to the combinations of the present invention, such as bistriazine-stilbene-diphenylethylene-disulfonic acid, bistriazolyl-stilbene-diphenylethylene-di Sulfuric acid, bisstyryl-biphenyl, bisbenzofuran 13 This paper size applies to the Chinese National Standard (CNS) Α4 size (210X297 cm). (Please read the precautions on the back before nt this page)

Π 527453 Printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs ¾ A7 B7 V. Description of the invention (,) Glycol, bisphenoxy derivative, bisbenzimidazolyl derivative, coumarin derivative or pyrazole Derivatives; dirt suspending agents, such as sodium carboxymethyl cellulose; salts for adjusting acid and acid, such as alkali or earth metal silicates: foaming agents, such as soap; adjusting spray drying and granulation properties Salts such as sodium sulfate; flavors; and, if appropriate, antistatic and softening agents; such as green clay; enzymes such as starch sugar; photobleaches; pigments; and / or toners. These ingredients must of course be stable to the bleaching system used. Particularly good detergent co-additives are polymers that are used to avoid transfer of labile dyes between fabrics during the wash cycle. A good example of such polymers is poly Vinylpyrrolidone is optionally modified by including anionic or cationic substituents, especially those having molecular weights ranging from 5000 to 60,000, especially from 10,000 to 50,000. Preferably, the use of this polymer is based on the weight of the detergent from 0.05 to 5%, preferably from 0.2 to 1.7% by weight. The detergent may additionally contain a so-called perboric acid A salt activator, such as TAGU, or preferably TAED. Its preferred use is from 0,05 to 5% by weight relative to the total weight of the detergent, especially from 0,2 to 1,7 weight. The manganese complex of formula (2) is a novel compound, and part of the manganese complex of formula (1) is also a novel compound (please read the precautions on the back again! This page)

---- I

1T The present invention therefore also relates to formula (3)

This paper size applies Chinese National Standard (CNS) A4 specification (210 × 297 mm) 527453 A7 B7 V. Description of the invention () or manganese compound of formula (2)

Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs where η is 1, 2, or 3; Α is an anion; ruler and ruler are cyano; halogen; hydroxyl; OR! Or COOL where R t has the meaning of the previous one Nitro; partially or fully fluorinated linear or branched C i -C8 alkyl; NR3R4 where R3 and R4 are the same or different and are hydrogen or linear or branched C i _C i 2 alkyl; -N + R must be R4 where R i, R3 and R4 have the same meaning as the previous one, or linear or branched C i -C8 alkylene-R2 where Rz is 〇Ri, COOR! Or NR3R4, and R ^ is hydrogen or C 1 -C4 alkyl, Y is -CX = CX- where X is cyano, · (CHA-NRKCH: ^ · where R 1 has the meaning of the previous one and Q is 1, 2, 3 or 4; formula-linear Or branched alkylene, where m is an integer and ranges from 1 to 8, and each R1 has the meaning of the previous one, but at least one R i is a C r ~ C 4 alkyl group; or has the following formula 1, 2_cyclohexene or phenylene residue ...

This paper size applies to Chinese National Standard (CNS) A4 specification (210X 297 male waste) (Please read the precautions on the back before this page)

Yan

I 527453 Μ __________ Β7 ______ V. Description of the Invention (, ν) where R7 is hydrogen, CH2OH or CH2NH2 or SOM, where M is hydrogen '鹸 metal atom, ammonium or cation formed by amine, but if R and R j Ci-C4 alkyl and Y are unsubstituted 1,2-cyclohexene residues, each η is 1, and Υ is a linear or branched alkylene of the formula, where m is an integer and ranges from 1 to 8 , And each R 1 has the meaning of the previous one; -CX = CX_ where X is cyano, linear or branched C 1 -C8 alkyl or bis (linear or branched C i-C8 alkyl) amine -(CHO ^ NUCHA- wherein R 1 has the meaning of the previous one and q is 1, 2, 3 or 4; or 1,2-cyclohexene or a phenylene residue having the formula: (please first Read the notes on the back again

Where R7 is hydrogen, CH2OH or CH2NH2 or SCbM, where M is hydrogen, an alkali metal atom, ammonium or a cation formed by an amine; R5 and Rs printed by the Consumer Cooperative of the Central Standard Bureau of the Ministry of Economic Affairs are hydrogen; Branch C i -C4 alkyl; unsubstituted aryl or aryl substituted with cyano, halogen, OR! Or COORi, nitro, linear or branched C 1 -C8 alkyl, NR3R4, where R3 and R4 are The same or different and respectively hydrogen or linear or branched C t _C 1 2 alkyl; -N + Ribb, where Ri, R3 and R4 have the same meaning as the previous one, or linear or branched C i -C8 alkylene -R2 where R2 is COOi ^ NR3R4. 16 This paper size applies to the Chinese National Standard (CNS) Λ4 specification (210X297 gong) Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 527453 A7 B7____ 5. Description of the invention (J) Formula (4) or (5) containing manganese compounds The ligands themselves are novel, and these ligands are also part of the invention. Therefore, the present invention is also related to the formula (4)

Where η is 1, 2 or 3; R and R > are cyano; halogen; hydroxyl; 0 or COOR: where R £ has the meaning of the previous one; nitro; partially or fully fluorinated linear or fraction Branch 〇t-C8 alkyl; NR3R4 in which R3 and Chi 4 are the same or different and are hydrogen or linear or branched C i -C i 2 alkyl; wherein R t, R3 and R4 have the same as the previous one Meaning, either linear or branched C i -C8 alkylene-Rz where Rz is 0Ri. (^ D or NR3R4, R is hydrogen or C i -C4 alkyl, Y is -CX = CX · where X is cyano,-(CI ^ VNUCHA • where R i has the meaning of the previous one and (! Is 1, 2, 3, or 4; Formula-[CdKU's linear or branched alkylene, where m is an integer and ranges from 1 to 8, and 17 (please read the precautions on the back first and then the page)

This paper size applies the Chinese National Standard (CNS) Λ4 specification (210 × 297 public power) 527453 A7 B7___ V. Description of the invention (rush) Each R i has the meaning of the previous one, but at least one R1 is C iC * alkyl ; Or 1,2-cyclohexene or phenylene residues of the formula: wherein R7 is hydrogen, CH2OH or CH2NH2 or SCbM, where M is hydrogen ', a 鹸 metal atom, ammonium or an amine-forming cation, but If R and R / are both Cl-G alkyl and Y is unsubstituted U-cyclohexene residue, each η is 1 ', Υ is linear or branched of formula-[C (R〇2] » Alkylene, where m is an integer and ranges from 1 to 8, and each R l has the meaning of the previous one; -CX = CX- where X is cyano, linear or branched C i -C8 alkyl or Bis (linear or branched C i -C8 alkyl) amino groups;-(O ^ VNRKCHsV where R i has the meaning of the previous one and Q is 1, 2, 3, or 4; or 1, 2, Cyclohexene or phenylene residue: or printed by the Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs

