DE3731506A1 - Bleach - Google Patents

Description

The present invention relates to a bleach and a bleaching detergent used for bleaching fibers and Laundry, especially for washing and bleaching fibrous Products are suitable.

In the prior art, various connections, such as B. hypochlorite, bleaching powder, hydrogen peroxide, Hydrogen peroxide addition compounds, such as. B. Sodium percarbonate, persulfates, isocyanic acid hydrochloride and organic peroxides are used as bleaching agents. From these compounds damage hydrogen peroxide and Hydrogen peroxide addition compounds the colors of dyed and patterned laundry hardly and therefore used as a bleach for laundry. You will namely widely used to fade discolorations and blacks Stains from tea, fruit juice or cosmetic pro products were caused, applied, but possess such compounds have the disadvantage that their bleaching effects  generally low at low temperatures are.

To solve the above difficulty, ver proposed different procedures in which different Activators the bleach to achieve an effective Bleach added at low temperatures will.

Examples of such processes include a process where a complex, the EDTA and a heavy metal, like e.g. B. contains iron, manganese or cobalt, as an activator for Promote the decomposition of hydrogen peroxide used is (U.S. Patent No. 3 15 664) and a method in which a Compound, the peracetic acid when reacting with water fabric peroxide generated in a bleaching bath, d. H. Carbon acid anhydride (US-PS 23 66 401) or an N-acylite Ver binding (Japanese Patent Publication No. 10165/1963) is used. However, the process does uses a heavy metal complex, a low share effectiveness and shows when bleaching at low Temperatures have an insufficient effect. This points further Procedure using an additive of a vinegar acid-generating compound a high activation effectiveness, but has disadvantages in that when Removing stains such as B. tea or fruit juice stain the oxidative effect of those contained in the bath active oxygen species is too high and therefore the dye-dyeing substances based on colored and must have laundry, oxidized at the same time, which leads to color changes.

On the other hand, it is known that sodium N-chloroto luol-P-sulfonamide, which is an N-halosulfonamide derivative, for desizing and bleach cleaning of fibers is used (Japanese Unexamined Patent Publication No. 110979/1969). Furthermore, a process was initiated  proposed a compound that is a halogen ion generated such. B. hypochlorite or a halogenated Isocyanurate, which is added to the detergents, under Use of a sulfonamide derivative is stabilized (Japanese Unexamined Patent Publication 14299/1986). When these techniques are applied, is however, it is impossible to get a bleach that excellent bleaching effect at low temperatures shows, but the colors of dyed and patterned Laundry does not attack.

The present invention is therefore based on the object reason to provide a bleach that excellent when bleaching at low temperatures Has effect, but the colors of colored and barely affected clothes. This task and others Purposes of the present invention will become apparent from the following description clearly.

Hydroxyl radicals (· OH) and singlet oxygen (¹O₂) are known as active oxygen types, which from the Per oxide compounds are released and bleaching effects demonstrate. The inventors of the present invention have found that of these species · OH from the point of view of User created problems in that it is very high has an oxidative effect and both on the coloring sub punch high spots and stains Has bleaching effect, which leads to a change in color colored and patterned laundry. On the other hand also found that ¹O₂ is mild compared to · OH oxidative effect and a slight bleaching effect on the Has coloring dyes, but sufficient high bleaching effect on discolouring things like Stains. As a result of research based The above findings have now been found that with the combination of hydrogen peroxide or one Addition product thereof with a specific activator  effective singlet oxygen is generated, and this observation led to the present invention.

According to the present invention, a bleaching agent provided that includes:

• (A) hydrogen peroxide and / or a hydrogen peroxide Addition connection and
• (B) at least one activator which is an oxygen-containing heterocyclic compound in which the hydrogen atom of the secondary amino group is replaced by a halogen atom or a non-heterocyclic N-halo-amine compound, the hydrolysis constant of the activator being in the range from 1 × 10 ^-10 up to 5 × 10 ^-6 (at 25 ° C). A bleaching detergent is also provided which contains the agent described above.

The hydrogen peroxide addition compound from stock share (A) is a compound that contains hydrogen peroxide releases an aqueous bath. Examples of such Compounds include percarbonates, perborates, perphos phate and hydrogen peroxide addition compounds from Urea. Examples of such salts include sodium salts, potassium salts, lithium salts and calcium salts. Under these compounds will be sodium percarbonate or Sodium perborate is preferred.

The present invention is by combining one of the above-described hydrogen peroxide addition products of a mixture of two or more addition products and / or hydrogen peroxide with an activator as component (B), which is a nitrogen-containing heterocyclic compound in which the hydrogen atom the secondary amino group in the heterocycle is substituted by a halogen and which has a hydrolysis constant of 1 × 10 ^-10 to 5 × 10 ^-6 (at 25 ° C.). A preferred compound used as the nitrogen-containing heterocyclic compound (B-1) of the component (B) in which the hydrogen atom of the secondary amino group in the heterocycle is substituted by a halogen atom is a 1-halopiperidine derivative of the following formula (I ):

in which R₁ to R₆ are each hydrogen or an alkyl mean group and may be the same or different. R₁ and R₂ or R₃ and R₄ can be formed together of the following carbon rings to which they are attached are bound, be bound:

X₁ represents a halogen atom and Z represents a group of the following formulas:

where Y is an alkoxyl, hydroxyl or carboxyl group,

R₈ is an alkyl radical having 1 to 16 carbon atoms or phenyl; R₉ and R₁₀ can be the same or different and each C _m H _{2 m +1} , C _m H _{2 m} OH, C _m H _{2 m -1} (OH) ₂, C _m H _{2 m} COOM₁ (where M₁ H or an alkali means metal), or an alkanoyl group, R₁₁ and R₁₂ may be the same or different and each represents C _m H _{2 m +1} , C _m H _{2 m} OH or C _m H _{2 m} ; R₁₃ represents a hydrogen atom or C _m H _{2 m +1} ; m is an integer from 1 to 4 and A ^{- represents} an anionic radical, e.g. B. Cl ^-1 , CH₃COO or

Preferably, a 1-halopiperidine derivative of a ge hindered type of formula (I) used, wherein R₁ to R₄ each an alkyl group, R₅ and R₆ each a water substance atom and Z a group:

The use of a 1-halopipe is particularly preferred hindered derivative of the type (I) in which R₁ to R₄ each have a methyl group, R₅ and R₆ each is a hydrogen atom, X₁ is a chlorine atom, Z is the same

and Y is a hydroxyl group, a lower alkoxyl group,

mean.

