JPH0813996B2 - Bleach composition - Google Patents

Description

TECHNICAL FIELD The present invention relates to a bleaching composition and a bleaching / cleaning composition which are preferably used for bleaching fibers, clothes and the like, particularly for laundry bleaching of textile products. .

[Conventional technology]

As a bleaching agent, hypochlorite, coconut powder,
Various compounds such as hydrogen peroxide, hydrogen peroxide adducts such as sodium percarbonate, persulfates, isocyanuric hydrochloride, and organic peroxides are used. Of these compounds, hydrogen peroxide and hydrogen peroxide adducts are less likely to cause discoloration of colored patterns, so they can be used as a bleaching agent for clothing, that is, to remove bleaching and darkening due to black tea, fruit juice, cosmetics, etc. adhering to clothing. It is widely used to However, these compounds generally have a problem that the bleaching effect is low at low temperatures.

Therefore, in order to solve the above problems, various methods of adding various activators to effect effective bleaching at low temperatures have been proposed.

For example, a method of accelerating the decomposition of hydrogen peroxide by using a heavy metal such as iron, manganese, or cobalt and a complex such as EDTA as an activator (US Pat. No. 315664), a carboxylic acid anhydride (US Pat. No. 2362401). ), N-acylated compound (Japanese Patent Publication No. 38
No. 10165), a method of using a compound that reacts with hydrogen peroxide in a bleaching bath to generate peracetic acid is known. However, the method using a heavy metal complex has a low activation effect and cannot obtain a sufficient low temperature bleaching effect. or,
Although the activation effect is high with the method of adding a peracetic acid-forming compound, when removing stains such as tea or fruit juice,
The oxygen active species in the bath have too high an oxidizing effect, and at the same time, they also oxidize the dye pigments present on the clothing of the colored pattern, which eventually causes a discoloration and fading phenomenon.

On the other hand, it is known that paratoluenesulfochlorosodium amide, which is one of N-halosulfonamide derivatives, is used for desizing and bleaching and refining treatment of fibers (Japanese Patent Application Laid-Open No. S60-18753).
49-110979). Further, a method for stabilizing a halogen ion generating compound added to a detergent composition, specifically, hypochlorite, halogenated isocyanurate, etc., by using the sulfonamide derivative (JP-A-61-14299). ) Is proposed. However, even if these techniques are used, it is not possible to obtain a bleaching agent which has an excellent bleaching effect at low temperatures and which does not cause discoloration or fading of the color pattern.

[Problems to be solved by the invention]

Therefore, an object of the present invention is to provide a bleaching composition which exhibits an excellent bleaching effect even at a low temperature and which hardly causes discoloration or fading of a color pattern.

[Means for solving problems]

Hydroxy radicals (.OH) and singlet oxygen ( ¹ O ₂ ) are known as active oxygen species that are released from peroxygen compounds and have a bleaching effect. The present inventors
Found that there is a problem in terms of consumption science as a result of having an excessively high oxidative effect and exhibiting a high bleaching effect against both stain stain pigments and dye pigments, which also causes fading of clothing with colored patterns. On the other hand, it was also found that the oxidative effect of ¹ O ₂ is milder than that of · OH, and the bleaching effect on dye pigments is low, but the bleaching effect on stain stain pigments is sufficiently high. Further examination based on the above findings,
It was found that singlet oxygen is effectively generated when hydrogen peroxide or its adduct is combined with a specific activator, and the present invention has been completed based on this finding.

That is, the present invention provides (A) hydrogen peroxide and / or a hydrogen peroxide additive, and (B) a nitrogen-containing heteroalicyclic compound in which a hydrogen atom of a secondary amino group in the heterocycle is substituted with a halogen atom. Or a non-heterocyclic N-halo-hindered amine compound having a hydrohalous acid formation hydrolysis equilibrium constant of 1 × 10 ^{−10 to} 5
There is provided a bleaching agent composition comprising at least one activator in the range of × 10 ^-6 (25 ° C), and a bleaching detergent composition containing the composition.