Where R7 is hydrogen, CH2OH or CH2NH2 or SChM, where M is hydrogen, a gold atom, ammonium or a cation formed by an amine,

Rs and 1 ^ 6 are hydrogen; linear or branched C i -C4 alkyl: unsubstituted aryl or via cyano, halogen, OR! Or COOL, nitro, linear or branched (: i-C8 Alkyl group, aryl group substituted by NR3R4, where R3 and R4 are 18 This paper size applies Chinese National Standard (CNS) Λ4 specification (210X297 ^^) 527453 A7 B7 5. Description of the invention (in) Same or different and is hydrogen or Linear or branched C1-Ciz alkyl; N + LR must, where Ri, R3 and R4 have the same meaning as the previous one, or linear or branched Ci-C8 alkylene-R2 where R2 is 01, C00R! Or NRA. Preferred compounds of formula (4) are the following:

(2b) • N _ Μ- Ν Ν V HO (2c)

OH Ν

^ ΟΗ ΗΟ Ν (Please read the note on the back first)

I --- H > ^ I Order Printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs Ν = χρ-Ν (2d)

Ν (2e) This paper size applies to the Chinese National Standard (CNS) Λ4 specification (210X 297 gong) 527453 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs A7 __B7 V. Description of the invention (々)

20 (Please read the notes on the back first

、 -Mouth This paper size applies to Chinese National Standard (CNS) A4 specification (210X 297 gong) 527453 A7 _B7 V. Description of the invention (J) Compared to the compound of formula (5),

(Please read the precautions on this page first)

Printed by the Consumer Standards Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs ¾ The following examples are used to illustrate the invention; unless otherwise specified, the parts and percentages are reset. Preparation of new ligands: Ligand 2 a: a) Preparation of corresponding anhydrides First, the starting compound N, N · dibutyl-4-aminohydroxy-benzoic acid needs to pass through N, N-dibutyl It is prepared by the action of Vi-3-smeyer formazanyl-3-aminoamidine. The preparation of Wisme reagent is made by slowly adding 4.7 ml (0.0497 mol) of phosphorus oxychloride to 15 ml (0.189 mol) of N, Nl · dimethylformaldehyde under stirring at room temperature for 15 minutes. Lamine. Stirring was continued for 30 minutes before the use of the Wismarsin reagent. According to the procedure described in EP 0356173, 11 g (0.497 mol) of N, N · dibutyl-3_aminophenol prepared by alkylating 3-aminophenol was dissolved in 13 ml of Ν, Ν · dimethyl 21 This paper is in accordance with the Chinese National Standard (〇 奶) 84 Regulations (210 乂 297 cm), 1T 527453 Α7 Β7 Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs (Β) Formamidine. This solution was added dropwise to the above-mentioned Wismar reagent at room temperature. The solution was stirred for 3 hours, heated to 50 ° C for 10 minutes, then the solution was cooled to room temperature and stirred for another 2 hours. Then, the reaction mixture was poured into 70 g of ice and stirred for 1 hour. The aqueous layer was extracted three times with 100 ml of chloroform. The combined organic mash was evaporated in vacuo. The crude product was purified by column chromatography (450 g of silica gel, and the eluent was a hexane / ethyl acetate 15: 1 volume ratio to obtain 3.2 g (26%) of N, N-dibutyl · 4- Aminohydrobenzaldehyde is an orange oily compound. B) Ligand 2 a is prepared at 55 ° C, 1 g (0.004 moles) of N, N-dibutyl-4-amino-2. -A solution of hydroxybenzaldehyde in 2 ml of ethanol was added dropwise to 0.13 ml (0.00191 mol) of ethylenediamine. The resulting Chenghuang solution was maintained at 60-65 ° C with stirring for 4 hours. The solution was cooled and the formed precipitate was dried and dried to give 540 mg (54%) of a slightly brown solid. 13C NMR (CDCb): 5 = 14 · 0 (aliphatic CHb), 20 · 2, 29 · 5, 50 · 8, 58.2 (aliphatic CH2), 98 · 2, 103 · 1, 132.9 (tertiary Aryl-C), 108.2, 151.9, 165.7 (quaternary aryl-C), 164.3 (Q = N). Theoretical 値 C 73 · 52 Η 9.65 Ν 1〇 · 72 Experiment 値 C 73 · 14 Η 9.34 Ν 10.55 Ligand 2 b The corresponding anhydride is prepared according to the steps described in EP 0356173 (13 g (0.04255)) Mol) N, N-dibutyl-3-aminophenol in 30 ml of chloroform solution with 6.7 g (0.04255 mol) phosphorus oxychloride and 12.4 g (0 · 169 22) Standard (CNS) Λ4 ^ grid (210X 297 public rubbish) 527453 Printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs A7 B7 V. Description of the invention (J) Moore N, N · dimethylmethanamine treatment and The purification procedure was as described in Compound 2a. Purification was performed by column chromatography and using chlorobenzene / ethyl acetate / ethanol (90: 5: 5 volume ratio). 1.78 g (13%) of N, N-heptyl-4-amino-2.hydroxy-benzaldehyde was obtained as a green oily compound. A solution of 0.8 g (0.024 mol) of N, N-heptyl-4-amino-2-hydroxy-benzaldehyde in 1 ml of ethanol was treated and purified as described in compound 2a. The obtained 720 mg (91%) of the ligand was a brown oily substance which was slowly crystallized after being stored at 5 ° C for three days. 13C NMR (CDC13): < 5 = 14 · 1 (aliphatic CH3), 22 · 6, 27.1, 29 · 2, 31.9, 51.0, 57.7 (aliphatic CH0, 98.3, 103 · 2, 133.0 (tertiary aryl-C), 108 · 2, 152.1, 166.5 (quaternary aryl-C), 164.3 (£ = N) 0 theory 値 C 76 · 47 Η 10 · 79 Ν 8 · 11 Experiment 値 C 76 · 18 Η 10 · 60 Ν 7.95 Ligand 2 c At 50 ° C, 2 g (0.01221 mole) of 5. · dimethylamino group- 2-Hydroxybenzaldehyde [prepared according to valence / eight Ac · //? /? · 51 (1978) 2433] A stirred solution of 6 ml of ethanol was added dropwise to 0.35 ml (0.0058 mole) of ethylene glycol Amine. An orange suspension was formed and stirred at 60 ° C for 4 hours. The suspension was cooled to room temperature, filtered and dried under vacuum at 30 ° C. The pure ligand obtained was a yellow solid (1.77 g 87%) 13C NMR (CDCh): δ = 45 · 0 (aliphatic NCH;), 60.0 (aliphatic CH2), 116 · 2, 117.2, 116 · 6 (tertiary aryl-C), 118.4, 144.2, 153.3 (quaternary aryl-C), 166.8 (ς = Ν) 〇23 (Please read the precautions on the back before HR page)