Examples of the alkyl group in those described above Formulas belong to groups with 1 to 12 carbon atoms, preferably 1 to 4 carbon atoms, in particular a methyl group; and examples of the lower alkoxyl group include groups of 1 to 4 carbon atoms. Examples of the lower alkanoyl group include Groups with 2 to 8 carbon atoms.  

An example of the sugar residue is

The compound of formula (I) described above can e.g. B. made by the method described below will.

An amine compound used as a raw material (<NH) is dissolved in an inactive solvent and, if solid carbon dioxide is then necessary for the so obtained Solution added to produce the desired N-halo gene connection (<N-X). There is no particular limit for the active solvent used, if only does not participate in the reaction, but is preferred Examples of this solvent include water, Halogenated alcohols and mixed solvents Hydrocarbons and water.

Examples of halogenating agents include alkali or alkaline earth metal salts of subhalogenous acids.

The reaction temperature is in the range from 0 ° C to Room temperature and the time required for the reaction is in the range of 30 minutes to 5 hours.

After complete reaction, the desired product from the reaction mixture using conventional methods be won. For example, the water soluble organic solvents from the reaction mixture extra and the solvent can be dried of the extract obtained are removed to obtain the Product connection. If necessary, the ver binding then z. B. by acid chromatography, Destilla tion or recrystallization.  

The ammonium salt of the product compound can be dissolved that obtained by the method described above N-halogen compound in an inactive solvent and Reaction with an acid or an ester thereof be preserved.

There is no particular limitation on the inactive Solvent, provided it is not only in the reaction participates; to preferred examples of the solvent include alcohols such as B. methanol and ethanol. To complete reaction can the product compound from the Reaction mixture obtained by a conventional method will. For example, the product connection can be made after complete reaction by concentrating the solution be obtained by means of the reaction mixture, and if necessary, it can then be purified by recrystallization will.

Examples of the compound expressed by formula (I) are given below:
(1- (chloropiperidine derivatives) 1-chloropiperidine:

1-chloro-2,2,6-trimethyl-6-isobutylpiperidine:

1-chloro-4-oxo-2,2,6,6-tetramethylpiperidine:

1-chloro-4-oxo-2,2,6-trimethyl-6-n-hexylpiperidine:

6-chloro-6-aza-7,7-dimethyl-9-oxo-spiro [4.5] decane:

1-chloro-1-aza-2,2-dimethyl-4-oxo-spiro [5.5] undecane:

1-chloro-4-hydroxy-2,2,6,6-tetramethylpiperidine:

1-chloro-4-hydroxyimino-2,2,6,6-tetramethylpiperidine:

1-chloro-1-aza-2,2-dimethyl-4-hydroxyimino-spiro [5.5] undecane:

1-chloro-4-hydroxy-4-cyano-2,2,6,6-tetramethylpiperidine:

1-chloro-1-aza-2,2-dimethyl-4-hydroxy-4-cyano-spiro [5.5] undecane:

1-chloro-4-amino-4-cyano-2,2,6,6-tetramethylpiperidine:

1-O- (1′-chloro-2 ′, 2 ′, 6 ′, 6′-tetramethyl-4′-piperidyl) glycoside:

1-chloro-2,2,6,6-tetramethyl-4-piperidyl phosphate:

1-chloro-2,2,6,6-tetramethyl-4-isothiocyanatopiperidine:

1-chloro-4- [N- (2-hydroxyethyl) methylamino] -2,2,6,6-tetramethylpiperidine:

1-chloro-4- [N- (2,3-dihydroxypropyl) methylamino] -2,2,6,6-tetramethylp-iperidine:

1-chloro-4- [N- (2-hydroxyethyl) butylamino] -2,2,6,6-tetramethylpiperid-in:

1-chloro-4- [N- (2,3-dihydroxypropyl) butylamino] -2,2,6,6-tetramethylpiperidine:

1-chloro-4- [N, N-bis (2-hydroxyethyl) amino] -2,2,6,6-tetramethylpiperid-in:

1-chloro-4- [N- (2-hydroxyethyl) -N- (2,3-dihydroxypropyl) amino] -2,2,6,6-- tetramethylpiperidine:

1-chloro-4- [N-acetyl-N-methylamino] -2,2,6,6-tetramethylpiperidine:

1-chloro-4- [N-acetyl-N-butylamino] -2,2,6,6-tetramethylpiperidine:

Trimethyl- (1-chloro-2,2,6,6-tetramethyl-4-piperidyl) ammonium - paratoluosulfonate:

Dimethyl- (1-chloro-2,2,6,6-tetramethyl-4-piperidyl) ammonium - chloride:

Dimethyl-1 (1-chloro-2,2,6,6-tetramethyl-4-piperidyl) ammonium acetate:

Methyl- (2-hydroxyethyl) - (1-chloro-2,2,6,6-tetramethyl-4-piperidyl) - ammonium chloride:

Di (2-hydroxyethyl) - (1-chloro-2,2,6,6-tetramethyl-4-piperidyl- ammonium chloride:

Dimethyl-benzyl- (1-chloro-2,2,6,6-tetramethyl-4-piperidyl) - ammonium bromide:

Spiro [4.4] -8-chloro-2-hydroxymethyl-7,7,9,9-tetramethyl-8-aza-1,4- dioxadecan:

1-chloro-4-methoxy-2,2,6,6-tetramethylpiperidine:

1-chloro-4- [N, N-bis (sodium oxycarbonylmethyl) amino] -2,2,6,6- tetramethylpiperidine:

(Morpholine derivatives :)
1-chloromorpholine:

(Diazacycloheptanone derivatives)
1-chloro-2,2,7,7-tetramethyl-1,4-diazacycloheptan-5-one:

These compounds are made up individually or as a mixture two or more connections are used. From the above Compounds described are preferred compounds: 1-chloro-piperidine, 1-chloro-2-methylpiperidine, 1-chloro-3,5-dimethylpiperidine, 1-chloro-isonipeconic acid, 1-chloromorpholine, 1-chloro-caprolactam, 1-chloro-hexamethyleneimine, 1-chloro-4-, N-2,3-dihydroxypropyl) butylamino.-2,2,6,6- tetramethylpiperidine, 1-chloro-4-, N, N, -bis (sodium oxycarbonylmethyl) amino.-2,2,6,6-tetramethylpiperidine, Spiro, 4.5-8-chloro-2-hydroxymethyl-7,7,9,9-tetramethyl- 8-aza-1,4-dioxadecane,  1-chloro-4-methoxy-2,2,6,6-tetramethylpiperidine, 1-chloro-4-hydroxy-2,2,6,6-tetramethylpiperidine, 1-chloro-4-, N- (2-hydroxyethyl) methylamino.-2,2,6,6- tetramethylpiperidine, 1-chloro-4-, N- (2,3-dihydroxypropyl) methylamino.-2,2,6,6-tetramethylpiperidine, 1-chloro-4-, N, N-bis (2-hydroxyethyl) amino.-2,2,6,6- tetramethylpiperidine or trimethyl- (1-chloro-2,2,6,6- tetramethyl-4-piperidyl) ammonium paratoluenesulfonate. Among these compounds, the following are particularly preferred: 1-chloro-hexamethyleneimine, 1-chloro-4-hydroxy-2,2,6,6- tetramethylpiperidine, 1-chloro, N- (2-hydroxyethyl) methylamino.-2,2,6,6- tetramethylpiperidine, 1-chloro-4-, N- (2,3-dihydroxypropyl) methylamino.-2,2,6,6-tetramethylpiperidine, 1-chloro-4-, N, N-bis (2-hydroxyethyl) amino.-2,2,6,6- tetramethylpiperidine and trimethyl- (1-chloro-2,2,6,6- tetramethyl-4-piperidyl) ammonium paratoluenesulfonate.

Furthermore, the N-halogen-hindered amine compound (B-2) as component (B) the hindered amine compound following formula (II) or (III), in which at least one Hydrogen atom of the amino group through a halogen sub is constituted:

wherein R₂₁, R₂₂ and R₂₃ each -COOH, -C _n H _{2 n +1} , -C- (C _n H _{2 n +1} ) ₃, -C _n H _{2 n} OH, -CH₂-C- (C _n H _{2 n +1} ) ₃, -C _n H _{2 n} COOH, -OC _n H _{2 n +1} or -COOR₂₅ mean (where R₂₅ represents an alkyl group with 1 to 9 carbon atoms), R₂₄ means, -H, -OH , -F, -Cl, -Br, -I, -C _n H _{2 n +1} , -C- (C _n H _{2 n +1} ) ₃, -C _n H _{2 n} OH, -CH₂, -C- (C _n H _{2 n +1} ) ₃, -C _n H _{2 n -1} (OH) ₂, -C₂H₄O) _n H, -C _n H _{2 n} COOH, -C _n H _{2 n} COOR₂₆ (where R₂₆ is an alkyl group with 1 to 9 carbon atoms means), -C _n H _{2 n} -SO₃M₂, -C _n H _{2 n} OSO₃M₂, C _n H _{2 n} PO₃, H or -C _n H _{2 n} CB; n is an integer from 1 to 9; M₂ is H or an alkali metal and X₂ means a halogen atom.

For examples of compound (B-2) with the above be written formula include the following N-halo-t-alkyl amines and their derivatives:  

3- (N-chloro-t-butylamino) -1-methyl-1,2-propanediol:

3- (N-chloro-t-butylamino) -1,1-dimethyl-1,2-propanediol:

These compounds are used individually or as a mixture of two or more connections are used. Among the above Compounds described are preferred compounds: N-chloro-t-butylamine, 2- (N-chloro-t-butylamino) ethanol, 3- (N-chloro-t-butylamino) -1,2-propanediol, 2- (N-chloro-t-butylamino) acetic acid and 2- (N-chloro-t-butylamino) methanesulfonic acid. The verb Applications (B-1) and (B-2) can be used in combination will.

These compounds (B-1 and B-2) are characterized records that it is the part bulky chemical Have structure adjacent to the H-halo amino group, such as is shown in the examples described above.

The amount of the activator used as component (B) is preferably 0.05 to 4.0 mol, in particular 0.1 up to 1.5 moles, based on one mole of water used peroxide or the hydrogen peroxide that comes from the generated hydrogen peroxide addition product has been.