The hydrogen peroxide adduct of the component (A) used in the present invention is a compound that releases hydrogen peroxide in a water bath.
Examples thereof include perborates, perphosphates, and hydrogen peroxide adducts of urea. Incidentally, as the above-mentioned salt, sodium salt,
Examples thereof include potassium salt, lithium salt, calcium salt and the like. Of these, sodium percarbonate and sodium perborate are preferably used in the present invention.

The present invention relates to a nitrogen-containing complex fat in which the hydrogen atom of the secondary amino group in the heterocycle is replaced by a halogen atom in one or a mixture of two or more hydrogen peroxide adducts described above and / or hydrogen peroxide. A cyclic compound, characterized by being combined with an activator of component (B), which has a hydrohalous acid formation hydrolysis equilibrium constant of 1 × 10 ^{−10 to} 5 × 10 ⁻⁶ (25 ° C.). To do. Here, the second of the components (B) in the heterocycle
As the nitrogen-containing heteroalicyclic compound (B-1) in which the hydrogen atom of the amino group is substituted with a halogen atom, the compound represented by the general formula [I] is preferable.

(In the formula, R _{1 to} R ₆ are hydrogen or an alkyl group, and these may be the same or different. Further, R ₁ and R ₂ or R ₃ and
R ₄ together with their attached carbon atom May be formed. X ₁ is halogen, Z is Is a group represented by. Wherein Y is an alkoxyl group, hydroxy carboxyl group, -NCS, -CONH _2, -O-sugar residue, Or R ₈ is an alkyl group having 1 to 16 carbon atoms or a phenyl group, R ₉ and R ₁₀ may be the same or different, C _m H _{2m + 1} , C _m H _2m OH , C _m H _2m-1 (OH) ₂ , C _m H _2m
COOM ₁ (M ₁ is H or an alkali metal) or a lower alkanoyl group, R ₁₁ and R ₁₂ are the same or different, and are C _m
H _{2m + 1} or C _m H _2m OH, R ₁₃ is a hydrogen atom or C _m H
_{2m + 1} , m is 1 to 4, A ⁻ is an anion residue, for example, Cl
^-, CH ₃ COO ^-, Etc.). A 1-halopiperidine derivative represented by:

In the above formula [I], R _{1 to} R ₄ are alkyl groups, R ₅ and R ₆ are hydrogen, and Z is A hindered 1-halopiperidine derivative which is a group represented by is preferable. Further, R _{1 to} R ₄ in the above formula [I]
Is a methyl group, R ₅ and R ₆ are hydrogen, X ₁ is chlorine, and Z is And Y is a hydroxyl group, a lower alkoxyl group, A hindered 1-halopiperidine derivative which is a group represented by is particularly preferable.

In the above formula, examples of the alkyl group include those having 1 to 12 carbon atoms, preferably 1 to 4 carbon atoms, particularly preferably methyl group, and the lower alkoxyl group having 1 to 4 carbon atoms. Can be given. Further, examples of the lower alkanoyl group include those having 2 to 8 carbon atoms. Also, as the sugar residue, Is exemplified.

The compound represented by the above general formula [I] can be produced, for example, by the following method. That is, a target N-halogen compound (NX) can be produced by dissolving a raw material amine compound (NH) in an inert solvent and adding a halogenating agent and then solid carbonic acid if necessary. it can. The inert solvent used is not particularly limited as long as it does not participate in the reaction, but preferred examples thereof include water, alcohol, and a halogenated hydrocarbon-water mixed solvent.

Examples of the halogenating agent include an alkali or alkaline earth metal salt of hypohalous acid.

The reaction temperature is 0 ° C to room temperature, and the time required for the reaction is
30 minutes to 5 hours.

After completion of the reaction, the target compound can be collected from the reaction mixture by a conventional method. For example, it can be obtained by extracting a water-insoluble organic solvent from the reaction mixture, drying the obtained extract, and distilling the solvent from the extract.
Further, if necessary, it is purified by, for example, column chromatography, distillation and recrystallization.

The ammonium salt is produced by dissolving the N-halogen compound obtained by the above method in an inert solvent and reacting it with an acid or its ester.