The paper size of the edition applies to the Chinese National Standard (CNS) Λ4 grid (210X 297 gong) 527453 Α7 Β7 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the invention (/) Theory 67/77 Η 7 · 39 N 15.81 Experiment 値 C 67.56 Η 7.35 Ν 15 · 25 Ligand 2 d 2 · 5 g (0.015 mol) of N, N · dimethyl · 4-amino-2-hydroxy-benzaldehyde at 7 A solution of ml of ethanol was added to a solution of 0.82 g (0.00721 mole) of diaminomaleic dinitrile in 14 ml of methanol over two minutes. The reaction mixture was heated at 65 ° C for 5 hours. The obtained brown suspension was cooled, dried and dried to obtain a brown solid hip (2.03 g, 70%). 13C NMR (CDC13): 5 = 40.0 (aliphatic NCH3), 110.4, 115 · 1 (aliphatic quaternary C), 98 · 2, 105.8, 133.0 (tertiary aryl-C), 110 · 4, 115 · 1,161 · 2 (quaternary aryl-C), 156.2 (C = N). Ligand 2 e 5.0 g (0.0259 mol) of 4-diethylamino-2-hydroxy-benzaldehyde in 12 ml of ethanol solution with 1.66 g (0.0123 mol) of bis- (3-Aminopropyl) amine treatment and purification steps were as described for ligand 2a. The crude product was dried under high vacuum to give 5.7 g (98%) of a red oil. 13C NMR (CDCls): 6 = 12 · 8 (aliphatic CHO, 31.1, 44 · 5, 47.2, 53.6 (aliphatic CH2), 98 · 7, 103.1, 133.2 (tertiary aryl- C), 108 · 2, 152.2, 169 · 0 (quaternary aryl-C), 162.5 (ς = N). Theoretical 値 C 68 · 77 Η 9.00 Ν Η.32 Experiment 値 C 67 · 09 Η 8.66 Ν 13 · 38 (the substance contains 1.52% water) Ligand 2 ί 81 · 24 prepared according to Beilstein (E IV, Volume 8, 223) 24 Chinese National Standard (CNS) A4 ^ (21〇 × 29ϋ ^) ~ 527453 Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs μ Β7 V. Description of the Invention (/) g (0.00517 mol) 4. Chloro-2-hydroxy-benzaldehyde in 2.5 ml of ethanol The solution was treated with 0.29 g (0.00246 mol) of trans-1,2, diaminohexanoic acid, and the purification steps were as described in ligand 2a. The ligand slowly crystallized under standing Yellow oil (0.96 g, 100%). 13C NMR (CDCL ·): (5 = 24.1, 32 · 9 (CH2), 54 · 6, 72.4 (CH), 117.0, 138.1, 162.0 (Quaternary aryl_C), 117.2, 118 · 9 (tertiary aryl—C), 164.0 (Q = N) ° Theory 値 C 61 · 39 Η 5 · 15 Ν 7 · 16 C 1 18 12 Experiment 値 C 61.50 Η 5.34 Ν 7.70 C 1 17.26 2g of ligand At room temperature, 2 g (0.013 mole) of 2-hydroxy · 4-methoxybenzaldehyde in 10 ml of ethanol The stirred solution was added with 579 mg (0.0065 mol) of 1,2 · diethylamino-2-methylpropane in one portion. The solution was heated at 60 ° C for 3 hours and cooled to room temperature. It was evaporated and dried under high vacuum to give the ligand as a reddish brown oil (2.58 g, 100%). 〇13C NMR (CDC13): ά = 25 · 3 ((QH3) 2C-), 55 · 3 ( OCHO, 59.2 (aliphatic quaternary C), 69.2 (NCH2), 101.2, 10L4 (tertiary aryl-C), 106.3, 106.4 (quaternary aryl-C), 112 · 2, 112 · 3 (quaternary aryl-C), 132 · 9, 133 · 1 (tertiary aryl-C), 160 · 3, 165 · 6 (ς = N), 163.7, 163 · 9 (quaternary aryl-C), 165.0, 166.7 (quaternary aryl-C). Theoretical 値 C 67 · 39 Η 6.79 Ν 7.86 Experiment 値 C 67 · 51 Η 6.91 Ν 7.69 25 ^ The paper size applies to the Chinese National Standard (CNS) A4 «L (210 × 297 ^ ΓYou) (please read the precautions on the back first and then the page line 527453. A7 B7 printed by Sakusha Co., Ltd. 5. Description of the invention (γ) Ligand 2 h 2 g (0.001 mol) of 4 · diethylamino-2-hydroxy-benzaldehyde and 456 mg (0 · 00517) 1,2-diethylamino-2-methylpropane was treated and purified in the same manner as described for the ligand 2 g. The obtained ligand was a red-brown solid (1.9 g, 84%). 13C NMR (CDCh): 5 = 12 · 7 (CHsCHbN), 25 · 4 ((CH3) 2C ·), 44.4 (NGH2CH3), 58.4 (fourth order C), 68 · 6 (NCH〇, 98 · 1 , 98 · 6 (tertiary aryl-C), 103 · 0, 103.1 (tertiary aryl-C), 108 · 3, 108 · 4 (quaternary aryl-C), 133.1, 133 · 4 (tertiary aryl-C), 151.6, 151.9 (quaternary aryl-C), 158.9, 164.5 (ί! = Ν), 166.0, 168 · 4 (quaternary aryl-C) Base-C). Theoretical 値 C 71 · 91 Η 8.74 Ν 12.72 Experiment 値 C 70 · 88 Η 8.65 Ν 12 · 35 Ligand 2 i at 5 ° C with stirring, 1.21 g (0 · 006mol) 4-diethylamino-2 · hydroxy-benzaldehyde is dissolved in 2 ml of ethanol. At this temperature, 2,3 · diamino · 2,3-dimethyl · butane (Prepared by Beilstein E IV, volume 4, 1354) was added in 2 ml of ethanol in 30 minutes. The reaction mixture was heated to 70 ° C for 3 hours and stirred at room temperature for another 8 hours. The resulting suspension was filtered, and the precipitate was washed with cold ethanol and dried under high vacuum to give a brown solid (890 mg, 66%). 13C NMR (CDC10: (5 = 12 · 8, 23.0 (OL ·), 44 · 5 (CH2), 6 3 · 3 (quaternary aliphatic C), 98 · 6, 103.0, 133.5 (tertiary aryl-C), 108 · 2, 152.1, 169.1 (quaternary aryl-C), 158.9 (£ = N). 26 This paper size applies the Chinese National Standard (CNS) Λ4 specification (210 × 297 mm) ~ (Please read the precautions on the back before printing on page 527453, printed by the Staff Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs ^ A7 B7 V. Description of the invention (4) Theoretical 値 C 72.07 Η 9.07 N 12.01 賫 Test 値 C 71.78 Η 9.03 Ν 11.88 Ligand 2 j 974 mg (0.045 mol) of 2,3,6,7-tetrahydro-8- A solution of hydroxy-111,511-benzo [ij] quinazine-9-carboxaldehyde in 30 ml of methanol was added to a solution of 148 mg (0.0025 mole) of ethylenediamine. The reaction mixture was heated at reflux for 1 hour. The formed precipitate was filtered and crystallized from 100 ml of methanol to obtain 590 mg (29%) of yellow crystals. 13C NMR (CDC13): 5 = 20 · 4, 21.3, 22 · 2, 27 · 2, 49 · 8, 50 · 1, 58 · 2 (ς 2), 106 · 8, 107 · 9, 112.2, 129.0, 146.4, 164.3 (C = N). Theoretical 値 C 73.33 Η 7.47 Ν 12.22 Experiment 値 C 73 · 37 Η 7.54 Ν 12.22 ligand 2 k 1.95 g (0 · 0 (Π14 Mo ) 8-Hydroxy-1,1,7,7-tetramethylquinazine carboxaldehyde in 60 ml of methanol as described in Ligand 2j, with 236 mg (0.0393 mmol) Ethylenediamine reaction. The precipitate was filtered and washed with methanol to give 1.52 g (75%). 13C NMR (CDC10: 5 = 28 · 5 (―grade C), 3L2 (―grade C), 31 · 7, 32 · 2, 36 · 6, 40 · 1, 47 · 4, 58 · 9, 108 · 7 , 114 · 8, 121 · 6, 127 · 5, 145 · 7, 161.2, 165.4 (Li = N). Ligand 2 1 5-0 g (0 · 355 5 mol) 2,4 -Dihydroxy-benzaldehyde in a solution of 17 ml of methanol with 1.97 g (0.069 mol) of trans-U-diamino group 27 ^ Paper size applies Chinese National Standard (CNS) A4 specification (210X29 ? Public) (Please read the precautions on the back before iSBF this page) 丨 Best line 527453 Δ7 A 7 B7 V. Description of the invention (艸) Cyclohexane treatment and heating at 65 ° C for 5 hours. Yellow suspension Was formed 'It was cooled to 2 ° C. The precipitate was filtered, washed with ethanol and dried to give 5.9 g (99%) of a yellow solid. 13C NMR (DMSO-d6): 5 = 24 · 9, 33 · 6 (CH!), 7L3 (CH), 103.3, 107.8, 134.1 (tertiary aryl-C), 112 · 0, 162.6 (quaternary aryl-C), 164.9 (C = N) Ligand 2 m 5 g (0.025 mole) of 4-diethylamino · 2 · hydroxy-benzaldehyde in a solution of 12 ml of ethanol with 0.92 g (0.0123 mole) of 1,2- Diaminopropyl Treated and heated at 65 ° C for 5 hours. The solution was cooled and stirred for 8 hours. The solution was concentrated to give 4.68 g (90%) of a brown solid. 13C NMR (CDCls): 5 = 12 · 7, 20.3 (CH3) , 44 · 5, 63.8 (CH2), 98 · 2, 103 · 1, 133.1 (tertiary aryl-C), 108 · 3, 15L5, 165.5 (quaternary aryl-C), 162 · 5 (G = N). The following ligands are known compounds.- (Please read the precautions on the back before Jr ·