It is believed that the excellent effects that are shown by the bleaching agent according to the invention, are based on the following functional mechanism:

The activator of the present invention is hydrolyzed in water and releases ions of hypohalous acid (OX ^- ) according to the following equation (1):

N-X + H₂O → N-H + OX ^- + H⁺ (1)

OX ^- then reacts with hydrogen peroxide, which is simultaneously present in water, with release of ¹O₂ according to the following equation (2):

OX ^- + H₂O₂ → X ^- + H₂O + ¹O₂ (2)

Since the ¹O₂ released here has a very short lifespan of a few microseconds in water and is inactivated to oxygen in the ground state (³O₂), which has a limited bleaching effect, the reaction according to equation (2) must take place continuously in order to release ¹O₂ at a reasonable rate to bleach stains in laundry during the time it takes to bleach. Therefore, the hydrolysis constant (Kh) of an organic chlorine compound subjected to hydrolysis according to equation (1) must be in the range of values which is not too large and the whole concentration of OX ^- in a bath must be kept at an appropriate value . If e.g. B. a dichloroisocyanurate, which is an organic chlorine compound with a high hydrolysis constant (Kh), the ¹O₂ released is largely inactivated and thus shows no satisfactory bleaching effect, since the rate of production of ¹O₂ is too high.

In the same way, the reaction of an organic chlorine compound with an appropriate hydrolysis constant (Kh) with hydrogen peroxide can release at an appropriate rate ¹O₂, which has a high degree of decolorization for the coloring elements of stains and a low degree of discoloration of coloring elements. Component (B) which is used according to the invention preferably has a hydrolysis constant (Kh) of 1.0 × 10 ^-10 to 5.0 × 10 ^-6 (at 25 ° C.), in particular 1.0 × 10 ^-8 to 1.0 × 10 ^-6 ( at 25 ° C).

The hydrolysis constant of compound (B) can e.g. B. after the method described in J. Chem. Soc., 127, 98 (1925) be measured.

The principle of this method is described below.

If the precursor amine of a chloroamine, its Kh too is measured, a solution of dichloramine T with a known hydrolysis equilibrium constants in one Condition of the dissolution equilibrium is added the chloroamine in the solution so that it produces dichloro amine T displaced from the dissolution equilibrium and in maintains a new state of equilibrium. If the conc chloride after iodine staining The method obtained is titrated, the concentration obtained Chloride as follows:

2 a + b + x = T / 2 (3),

where a is the concentration of unhydrolyzed dichloroamine T, b is the concentration of monochlorosulfone amide, x is the concentration of chloroamine produced and T is the amount of sodium thiosulfate required for the titration.

Therefore, the increase S of the titration value generated by the addition of the precursor amine is expressed by the following equation:

S = b + x = T / 2-2 a (4)

The hydrolysis constants K₁, K₂ in the first and second Stage of dichloramine T are known, as in J. Chem. Soc., 125, 1899 (1924).  

where h is the concentration of HC10 and c is the concentration of sulfonamide.

From equations (5) and (6) the following equation can be made will be obtained:

On the other hand, a , which is the saturation solubility of dichloramine T , can be measured:

a = 0.97 × 10 ^-3 (M) (8)

Since x is equivalent to the concentration of HC10 produced from dichloramine T , the following also applies

x = b + 2 c (9)

From equations (4) to (9) one obtains:

b ² + 15.84 × 10 ^-3 b - 7.92 × 10 ^-3 S = 0 (10)

Since s can be measured and b, x and h can be obtained from equations (10), (4) and (5) respectively, the searched Kh of chloramine is expressed by the following equation (11):

wherein d can be obtained from the concentration of the amine precursor added.

A solution is preferably used in which the Component (B) in an amount of 0.01 g or more preferably 0.1 g or more, in particular 1 g or more, based on 100 g of a 0.01% aqueous solution of Constituent (A) is solved.

The bleaching agent according to the invention can be used as such or can be used as a bleaching agent in a mixture with commonly used components. In this case, the addition of 1 to 5% of a surfactant, such as. B. Polyoxyethylene nonylphenyl ether (average oxyethylene chain length p = 5 to 30) with advantage to promote the penetration of sheet metal components in laundry in water and improve the effect of stain removal.

Furthermore, the bleaching agent according to the invention can be used as Bleaching effect of granular detergent components be added. In other words, the bleaching can medium desirably as a bleaching detergent 0.1 to 0.3% by weight of component (A), 0.1 to 0.3% by weight of the Component (A), 0.1 to 30% by weight of component (B), 0.1 to 50% of at least one surfactant from the group Anio surfactants, nonio surfactants and ampholytic surfactants, as well as commonly used components, such as. B. Zeolite, an alkali picture, a perfume and a color contain fabric.

If further the bleaching agent according to the invention one enzyme-containing detergent is added, the Dirt, e.g. B. Protein removing effect by Enzyme effect that affects the item to be washed achieved, which makes it an excellent bleaching effect can be held. Because alkali protease that in the on  industry related to this invention to a large extent is known to be inactivated by active chlorine it is difficult to say that the one in the Activator preferably used for the present invention is an enzyme when used alone. It was however found that a system of the present invention where the activator in combination with water Peroxide is used, only a slight disadvantage Has an influence on an enzyme and is adequate Has bleaching effect.

Examples of the anio surfactants described above include chain-shaped alkylbenzenesulfonates, in which the Alkyl has 9 to 15 carbon atoms (C), alkyl sulfates (in particular C₁₀ to C₂₂), olefin sulfonates (in particular C₁₀ to C₂₄), alkane and / or hydroxyalkanesulfonates (in particular C₁₀ to C₂₄). Alkylphenoxy ether sulfates (In particular with C₈ to C₁₂ alkyl groups and 1 to 10 Ethylene oxide units), alkyl ether sulfates (in particular with C₁₀ to C₂₀ alkyl groups and 1 to 10, preferably 2 up to 4 ethylene oxide units), and mixtures of one or several types of soap (especially C₁₂ to C₂₀).