The inert solvent is not particularly limited as long as it does not participate in the reaction, but alcohols such as methanol and ethanol are preferable. After completion of the reaction, the target compound can be collected from the reaction mixture by a conventional method.
For example, after completion of the reaction, the solvent can be concentrated from the reaction mixture to obtain the desired product, and if necessary, purified by recrystallization or the like.

Next, specific examples of the compound represented by the general formula [I] are shown.

1-chloro-piperidine: 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-2,26,6-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-isothiocyanate piperidine: 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- (2-hydroxyethyl) butylamino] -2,2,6,6-tetramethylpiperidine: 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-tetramethylpiperidine: 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 paratoluene sulfonate: Dimethyl- (1-chloro-2,2,6,6-tetramethyl-4-piperidyl) ammonium chloride: Dimethyl- (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-2.2.2
6.6-Tetramethyl-4-piperidyl) ammonium chloride: 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- [N, N-bis (sodiumoxycarbonylmethyl) amino] -2,2,6,6-tetramethylpiperidine: 1-chloro-piperidine derivatives such as: 1-chloro-morpholine: Morpholine derivatives such as; Hexamethyleneimine derivatives such as 1-chloro-2,2,7,7-tetramethyl-1,4-
Diazacycloheptan-5-one: Diazacycloheptanone derivatives such as: These are used as one kind or as a mixture of two or more kinds. Of the above compounds, preferred are 1-chloro-piperidine, 1-chloro-2-methylpiperidine, 1-chloro-3,5-dimethylpiperidine, 1-chloro-isonipecotic 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 (sodiumoxycarbonylmethyl) 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, trimethyl- (1-
Chloro-2,2,6,6-tetramethyl-4-piperidyl) ammonium paratoluene sulfonate. Among these, particularly preferred are 1-chloro-hexamethyleneimine, 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, trimethyl- (1-chloro-2,2,6,6-tetramethyl-4-piperidyl) ammonium paratoluenesulfonate.

In addition, as the non-heterocyclic N-halo-hindered amine compound (B-2) in the component (B), the following general formula [II]
Alternatively, it means a hindered amine compound in which the hydrogen atom of the amino group represented by [III] is substituted with at least one halogen atom.

(In the formula, R ₂₁ , R ₂₂ , and R ₂₃ are -COOH and -C, respectively.
_{n H 2n + 1, -CC n} H 2n + 1) 3, -C n H 2n OH, -CH 2 -CC
_{n H 2n + 1) 3,} -C n H 2n COOH, -OC n H 2n + 1 or -COOR ₂₅ (R
₂₅ is a group represented by a C _1-9 alkyl group), and n is an integer of 1-9. R ₂₄ is -H, -OH, -F,
_{-Cl, -Br, -I, -C n} H 2n + 1, -CC n H 2n + 1) 3, -
_{C n H 2n OH, -CH 2} -CC n H 2n + 1) 3, -C n H 2n-1 (O
H) ₂ , (C ₂ H ₄ O) _n H, -C _n H _2n COOH, -C _n H _2n COOR ₂₆ (R
₂₆ is an alkyl group of _{C 1~9) -C n H 2n -SO} 3 M 2, -C n H 2n O
A group represented by _{SO 3 M 2, C n H} 2n PO 3 H or -C _n H _2n CN,
n is an integer of 1-9. M ₂ is H or alkali metal, X ₂
Represents halogen. Specific examples of the compound (B-2) represented by the above general formula include the following N-halo-t-alkylamines and their derivatives.

3N-chloro-t-butylamino 1-methyl-1,2
-Propanediol: 3N-chloro-t-butylamino 1,1-dimethyl-
1,2-propanediol: These compounds are used alone or as a mixture of two or more. Among the above compounds, preferred are N-chloro-t-butylamine, 2N-chloro-
Examples include t-butylaminoethanol, 3N-chloro-t-butylamino 1,2-propanediol, 2N-chloro-t-butylaminoacetic acid, and 2N-chloro-t-butylaminomethanesulfonic acid. In addition, (B-
The compound 1) and the compound (B-2) can be used in combination.

These compounds (B-1 and B-2) are characterized by having a bulky chemical structure moiety near the N-halo-amino group as shown in the above specific examples.