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Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs

HO

28

OH line

This paper size applies to Chinese National Standard (CNS) 527453 A7 B7 V. Description of Invention (β)

This paper size applies Chinese National Standard (CNS) Λ4 specification (21 OX 297 gong) 74 2 5 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs ¾ A7 B7 V. Description of invention (public) The preparation of these ligands is based on Known literature steps: All the ligands described are converted to its manganese complex. The basis for the synthesis of these complexes is described in, for example, the document E · N · Jacobsen and his research colleagues in J · Org · Chem ·, 59 (1994) 1939 or in the patent 03--2-2,296,015. As an example of the standard procedure, the synthesis of manganese complex 1 b was as follows: 667 mg of ligand 3 was dissolved in 10 ml of a stirred solution of ethanol and 465 mg of manganese-E-acetate-tetrahydrate was added. . The reaction solution was heated at 65-70 ° C for 4 hours. The solution was then evaporated and the residue was dissolved in 40 ml of water. The solution was treated with 3.7 g of sodium chloride. The resulting precipitate was filtered and dried in vacuo. The obtained manganese complex was a reddish brown powder (820 mg, 86%). Example 1 Each test compound was then evaluated according to the following method to determine its reactivity as a dye transfer inhibitor. 7.5 g of white cotton was rinsed in 80 ml of washing liquid. The lotion contains 8.6 millimoles / liter Η200, a test dye solution, and 7.5 g / liter of standard detergent ECE phosphate-free (456IEC) EMPA, Switzerland: 9.74% sodium linear alkylbenzene sulfonate ( Marlon A375); 5.19% ethoxylated C i 2-C i 8 fatty alcohols (7 moles E0); 3.64% sodium soap; 6.49% silicic acid inhibitor; 32.47% sodium aluminosilicate zeolite 4 A: 11.82 % Sodium carbonate; 5.19% sodium salt of acrylic acid / maleic acid copolymer (Sokolan CP 5) 30 This paper size is applicable to China National Standard (CNS) Λ4 specification (210X 297 male H ~ '(Please read the back Note again

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527453 A7 ____B7 printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the invention (4) 3.38% sodium silicate (SiCb: Na2〇 = 3.3: 1); 1.30% carboxymethyl cellulose; 0.26% EDTA; 7.40% sodium sulfate: 12.21% water; 0.65% proteolytic enzyme metal ball 0.26% fluorescent whitening agent 20.0% sodium percarbonate; and 3.0% TAED. The rinse was performed at 40 ° C for more than 30 minutes in a beaker of a LINITEST device. The dye transfer inhibitor tested was added at 5 micromoles / liter. The commercial test dye used is Cuprophenyl Brown 2GL (Dye 1) and its use level is 10 mg / L 250% formulation, or Reactive Blue 238 (Dye 2) and its Use a 100% formulation at a level of 6 mg / L. The reflectance spectra of individual test samples were measured with a SPECTRAFLASH 2000 instrument and converted to whiteness 値 according to CIE standard procedures. DTI (dye transfer inhibition) efficiency percentage (a) is then calculated according to the following equation: a = {[Y (E)-Y (A) / [Y (W)-Y (A)]] X 100 Among them, Y (W), Y (A) and Y (E) are respectively the fabric washed with no dye transfer inhibitor and the fabric washed with dye transfer inhibitor before the treatment. Degrees. The percentage of a 値 is expressed as a completely ineffective dye transfer inhibitor. When this compound is added to the lotion, it can make 31 paper sizes suitable for household use (CNS). (~ (Please read the precautions on the back first) (Continued on this page)