Examples of nonionic surfactants include the condensate tion products of ethylene oxide and propylene oxide (more typical example 5 to 30 units) and aliphatic or aromatic alcohols or aliphatic amines or amides. Among these substances have aliphatic compounds preferably C₈ to C₁₂ chains in their hydrophobic ali have phatic proportions and aromatic compounds preferably alkyl aromatic groups with C₆ to C₁₂- Chains.

Examples of the ampholytic surfactants include water soluble derivatives of cationic aliphatic quaternary ammonium, phosphonium and sulfonium compounds bonds, each containing the aliphatic portion  is a straight or branched chain, a substituent C₈ to C₁₈, and an anionic water-soluble Group, especially a sulfonate group, at one end is present, such as. B. alkyl hydroxy propane sulfonates and Alkyl dimethyl ammonium hydroxypropane sulfonates.

Examples of the detergent builders include sodium sulfate, sodium carbonate, sodium silicate, sodium pyro phosphate, sodium tripolyphosphate, nitriloacetic acid and their water-soluble salts, sodium ethylenediaminetetra acetate and various aluminosilicates, such as. B. Zeolite A. In this context, the bleach detergent contains preferably a builder in an amount of 5 to 90 % By weight.

Typical examples of enzymes include protease, such as e.g. B. Alkalase, produced by Novo Corp., Esperase, Sabinase and alkali cellulase. In this regard, it can Bleach detergent is an enzyme in an amount of 0.01 to Contain 10% by weight.

The bleaching process involves dissolving or dispersing yaw the agent in water and immerse the textile weave in the solution. The amount of bleach used medium can match the desired degree of bleaching to get voted. In addition, a temperature in the Range from 20 to 40 ° C, however, can of course a temperature above 40 ° C can be used.

The present invention can be excellent Bleaching effect at a relatively low temperature and is extremely suitable for household laundry, since they have no discoloration of colored and patterned Laundry produces what you experience when conventional Activators are used. Furthermore, since the present Invention not only free from any tendency to produce discoloration of colored and patterned laundry,  but can bleach textile fibers or cellulose fibers, while reducing embrittlement at the same time, it is for bleaching industrial threads and fabrics and for Suitable for bleaching in paper manufacturing processes.

It is therefore obvious that the inventive Bleach can be used widely and also suitable for use as a bleach for laundry are. This bleach is also an additive for ver different detergents can be used.

The present invention will now be illustrated by examples described, although not on these examples is limited.

Manufacturing examples

Examples of the various preferred activators, which are used in the present invention described below.

Production Example 1 1-chloro-4-, N, N-bis (2-hydroxyethyl) amino.-2,2,6,6, -tetramethylpiperidine

3.82 g of 4-N, N-bis (2-hydroxymethyl) amino-2,2,6,6-tetra methyl piperidine are in a mixed solvent dissolved from 30 ml dichloroethane and 10 ml H₂O and 1.85 g Calcium hypochrorite (bleaching powder) gradually becomes the obtained solution added with stirring and ice cooling.

0.85 g of solid carbon dioxide was then added to the mixture sets, followed by stirring at 0 ° C for 15 minutes and then at room temperature for one hour. After full constant reaction, the reaction mixture with Extracted dichloromethane and then the organic layer  dried with sodium sulfate. The oily substance that by distilling off dichloromethane from the organic Layer obtained was a silica gel column subjected to chromatography (extractant: ethyl acetate: triethylamine = 30: 1). The product was then from a mixed solution of hexane and ether (10: 1) recrystallized; the desired substance was obtained as Crystals with a melting point of 54 to 56 ° C.

The corresponding amine compounds were subjected to the reactions described above, and the crude products obtained were each purified by column chromatography and, if necessary, by distillation and recrystallization, thereby containing the desired substances described below.
1-Chloro-4-N- (2-hydroxyethyl) methylamino-2,2,6,6-tetramethylpiperidine: F = 37-39 ° C
1-Chloro-4-N- (2,3-dihydroxypropyl) methylamino-2,2,6,6-tetramethylpiperidine: F = 106-107 ° C
1-Chloro-4-N- (2,3-dihydroxypropyl) butylamino-2,2,6,6-tetramethylpiperidine: TLC Rf = 0.46
(Silica gel, ethyl acetate: ethanol: triethylamine = 20: 1: 1)
Spiro-4.5-8-chloro-2-hydroxymethyl-7,7,9,9-tetramethyl-8-aza-1,4-dioxadecane: TLC Rf = 0.34
(Silica gel, ether: hexane = 2: 1)
1-chloro-4-methoxy-2,2,6,6-tetramethylpiperidine: TLC Rf = 0.42 (silica gel, hexane: ethyl acetate = 10: 1)
3- (N-Chloro-N-cyclohexylamino) -1,2-propanediol: F = 55-57 ° C
3- (N-Chloro-Nt-butylamino) -1,2-propanediol: F = 72-73.5 ° C

Production Example 2 1-chloro-4-N, N-bis (sodium oxycarbonylmethyl) amino 2,2,6,6-tetramethylpiperidine

0.78 g of sodium hydroxide and 3.41 g of 1-chloro-4-N, N-bis (ethoxycarbonylmethyl) amino-2,2,6,6-tetramethylpiperidine obtained from 4-N, N-bis (ethoxycarbonylmethyl) amino - 2,2,6,6-tetramethylpiperidine according to the same procedure as used in Preparation Example 1 was dissolved in 30 ml of ethanol and the mixture was then stirred at room temperature for 15 hours. The insoluble substance obtained was filtered off, washed with ethanol and then with diethyl ether and then dried under reduced pressure. The desired substance was obtained in the form of crystals, which showed the characteristic IR absorption at 1598 cm ^-1 and 1428 cm ^-1 (absorption of -COO ^- ).