The amount of the activator used as the component (B) is 0.05 to 4.0 mol, preferably 0.1 to 1.5 mol, relative to 1 mol of hydrogen peroxide generated from the hydrogen peroxide or hydrogen peroxide adduct used. It is desirable to use.

The mechanism of action by which the bleaching agent composition of the present invention exhibits excellent effects is presumed to be based on the following reasons.

That is, the activator of the present invention causes hydrolysis as shown by the following formula in water and releases hypohalite ion (OX ⁻ ).

Next, OX ⁻ reacts with hydrogen peroxide coexisting in water as shown in the following formula, and releases ¹ O ₂ .

OX ⁻ ＋ H ₂ O ₂ → X ⁻ ＋ H ₂ O + ¹ O ₂ (2) The released ¹ O ₂ has a short life in water of several μsec and is deactivated and triplet oxygen with a small bleaching activity ( since the ³ O _2), in order to bleach the stains stains on fabric, (2) reaction occurs continuously during the time of bleaching stains formula, ^{necessary 1} O ₂ is released at a moderate rate There is. To do this,
The hydrolysis equilibrium constant (Kh) of the organochlorine compound represented by the formula (1) to be hydrolyzed is within a range that is not excessively large, and it is necessary that the concentration of OX ^{− in} the bath is appropriately maintained. For example, when dichloroisocyanurate, which is an organic chlorine compound with a large hydrolysis equilibrium constant (Kh), is used, the rate of ¹ O ₂ generation is too high, and most of the released ¹ O ₂ is deactivated. Therefore, it does not show an effective bleaching effect.

By reacting an organic chlorine compounds having such moderate hydrolysis equilibrium constant (Kh) and hydrogen peroxide, high fading effect on stains dirty dye, the ¹ O ₂ low fading effect on dye pigments at moderate speed Although it can be released, the hydrolysis equilibrium constant (Kh) of the component (B) in the present invention is 1.0 × 1.0 ^{-10 to} 5.0 × 10 ^-6 (25 ° C.),
It is preferably in the range of 1.0 × 10 ^{−8 to} 1.0 × 10 ⁻⁶ (25 ° C.).

The hydrolysis equilibrium constant (Kh) of the component (B) is, for example, J.Ch.
It is measured by the method described in em.Soc., 127 , 98 (1925).

The principle is that when a precursor amine of chloramines for which Kh is to be calculated is added to a dichloramine T solution with a known hydrolysis equilibrium constant in the dissolution equilibrium state, chloramine is generated in the solution, and the dissolution equilibrium of dichloramine T shifts. , Is kept in a new equilibrium state. When the chloride concentration is titrated by the iodine coloring method in this state, the obtained chloride concentration is as shown in the following formula.

2a + b + x = T / 2 (3) where a is the concentration of non-hydrolyzed dichloramine T, b is the concentration of monochlorosulfonamino, x is the concentration of chloramine produced, and T is the amount of sodium thiosulfate solution used for titration. Show. Therefore, the titration increment S due to the addition of the precursor amine S
Is S = b + x = T / 2−2a (4)

Hydrolysis equilibrium constants of the first and second stages of dichloramine T
K ₁ and K ₂ are known as described in J. Chem, Soc., 125 , 1899 (1924).

Here, h is the concentration of HClO, c is the concentration of sulfonamide (5), (6), and the following relationship is obtained.

On the other hand, a is the saturated solubility of dichloramine T, which is actually measured.

a = 0.97 × 10 ⁻³ (M) (8) Furthermore, since x is equal to the concentration of HClO generated from dichloramine T, x = b + 2c (9) From formulas (4) to (9), b ² + 15.84 seek S by ^{× 10 -3 b-7.92 × 10} -3 S = 0 ... (10) measured, (10) obtains a b by formula, x is from equation (4), h is (5) Since it is required more, Kh of the target chloramines is Here, d is determined by the concentration of the added precursor amine.

The component (B) is 100 g of a 0.01% aqueous solution of the component A.
On the other hand, it is preferable to use one that dissolves 0.01 g or more, preferably 0.1 g or more, and particularly preferably 1 g or more.