527453 A7 B7 5. Description of the invention (ii) The dye is completely transferred to the white material. In contrast, 100% 値 represents a perfect dye transfer inhibitor. The dye was not transferred to the white material when the compound was added to the lotion. The results obtained are shown in the following table. 10 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs. Table 1 DTI efficiency of dye transfer tests (a) Inhibitor dye 1 Dye 2 Inhibitor 1 (A) 90 98 Inhibitor 1 (B ) 82 87 Inhibitor 1 (C) 80 85 Inhibitor 1 (D) 84 86 Manganese complex ligand 2a 71 2b 78 2c 70 2d 73 2e 68 2f 84 2g 80 2h 87 2i 69 2j 90 2k 77 21 85 2m 85 (Please read the notes on the back before this page)

This paper size applies the Chinese National Standard (CNS) Λ4 specification (210/297 g ^ 1 527453 kl B7 V. Description of the invention (called) Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs. Table 1 b: Derived from the known ligand Manganese complex DT1- efficiency DTI efficiency 撕 3a 92 3b 74 3c 76 3d 61 3e 78 3f (ligand of manganese complex lb) See Table 1 3g (ligand of manganese complex lc) see Table 1 3h (ligand of manganese complex la) See Table 1 3i (ligand of manganese complex Id) See table 1 3j_ 97 The results in Table 1 clearly illustrate the manganese complex of the present invention as a dye Transfer inhibitors show excellent results. (Please read the precautions on the back before

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33 The size of this paper mark applies to the Chinese National Standard (CNS) Λ4 specification (210X 297 public power) 527453 B7 V. Description of the invention (π) Window Example 2 Repeat the procedure of Example 1 except that the inhibitor 1 (A) is used And 1 (B), and the use of these inhibitors is different for Guang Fanyi. The results obtained are shown in Table 2 below. Table 2 Dye transfer inhibitor concentrations tested / mol / 1 DTI efficiency (a) Dye 1 Dye 2 Inhibitor 1 (A) 5 59 64 10 69 85 20 83 95 30 90 103 50 90 98 70 98 105 Inhibitor 1 (B) 5 50 43 10 61 76 20 76 78 30 77 78 50 82 87 70 82 88 (Please read the precautions on the back before

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Printed by the Consumers' Cooperative of the Central Bureau of Standards, Ministry of Economic Affairs. The results shown in Table 2 show that the manganese complex of formula (1) as a dye transfer inhibitor shows excellent results even when added at very low levels. This paper size applies the Chinese National Standard (CNS) Λ4 specification (210 × 297 gong) 527453 Employees' cooperation with the Central Bureau of Standards of the Ministry of Economic Affairs 枉 Printing 5. Description of the invention Ul) 眚 Example 3 Repeat the steps in Example 1 except that only The inhibitors 1 (A) and 1 (B) were used, and their efficiency in controlling the transfer of a wide range of dyes at different levels was tested. The results obtained are shown in Table 3 below. Table 3 DTI efficiency of dye concentration tested (a) β mol / 1 dye 1 (A) dye 2 (B) cuprous phenyl brown 2GL 250% 10 90 82 reactive blue 238 100% 6 98 87 reactive black 5 133 % ⑴ 12 80 65 Direct Black 22 400% (2) 6 76 73 Reactive Blue 19 Specialty 100% (3) 20 97 88 Acid Blue 113 180% (4) 6 96 90 Disperse Violet 1 100% (5) 6 90 72 (1) Reactive Black 5 (2) Direct Black 22 (3) Reactive Blue 19 Special (4) Acid Blue 113 (5) Disperse Violet 1 The results in Table 3 illustrate the manganese complex of formula (1) as dye transfer Inhibitors show excellent results when different ranges of dyes are added at different levels of resistance. 35 This paper size is applicable to Chinese National Standard (CNS) Λ4 specification (210 '乂 297 public momentum) (Please read the precautions on the back before this page), r 527453 A7 _B7____ 5. Description of the invention (: > > >) Example 4 The procedure of Example 1 was repeated at a washing temperature of 20 ° C. The results obtained are shown in Table 4 below. Table 4 DTI efficiency of dye transfer inhibitors tested (a) _ dye 1 dye 2 inhibitor 1 (A) 82 86 inhibitor 1 (B) 79 73 inhibitor 1 (C) 70 86 inhibitor 1 (D) 80 80 (Please read the precautions on the back page first) 丨 _ 丨 The results in Table 4 show that when the manganese complex of formula (1) is used as a dye transfer inhibitor, it will still show extreme temperature even at a washing temperature as low as 20 ° C. Good effect. Example 5 Repeat the procedure of Example 1 except that only inhibitors 1 (A) and 1 (B) are used, and the detergent composition used is reset by adding 4% TAED as a bleach activator. modified. The results obtained are shown in Table 5 below. Table 5 DTI efficiency of dye transfer inhibitors tested (a) Dye 1 Ί Dye 2 Inhibitor 1 (A) 99 100 Inhibitor 1 (B) 96 97 The results in Table 5 illustrate the manganese complex of formula (1) as Dye transfer 36 I paper size applies Chinese National Standard (CNS) Λ4 specification (210 × 297 mm) " *, ιτ Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 527453 A7 B7 V. Description of invention (q) Inhibitor display The excellent effects and their effectiveness are not impaired by the co-use with the activated bleaching system. Furthermore, the compatibility between the manganese complex of formula (1) and the activated bleaching system has an increased benefit. In particular, under the conditions described in Example 1, even if only the manganese complex of formula (1) of 20 // M was used, the bleaching promoting effect of TAED was maintained. Therefore, using tea-contaminated cotton test materials, the increase in whiteness (ΛΥ) obtained when no dye transfer inhibitor (control test) is present is 24; the inhibitor 1 (A) is 23; and the inhibitor is used 1 (B) is 24. Bao Shi Example 6 The steps of Example 1 were repeated, except that only inhibitors 1 (A) and 1 (B) were used, and the detergent composition used was added by 100 / M DEQUEST 2041 [ethylenediamine- Tetra- (methylenephosphonic acid)] is modified as a sequestering agent. The results obtained are shown in Table 6 below. Table 6 (Please read the notes on the back before