Production Example 3 Trimethyl- (1-chloro-2,2,6,6-tetramethyl-4-piperidyl) ammonium paratoluenesulfonate

1.57 g methyl paratoluenesulfonate and 1.79 g 1-chloro-4- dimethylamino-2,2,6,6-tetramethylpiperidine obtained from 4-Dimethylamino-2,2,6,6-tetramethylpiperidine according to the same method as in Preparation Example 1, were in 16 ml of methanol dissolved and the mixture then at room temperature temperature stirred for 15 hours. After more complete Reaction became the crystals by distilling off of methanol were obtained from the reaction mixture, by recrystallization from the methanol-diethyl system Ether cleaned; the desired substance was obtained in Form of crystals with a decomposition point at 202 up to 204 ° C.  

Examples

The following is the process of forming ver dirty cloth and stained cloth and the process for Measurement of the bleaching effect and the degree of discoloration, the in the examples and comparative examples according to the present invention have been described.

Formation of dirty cloth

Ten pieces of cotton cloth (pre-treated cloth, 20 × 30 cm), that had been cleaned by desizing placed in a dirt solution consisting of 20 g black Tea with 1 liter of water that boiled for 5 minutes extracted and then boiling for 30 minutes stained. Every dirty cloth was wrung out, dried with air and then cut into pieces of each Size 5 × 5 cm cut, which then ver in bleaching tests were applied.

Formation of colored cloth

0.75 g of a dye (C.I. No. Reactive Red-21) and 13.5 g of anhydrous sodium sulfate were placed in 450 ml of water dissolved and three pieces of cotton cloth (20 × 30 cm), the had been cleaned by desizing color solution obtained. The solution was 20 minutes held at 60 ° C for a long time and then 9 g of sodium were added carbonate added; then it became 60 minutes kept at 60 ° C for a long time. The tissue pieces were then made with Washed water and then with an aqueous 0.1% Acetic acid solution, in an aqueous 0.2% aniote dried for 5 minutes, washed with water, dried and then into pieces each 5 × 5 cm in size cut, which then used in the discoloration tests were.  

Bleaching tests (I) bleach

Predetermined amounts of hydrogen peroxide or one Hydrogen peroxide addition product and an activator were dissolved in 200 ml of water at 25 ° C. Five pieces of tissue contaminated with black tea were in put this water bath and then the for 30 minutes Subjected to bleaching treatment. The towels were then with Water washed and dried; bleached was obtained Cloths. The degree of reflection from each pretreated Cloth, cloth soiled with black tea and ge bleached cloth were made using a fotoelek trical reflectance meter (ELREPHO, provided by Carl Zeiss Co., Ltd.), measured and its bleaching ratio (%) was obtained by the equation (12) given below.

(II) bleaching detergent

A bleaching detergent became water with a hardness of 3 ° DH added at 25 ° C so that the concentration became 0.8% and a cloth soiled with black tea was put in it Water bath immersed in a bath ratio of 50 times and then left for 30 minutes. A clean one Knitted cotton and water with a hardness of 3 ° DH 25 ° C was then added to the water bath and the bath ratio and the concentration of detergent were set to 30 times or 0.15%, followed by washing with a Terg-O-Tometer (manufactured by U.S. Testing Co., Ltd.) for 10 minutes at 120 rpm. The pieces on Test wash treated this way was one minute dried long, with running water for one minute rinsed, dried again for a minute and then dried by ironing to bleached towels.

The degree of reflection of the pretreated wipes, with  black tea spotted towels and bleached towels was made using a photoelectric reflect tion knife (ELREPHO, manufactured by Carl Zeiss Co., Ltd.), measured and their bleaching ratio by the obtain the following equation (12):

If in this test the bleaching ratio increases by 5% could improve the white color itself can be observed with the naked eye and therefore could an improvement in the practical bleaching effect be achieved.

Method of measuring discoloration (I) bleach

Use the same bleaching bath as that in the bleaching test dete was made and then two colored pieces of cloth placed in the bath followed by bleaching treatment during 30 minutes. The towels were then washed with water and dried with air and their brightness and hue were then using a differential colorimeter (DICOM model ND504DE manufactured by Nihon Denshoku-kogyo Co., Ltd.). The degree of Discoloration was obtained from the following equation (13):  

in which mean:
Δ L: change in brightness before and after bleaching the fabrics
Δ a, Δ b: change in hue before and after bleaching the fabrics.

(A larger value for a means a reddish shade and a smaller value means a more thorough shade. A larger value for b means a yellow shade and a smaller value means a blue shade.)

If in this test the degree of discoloration is 10 or more was able to discolor itself Observation with the naked eye and therefore, a strong discoloration was really achieved.

(II) bleaching detergent

A colored piece of fabric was made at the four corners Attached needles. 0.5 g of each of the bleaching detergents Examples and comparative examples were made on this cloth sprinkled and water was then sprayed onto it. To Allow to stand for 15 minutes with water washed and then air dried. After drying the condition of the cloth was based on the under be written criteria evaluated for the purpose of measuring the Discoloration.

3 points: the one with the respective bleaching detergent in Contact parts became noticeable  discolored and many spots were observed. 2 points: in contact with any bleaching detergent standing parts were discolored and stained were clearly observed. 1 point: those in contact with the respective bleaching Detergent parts were minor discolored and few spots were observed. 0 points: those in contact with the respective bleaching Detergent parts were at all not discolored and no stains were too observe.

Example 1

The bleaching and decolorization tests were carried out using sodium percarbonate as a hydrogen peroxide addition compound and each of the various 1-chloro-stick containing heterocyclic compounds as an activator in accordance with the procedure described above. The total concentration at each activator and hydrogen peroxide generated from sodium percarbonate was 3.7 × 10 ^-2 mol / l and the ratio of these compounds is given in Table 1. The results obtained are shown in Table 1.

Table 1

As can be seen from Table 1, the comparison showed example in which no activator was used (No. 1), the means in which organic chlorine compounds with large hydrolysis constants used as activators were (No. 17 to No. 19), and the mean in which Tetraacetyl-glycoluril (TAGU), which forms peracetic acid, was used as an activator (No. 20) with respect to Comparative examples (No. 17 to 19) only slight discoloration of the dye, but a weak bleaching effect and the comparative example (No. 20) showed the examples (No. 17 to 19) opposite properties. However the agents according to the invention showed high bleaching effectiveness and only slight discoloration of the dye.

Example 2

A bleaching test was carried out in the same manner as in Example 1 carried out, however, as an activator of the compound (B) each the 1-chloro stick listed in Table 2 substance-containing heterocyclic compound was used. The results are shown in Table 2.  

Table 2

As can be seen from Table 2, each of the means showed Nos. 2 to 12, for the sodium percarbonate and the respective Activator in combination based on the present Invention were used excellent Bleaching effect and a low degree of discoloration compared with agent No. 1, in which no activator ver was applied and means No. 13, in which only one activator has been used.

Example 3

A bleaching test was carried out in the same manner as in Example 1 made, but each different organic Chlorine compounds of the N-chloro type were used. The Results obtained are summarized in Table 3 posed.  

Table 3

As can be seen from Table 3, the agents according to the invention, in which the respective activators were used together with sodium percarbonate, showed a high bleaching efficiency in comparison with the comparative example (No. 1), in which no activator was used. It was also found that agent # 9 using only the activator, agents # 23 and 25 using amines without a hindered amine structure as activators, agent # 26 in which tetraacetylglycoluril (TAGU ), which produces peracetic acid as an activator, and Compound No. 27, in which an activator with a hydrolysis equilibrium constant of 2.5 × 10 ^-5 producing a halogen acid was used, showed little bleaching efficiency and a high degree of discoloration, so that no good effects could be achieved. However, the agents according to the invention were able to maintain their bleaching effectiveness to a high degree and showed only little discoloration.

The hydrolysis constants of those used in Example 3 Compounds are given in Table 4.  

Table 4

Example 4

The bleaching detergents of Sample Nos. 1 to 7 shown in Table 6 were each made by mixing the granular detergent having the composition shown in Table 5, sodium perborate as a hydrogen peroxide addition product, and any heterocyclic compound containing 1-chloro-nitrogen as an activator in powder form were formed and the bleaching and discoloration tests were carried out using these agents. The results obtained are summarized in Table 6.
Ingredient content
(% By weight) LAS-NA ^{* 1} ) 10 AOS-Na ^{* 3} ) 10 zeolite (Type 4A) 16 sodium silicate 10 sodium carbonate 10 Thinopearl CBS-X ^{* 4} ) 0.2 enzyme (Alkalase 2.OT) ^{* 5} ) 0, 4 water 5 sodium sulfate residue

* 1) Sodium straight chain alkylbenzenesulfonate in which the alkyl has 12 carbon atoms. * 2) Sodium alkyl sulfate with 10 to 16 carbon atoms. * 3) Sodium α- olefin sulfonate with 14 to 18 carbon atoms. * 4) An optical brightener of the distyrylbiphenyl type. * 5) The enzyme was powder mixed after spraying and drying.

Table 6

Example 5

The bleaching detergents were prepared in the same way as in Example 4 prepared, however, that in Table 7 activators listed instead of the ver in Example 4 Activators were used and the bleaching tests have been carried out on these funds. The results are included in Table 7.  

Table 7

Example 6

The granular detergents having the compositions shown in Tables 8 and 9 were prepared and 5% sodium perborate monohydrate and 1-chloro-4-hydroxy-2,2,6,6-tetramethylpiperidine were added to each detergent to form a bleach detergent . The bleaching and staining tests were carried out by any means.
Ingredient content
(% By weight) LAS-NA7.0 fatty alcohol ethoxylate ^{* 1} ) 2.5 sodium soap ^{* 2} ) 2.5 sodium tripolyphosphate36 sodium silicate6 ethylene diamine tetraacetate (EDTA) 0.1 Thinopearl CBS-X0.2 sodium carboxymethyl cellulose 0.5 water 8 sodium sulfate residue

* 1) Fatty alcohol ethoxylate, where the alcohol has 16 to 18 carbon atoms and EO P = 7. * 2) Sodium salt of a fatty acid with 16 to 18 carbon atoms. Ingredient content
(% By weight) LAS-Na12 As-Na5 AES-Na ^{* 1} ) 5 zeolite12 sodium silicate15 sodium carbonate3 Thinopearl CBS-X0.2 water5 sodium sulfate residue

* 1) Sodium alkyl ether sulfate with 12 to 15 carbon atoms and EO P = 3.

When adding a hydrogen peroxide addition product and an activator according to the present invention the granular given in Tables 8 and 9 Detergent bases became an excellent bleaching agent hold and excellent decolorization properties shown that of agent No. 1 given in Table 6 were the same.

Example 7

Bleaching detergents were prepared in the same way as in the Examples 4 and 6, but using sodium per carbonate as a hydrogen peroxide addition compound ver was applied. When performing the bleaching and decolorization Practice tests of the funds formed were excellent Observe effects related to each activator used tet.  

Example 8

A bleaching detergent was made in the same manner as in Example 5, but the sodium percar bonat used instead of sodium perborate monohydrate was used and N-chloro-t-butylamine as an activator has been. When performing the bleach test with this agent same effects as in No. 1 of Example 5 aims.