、 1T Consumption cooperation with employees of the Central Bureau of Standards, Ministry of Economic Affairs. DTI efficiency of dye transfer inhibitors tested by Du Printing (a) Dye 1 Dye 2 Inhibitor 1 (Α) DEQUEST is not stored 20 / mol / 1 83 89 50 β mol / 1 90 93 20 β mol / 1 95 95 50 u mol / 1 98 98 Inhibitor 1 (Β) No DEQUEST stored DEQUEST 20 / z mol / 1 76 82 50 μ mol / 1 82 87 20 β mol / 1 78 79 50 u mol / 1 87 83 37

This paper size applies the Chinese National Standard (CNS) Λ4 specification (210 × 297 gong) 527453 Μ ___B7 V. Description of the invention (4) The results shown in Table 6 show that the manganese complex of formula (1) shows extremely polar when used as a dye transfer inhibitor. The good effects and their effectiveness are not impaired by the co-use with sequestrants. Sequestering agents are often found in detergent formulations, and their presence can often result in higher alphas being observed. This is because heavy metal ions are masked, and therefore the presence of peroxide oxygen is not depleted by useless degradation. Example 7 The procedure of Example 1 was repeated, except that only inhibitors 1 (A) and 1 (B) were used, and the use of H2O2 in the detergent was different. The results obtained are shown in Table 7 below. Table 7 (Please read the precautions on the back first, then the concentration of 002 β mol / 1 DTI% (rate (a) inhibitor 1 (A) inhibitor 1 (B) dye 1 Material 2 Dye 1 Dye 2 2.1 84 85 65 60 4.3 86 88 83 79 8.6 89 89 85 82 The Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs printed on Table 7 shows the results, even if it is stored in the detergent formulation H2〇2 The habitual amount is reduced by 4 factors, and the effect of the manganese complex of formula (1) as a dye transfer inhibitor is still retained. Example ft Repeat the steps of Example 1 except that the inhibitors 1 (A) and 1 ( B), and a series of dyed cotton fabrics that are known to be very sensitive to bleaching systems are used. For comparison purposes, TAED is used instead of inhibitor 1 (A) 38 This paper applies Chinese national standard 隼 ([, 5) / \ 4 Specifications (210/297 Gong Zheng) 527453 Α7 Β7 5. The invention test (required) or 1 (B) similar tests were carried out. The washing treatment was performed five times with individual detergent compositions, and in individual The percentage of dye loss was measured after the fifth rinse was completed. The results obtained are shown below Table 8. Table 8 --------- I! (Please read the note box on the back and then the page) Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs * Vat Brown 001 When using a detergent containing a manganese complex of formula (1) as a dye transfer inhibitor, the observed dyeing loss was of the same order as when using a detergent containing TAED activated bleaching system as an experiment. The latter Detergent composition illustrates the technology of oxygen bleach, and its dye damage / usefulness balance is acceptable in the industry. After the fifth individual decontamination is completed, it is measured using the same test conditions The relative percentage of DP (average degree of polymerization) reduction is used to estimate the fiber damage β. The results obtained are shown in the following table. 9◊ 39 Dye% for threading test% Color preparation loss% Inhibitor 1 (A) Inhibitor 1 (B ) TAED Reactive Blue 017 16 17 15 Bucket Brown 001 * 0 4 2 Reactive Red 123 16 10 13 Direct Blue 085 18 14 14 This paper size applies to Chinese National Standard (CNS) Λ4 specification (210 × 297 mm) 527453 A7 B7 V. Description of the invention 4) Table 9 Relative% reduction of dye DP tested Inhibitor 1 (A) Inhibitor 1 (B) TAED Reactive Blue 017 4 12 5 Bucket Brown 001 18 20 19 Reactive Red 123 26 19 7 Direct Blue 085 0 1 2 The results in Table 9 indicate that when the detergent used contains a manganese complex of formula (1) as a dye transfer inhibitor, the observed dyed cotton material and the use of a detergent containing TAED activated bleaching system are: Experiments have the same order. (Please read the notes on the back first

Order-line printed by the Central Bureau of Standards of the Ministry of Economic Affairs, employee consumer cooperatives to print the Λ application date Ί Κ η, ~ Case No. 8Τ 1 / Category Bu 1 b / CVyo (The above blocks are filled by the Bureau) A4 C4 527453 Signed | Patent Specification Chinese Invention A new type of method for inhibiting the reabsorption of migration dyes in lotions, used in the method ^ Compound and detergent composition containing the compound English A process for inhibiting the re-absorption of migrating dyes in the wash liquor, the compounds used in said process and the detergent composition comprising said compfoun · name, nationality, invention, creator, residence, domicile 1. Frank Bahaman 5. Coneria Macauca 2. Joseph Danaher 6. Peter Huai Gartner 3. Martin Stoud 7. Gritricht% 4. Beat Fleurmut 8. Gut Schlingerf 1.5.7. Germany 2.3.4.6.8. Switzerland 1. Germany 79106 Freiburg. 148 Renner Street 2. Switzerland 4053 Basel. 25 Bachaufen Street 3. Switzerland 4054 Basel. Gmenmenhof 2. France 68220 Boucherville-Vige 14 Norber Street 5. Germany 79725 Laufenburg. 14 Chevrolet Street No. 6. Digert, 4457, 87 Main Street, Germany 79395, Neuburg, No. 2 Strasmus Street-· Binding Name (Name) Nationality 8. Switzerland 4125 Lyon, 64 Teckberger Street Ciba Butter Chemicals Holding Company Switzerland Line Applicant Residence, Residence (Office) Representative Name Switzerland 4057 Basel City 141 Kruebe St. 1 Ernst Athal 2 Hans- The size of this paper is applicable to China National Standard (CNS) A4 (21〇 × ^ 7mm)

Claims (1)