Claims (16)

1. Bleach containing:

• (A) hydrogen peroxide and / or a hydrogen peroxide addition compound, characterized by a content of
• (B) at least one activator which is a nitrogen-containing heterocyclic compound in which the hydrogen atom of the secondary amino group is substituted by a halogen atom or a non-heterocyclic N-halogen hindered amine, the hydrolysis constant of the activator being in the range of 1 × 10 ^-10 up to 5 × 10 ^-6 (at 25 ° C).

2. Bleaching agent according to claim 1, characterized in that that the activator is a 1-halopiperidine derivative is.   3. Bleaching agent according to claim 2, characterized in that the activator is a 1-halopiperidine derivative of the following formula (I): in which R₁ and R₆ each represent hydrogen or an alkyl group and are identical or different, R₁ and R₂ or R₃ and R₄ are bonded together to form the following rings under the influence of the carbon atoms to which they are attached: X₁ is a halogen atom and Z is a group of the following formula: where Y is an alkoxyl, hydroxyl or carboxyl group, or R₈ is an alkyl of 1 to 16 carbon atoms or phenyl; R₉ and R₁₀ can be the same or different and each C _m H _{2 m +1} , C _m H _{2 m} OH, C _m H _{2 m -1} (OH) ₂, C _m H _{2 m} COOM₁ (where M₁ H or an alkali metal means) or an alkanoyl group; R₁₁ and R₁₂ are the same or different and each represents C _m H _{2 m +1} , C _m H _{2 m} OH or C _m H _{2 m} ; R₁₃ represents a hydrogen atom or C _m H _{2 m +1} ; m is an integer from 1 to 4 and A ^{- is} an anionic radical. 4. Bleaching agent according to claim 3, characterized in that the 1-halopiperidine derivative is of the hindered type of the formula (I), in which R₁ to R₄ are each an alkyl group, R₅ and R₆ are each a hydrogen atom and Z: mean. 5. Bleaching agent according to claim 3 and / or 4, characterized in that the 1-halopiperidine derivative is of the hindered type of formula (I) in which R₁ and R₄ each have a methyl group, R₅ and R₆ each have a hydrogen atom, X₁ chlorine, Z and Y is a hydroxyl group, a lower alkoxyl group, 6. bleaching agent according to one of claims 1 to 5, characterized in that the activator is a ver bond or a mixture of 2 or more compounds the group 1-halopiperidine derivatives, 1-halohexa methyleneimine derivatives and 1-halodiazacycoheptonone Is derivatives. 7. Bleaching agent according to one of claims 1 to 6, characterized in that the non-heterocyclic N-halo hindered amine compound is a compound of the following formulas (II) or (III): wherein R₂₁, R₂₂ and R₂₃ each -COOH, -C _n H _{2 n +1} , -C- (C _n H _{2 n +13} ), C _n H _{2 n} OH, -CH₂-C- (C _n H _{2 n -1} ) ₃, -C _n H _{2 n} COOH, -OC _n H _{2 n +1} or -COOR₂₅ (in which R₂₅ represents an alkyl group with 1 to 9 carbon atoms), n is an integer from 1 to 9, R₂₄ -H, -OH, -F, -Cl, -Br, I, -C _n H _{2 n +1} , -C- (C _n H _{2 n +1} ) ₃, -C _n H _{2 n} OH, -CH₂-C- (C _n H _{2 n -1} ) ₃, -C _n H _{2 n -1} (OH) ₂, - (C₂H₄O) _n H, -C _n H _{2 n} COOH, -C _n H _{2 n} COOR₂₆ (where R₂₆ is one Alkyl group having 1 to 9 carbon atoms means -C _n H _{2 n} -SO₃N₂, -C _n H _{2 n} OSO₃N₂, C _n H _{2 n} PO₃M₂ or -C _n H _{2 n} CN, n is an integer from 1 to 9; M₂ H or an alkali metal and X₂ represent a halogen atom. 8. Bleaching agent according to one of claims 1 to 7, characterized in that the hydrolysis constant of the activator is 1.0 × 10 ^-8 to 1.0 × 10 ^-6 (at 25 ° C). 9. Bleaching agent according to one of claims 1 to 8, characterized characterized that the content of the stock partly (A) 50 to 99.5 wt .-% and the content of Constituent (B) is 50 to 0.5 wt .-%. 10. Bleaching agent according to claim 1, characterized in that that it is still a surfactant in an amount of  Contains 1 to 5 wt .-%. 11. Bleaching detergent, characterized by the content of:

• (A) 0.1 to 30% by weight of hydrogen peroxide and / or hydrogen peroxide addition compound and
• (B) 0.1 to 30% by weight of at least one activator which is a nitrogen-containing heterocyclic compound in which the hydrogen atom of the amino group is substituted by a halogen atom or a non-heterocyclic N-halo-hindered amine compound, the hydrolysis being constant of the activator is in the range of 1 × 10 ^-10 to 5 × 10 ^-6 (at 25 ° C).

12. bleaching detergent according to claim 11, characterized characterized in that the activator is a 1-halopiperidine is derivative. 13. bleaching detergent according to claim 11 and / or 12, characterized in that the activator is a ver bond or a mixture of two or more verbin solutions of 1-halopiperidine derivatives, 1-halohexa methyleneimine derivatives and / or 1-halodiazacyclo is heptanone derivatives. 14. bleaching detergent according to any one of claims 11 to 13, characterized by the additional content of a Surfactants in an amount of 0.1 to 50 wt .-%. 15. bleaching detergent according to any one of claims 11 to 14, characterized by the salary of a builder in an amount of 5 to 90% by weight. 16. bleaching detergent according to any one of claims 11 to 15, characterized by the content of an enzyme in an amount of 0.01 to 10% by weight.