527453 .4- 1. 1 C8 D8 (R) n · Patent application scope 1. A method for inhibiting the reabsorption of migration dyes in a lotion, which comprises introducing into the lotion containing a peroxide detergent one or more of 0.5 to 150 mg per liter of lotion having the formula Compounds (Please read the precautions on the back before transcribing this page) (2) Or where η is 1, 2 or 3; A is an anion; Rl is a gas or Cl-a radical 'Y is a linear or branched alkylene of formula-where m is an integer and ranges from 1 to 8, and each R i is hydrogen or OC4 alkyl, respectively; -CX = CX- where X is cyano, linear or branched C jl-C8 alkyl or di (linear or branched C 1-C 8 alkyl) amino group "- (CHbVNRKCtLV where Ri is hydrogen or CVC4 alkyl group and Q is 1, 2, 3 or 4; or U-cyclohexene or phenylene residue with the following formula: This paper size applies to China National Standard (CNS) A4 specifications (210 X 297 mm) A8B8C8D8 527453 6.Scope of patent application r7 or rK (please read the notes on the back before filling this page) where R7 is hydrogen, CH2OH or CH2NH2 or s〇3m, where μ is hydrogen, alkali metal atom, ammonium or cation formed by amine, R and R / is cyano; halogen; mesogen; 〇Ri or COOL where R 1 is hydrogen or C1-C4 alkyl; nitro; linear or branched or partially perfluorinated ◦ 1-C8 courtyard; Must be the same or different from R4 and hydrogen or linear or branched c 1 _C 1 2 alkyl; -N + HR4 where R i is hydrogen or OC4 alkyl, Rs and R4 · are the same or different and Hydrogen or linear or branched G-Cn alkyl, or linear or branched C 1 -C8 sub-radical 2 where R 2 is OR !, COOR1 or NR3R4, R 5 and R 6 are hydrogen respectively; linear or branched Branch C i ~ c 4 courtyard; unsubstituted aryl or square substituted with cyano, halogen, 0L or COO ^, nitro, linear or branched Ci-C8 courtyard, NR3R4 Are the same or different and are hydrogen or linear or branched C i -ci 2 courtyard; -N + R1R3R4 where R 1 is hydrogen or C1-C4 courtyard, R3 and r4 are the same or different and are hydrogen or linear respectively Or branch Cl_Cl2 courtyard, or Or M. C jl - C8 alkylene group -R2 wherein Rz is 〇Ri, (v) Xi bar or feet and feet but if NR3R4 j > are Ci - C4 alkyl time, each n is 1. 2. The method according to item 1 of the scope of patent application, wherein each liter of washing solution has one or more compounds of formula (1) or (2) from 1.5 to 75 mg per 2 D's scale applied to Chinese national standards ( CNS) A4 size (210 X 297 male) " 527453 028825 ABCD The scope of application is patented and introduced into the lotion. 3. The method according to item 2 of the scope of patent application, wherein one or more compounds of formula (1) or (2) from 7.5 to 40 mg per liter of lotion are introduced into the lotion. 4. The method according to item 1 of the scope of patent application, wherein the anion a is a dentate 'perchlorate, sulfate, nitrate, hydroxide, BF4 ·, PfV, or carboxylate. 5. The method according to item 4 of the scope of patent application, wherein the halide anion is chloride. 6. The method according to item 4 of the scope of patent application, wherein the carboxylate anion A is acetate, trifluoromethanesulfonate or tosylate. 7. The method according to item 1 of the scope of patent application, wherein Y is the formula _ [C (R〇2] 2 where is hydrogen or methyl, -CX = CX- where X is cyano,-where is hydrogen or methyl And Q is 1, 2, 3, or 4; or 1,2-cyclohexene or a phenylene residue having the formula: or 8. The method according to item 1 of the scope of patent application, wherein R or R / is ~ Methylamino, diethylamino, hydroxyl, methoxy, ethoxy, chlorine or nitro. 9-Method according to item 1 of the scope of patent application, wherein when n is 1, 'R or R / group It is at the 4-position of the individual benzene ring, but excludes that when the RSR > is nitro or Co2R2, the ruler or 11 > group is the 5-position of the individual benzene ring. This paper size applies the Chinese National Standard (CNS ) A4 size (210 X 297 mm) (Please read the precautions on the back before filling this page) 527453 A8 B8 C8 D8, patent application scope 10. The method according to item 1 of the patent application scope, wherein when η is 2, R or R / group is the 4,6-position of the individual benzene ring, but excludes when R or When R / is nitro or Co2R2, the R or R > group is at the 3,5-position of the individual benzene ring. 11. The method according to item 1 of the scope of patent application, wherein R or R > is-^ (Ci-Cl 2 · sinyl) amine. 12. The method according to item 11 of the application, wherein the alkyl portion of the di (C i -C i 2 alkyl) amino group contains 1 to 4 carbon atoms. 13. The method according to item 12 of the application, wherein the alkyl portion of the di (C i -C 12 alkyl) amino group contains 1 or 2 carbon atoms. 14. The method according to item 1 of the scope of patent application, wherein the compound of formula (1) is one or more compounds of the following formula (please read the precautions on the back before writing this page) (c2h5) 2n Cl ch9— ch9 (ch3) 2n N (CH3) 2 (1B) 4 This paper size is applicable to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) 527453 A8 B8 C8 D8 Patent application scope ch2-ch. OH (1C); wi 良 (c2h5) 2n Xi. , N = CH \ ^ \ .〇N (C2H5) 2 (1D) · (Please read the precautions on the back before writing this page) fcMn I Cl 15. —A detergent composition containing i) 5- 90% of A) anionic surfactant and / or B) non-ionic surfactant; ii) 5-70% C) synergist; iii) 0.1-30% D) peroxide; and iv ) 0.005-2% E) Compounds of formula (1) or (2) as defined in item 1 of the scope of the patent application, respectively, based on the weight of the total weight of the detergent. 16. The composition according to item 15 of the scope of patent application, which comprises i) 5-70% of A) anionic surfactant and / or B) non-ionic surfactant; ii) 5-50% of C) increase Auxiliary additives; This paper size applies Chinese National Standard (CNS) A4 specification (210 X 297 mm) A8B8C8D8 527453 6. Scope of patent application iii) M2% D) peroxide; and, iv) 0.02-1% E) The compounds of formula (1) or (2) according to item 1 of the scope of the patent application are based on the weight of the total weight of the detergent, respectively. a 17. The composition according to item 16 of the scope of the patent application, which includes i) 5-70% of A) anionic surfactant and B) non-ionic surfactant; ii) 5-40% of C) increase D) peroxides; and-, iv) 0 · 1-0 · 5% E) Shukang compounds of the formula (1) or (2) as defined in the first patent application scope, respectively, Based on the total weight of the detergent. 18. A composition according to item 15 of the scope of patent application, which comprises a combination of two or more compounds of formula (1) or (2) as defined by item 1 of the scope of patent application. 19. A composition according to item 15 of the scope of patent application, which comprises 0.5 to 5% by weight of a polymer useful for avoiding transfer of labile dyes between fabrics during a washing cycle. 20. The composition according to item 19 of the scope of patent application, which comprises 0.2-1.7% of a polymer. 21. The composition according to item 19 of the application, wherein the polymer is polyvinylpyrrolidone and optionally contains an anionic or cationic substituent. 22. The composition according to item 15 of the scope of patent application, in which the washing 6 ^ paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm) (Please read the precautions on the back before writing this page) , 1τί 527453 A8 B8 C8 D8, patent application scope agent is in powder or granular form. 23. A composition according to item 15 of the patent application, wherein the detergent is in a liquid form and contains 0-5% water. 24. According to the group of the scope of the applied patent No. 23, in which the washing is carried out; Lin Zhuan], shake 25. According to the scope of the patented scope of the No. 15 patent, the additional content agent is in a liquid form and contains 0-1 % Of water TAGU or TAED ΙίΛί 26.—Manganese complex of formula (3) or formula (2) R (R,) n ⑶ (2) (Please read the precautions on the back before writing this page), the word line where η is 1, 2, or 3; A is an anion; R and R / are cyano; halogen; hydroxyl; OR! Or 〇 ) 〇 仏 Among them, R 丄 This paper size is applicable to Chinese National Standard (CNS) A4 specification (210 X 297 mm) 527453 SI 6. The scope of patent application is hydrogen or Ci-c * courtyard; nitro, partial or perfluoro Linear or branched C 1 -C8 courtyard, NR3R4 where R3 and R4 are the same or not ^ and are hydrogen or linear or branched c!-Ci 2 alkyl; where R 1 is hydrogen or C1-C4 alkyl R3 and R4 are the same or different and are not hydrogen or a linear or branched CVCn alkyl group, or a linear or branched seven group: -c yenyl-R 2 where R 2 is OR !, C. 〇Ri or NR3R4, R i is hydrogen or C i -C4 alkyl, Y is -CX = CX- where X is cyano, where Ri is gas or C1-C4 and q is 1 '2' 3 or 4 ; ^ _ [c (p ^) 2] m is a linear or branched alkylene, where m is an integer and ranges from 1 to 8, and each R 1 is hydrogen or OC4 alkyl, but at least one R i Is ci-C + alkyl; or a 2-cyclohexene or phenylene residue having the formula: (Please read the notes on the back before filling this page) where R 7 is hydrogen, CH 2 0H or CHiNH 2 or SChM, where μ is hydrogen, alkali metal atom, ammonium or cation formed by amine, but 苕 R and r / All are C i -C * alkyl and Υ is an unsubstituted U-cyclohexene residue, each η is 1 ′, Υ is a linear or branched alkylene group of the formula-[ακ) 2μ, where m is Integer and range from 1 to 8, and each Ri is hydrogen or C ^ c4 radical respectively; -CX = CX- where X is amino 'linear or branched c 1-fluorenyl or di (linear or branched C i -c8 alkyl) amine group; 8 This paper size applies to Chinese National Standard (CNS) A4 specification (210 X 297 mm) 527453 A8 B8 C8 D8 6. Application scope-(CHUVNKCHOq-where Ri is hydrogen or OC4 alkyl And Q is 1, 2, 3 or 4; or 1,2-cyclohexene or a phenylene residue having the formula: Wherein R7 is hydrogen, CH2OH or CH2NH2 or SoM, where M is hydrogen, a metal atom, money or a cation formed by an amine, R5 and R6 are hydrogen respectively; linear or branched ci-c4 alkyl; Substituted aryl or cyano, halogen, OR! Or COOR !, nitro, linear or branched C 1 -C8 alkyl, NR3R4 substituted aryl, where R3 and R4 are the same or different and are hydrogen respectively Or linear or branched C i -C 1 2 alkyl; -N + RiR3R4, where Ri is hydrogen or C! -C4 alkyl, R3 and R4 are the same or different and are hydrogen or linear or branched CVCn alkyl , Or linear or branched Ci-C8 alkylene-R2 where R2 is OR !, COOR! Or NR3R4. 27.—A compound of formula (4) or formula (5), (Please read the precautions on the back before filling this page) 9 This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) 527453 A8 B8 C8 D8 (Please read the notes on the back before filling this page) where η is 1, 2 or 3; R and R > are cyano; halogen; hydroxyl; ORi or 0) 01 ^ where R i is hydrogen or C! -C4 alkyl; nitro; partially or fully fluorinated linear or branched C i -C8 alkyl; NR3R4 where R3 and R4 are the same or different and are hydrogen or linear or branched C 1-C 1 2 -N + RlR3R4 'wherein R 1 is hydrogen or C1-C4 radical, R3 and R4 are the same or different and are hydrogen or linear or branched Ci-Cn alkyl, or linear or branched C i-C8 Alkyl-R 2 where R 2 is ORi, C00R! Or NR3R4, R i is hydrogen or C i -C4 alkyl, Y is -CX = CX- where X is cyano,-(CH2) q-NRi- (CH2) q- where Ri is hydrogen or c! -C4 alkyl and q is 1,2,3 or 4; formula- [αι) 2μ linear or branched alkylene, where m is an integer and ranges from 1 To 8, and each Ri is hydrogen or C! -C4 alkyl, but at least one Ri is G-C4 alkyl: or 1,2-cyclohexene or phenylene residue having the formula: 10 This paper size applies to China National Standard (CNS) A4 specification (210 X 297 mm) 527453 A8 B8 C8 D8 6. Application scope of patent where R7 is hydrogen, CH2OH or CH2NH2 or SCbM, where M is hydrogen, alkali metal Atom, ammonium or cation formed by amine, but if R and R > are both C i _C4 alkyl and Υ is unsubstituted 1,2-cyclohexene residue, each η is 1, and Υ is of formula -[COl + K linear or branched alkylene, where m is an integer and ranges from 1 to 8, and each Ri is hydrogen or G-C4 alkyl, respectively; -CX = CX- where X is cyanide, Linear or branched C i -C8 alkyl or di (linear or branched C 1 -C 8 alkyl) amine;-(CH2) q-NRi_ (CH2) q- where Ri is hydrogen or Ci-C4 alkyl And Q is 1, 2, 3 or 4; or 1,2-cyclohexene or phenylene residue with the following formula: (Please read the precautions on the back before writing this page) Where R7 is hydrogen. 〇11 or 01 112 or 30 logic, where 1 ^ is hydrogen, alkali metal atom, ammonium or amine-forming cation, Rs and R 6 are hydrogen; linear or branched C 1 -C4 alkyl; Substituted aryl or aryl substituted with cyano, halogen, OR! Or COOR !, nitro, linear or branched C: -C8 alkyl, NR3R4, where R3 and R4 are the same or different and are hydrogen or Linear or branched C 1 -C i 2 alkyl; -N + LR3R4, where Ri is hydrogen or C1-C4 alkyl, R3 and R4 are the same or different and are hydrogen or linear or branched C! -Cn Alkyl, or linear or branched C i-C8 alkylene-R2 where Rz is, COOL or NR3R4 〇11 This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) 527453 A8 B8 C8 D8 Patent application scope 28.—A compound with the following formula This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) 527453 A8 B8 C8 D8 々, patent application scope (Please read the precautions on the back before writing this page), IT: 13 This paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm) 527453 A8 B8 C8 D8 (Please read the precautions on the back before copying this page) 14 This paper size applies to China National Standard (CNS) A4 (210 X 297 mm)