The bleaching composition of the present invention can be used as it is or as a bleaching agent by adding conventional components. At this time, if a surfactant such as polyoxyethylene nonylphenyl ether (average oxyethylene chain length = 5 to 30) is added in an amount of 1 to 5%, the penetration of the bleaching ingredient into the clothing in water can be promoted. Moreover, the effect of removing dirt is also improved, which is preferable.

The bleaching agent composition of the present invention can also be added as a bleaching effect imparting component to a powdery or granular detergent. That is, 0.1 to 30% by weight of component (A), 0.1 to 30% by weight of component (B), and 0.1 to 30% by weight of at least one surfactant selected from anionic surfactant, nonionic surfactant and amphoteric surfactant. 50%
And, it is preferably used as a bleaching detergent composition containing conventional components such as zeolite, alkali builder, fragrance, and dye.

Further, when the bleaching agent of the present invention is added to an enzyme-containing detergent, an excellent bleaching effect can be obtained in addition to the effect of removing stains such as proteins due to the enzyme effect on the object to be washed. Alkaline protease often used in the art is known to be inactivated by active chlorine, and it is difficult to say that the activator used in the present invention is preferable for the enzyme when used alone. It has been found that the combined use system gives a sufficient bleaching effect with almost no adverse effect on the enzyme effect.

Examples of the anionic surfactant include linear alkylbenzene sulfonates having an alkyl group having 9 to 15 carbon atoms (C), alkyl sulfates (especially C _{10 to} C ₂₂ ), olefin sulfonates (especially C _{10 to} C ₂₄ ), alkanes and (Or) hydroxyalkane sulfonate (especially C ₁₀ ~
C _24), alkyl phenoxy ether sulphates (in particular a C ₈ -C ₁₂ alkyl group and 1 to 10 ethylene oxide units), alkyl ether sulfates (especially C ₁₀
To C ₂₀ alkyl groups and 1 to 10, preferably 2 to 4 ethylene oxide units) and soaps (especially C ₁₂ to
C ₂₀ ) and the like, or a mixture of two or more thereof.

Nonionic surfactants include condensation products of ethylene oxide and propylene oxide (typically 5 to 30 units) with aliphatic or aromatic alcohols or aliphatic amines or amides. Of these, there are aliphatic compounds, which hydrophobic aliphatic moiety having a chain length of C ₈ -C _12, preferably those alkyl aromatic group having a chain length of C ₆ -C ₁₂ for the aromatic compound .

Examples of the amphoteric surfactant, the aliphatic moiety is a linear or branched chain, one substituent is C ₈ -C _18, and aliphatic one anionic water-solubilizing group, especially a sulphonate group Water-soluble derivatives of quaternary ammonium, phosphonium and sulfonium cationic compounds such as alkyl-hydroxy-propane-sulfonate and alkyl-dimethyl-ammonium-hydroxy-propane-sulfonate.

Examples of the cleaning builder include sodium sulfate, sodium carbonate, sodium silicate, sodium pyrophosphate,
Examples thereof include sodium tripolyphosphate, nitrilotriacetic acid and water-soluble salts thereof, sodium ethylenediaminetetraacetate, and various aluminosilicates such as zeolite A.

Enzymes such as Novo Alcalase, Esperase,
Typical examples include proteases such as sabinase and alkaline cellulases.

The bleaching operation consists of dissolving or dispersing the composition in water and immersing the textile fabric in it. The amount of bleach used at that time can be appropriately selected depending on the desired degree of bleaching. A bleaching temperature of 20 to 40 ° C is sufficient, but it may be higher.

〔The invention's effect〕

According to the present invention, an excellent bleaching effect can be obtained at a relatively low temperature, and at the same time, it does not cause discoloration or discoloration of a colored pattern as in the case of using a conventional activator. It is extremely suitable for washing. Further, according to the present invention, not only does not cause discoloration and fading of the colored pattern, but it is possible to bleach while reducing embrittlement of the woven fibers and pulp fibers,
It is also suitable for bleaching industrial threads, fabrics and bleaching in the papermaking process.

Therefore, the bleaching composition of the present invention can be used not only in a wide range of applications but also as a bleaching agent for clothing. Further, it is also useful as an additive for various detergents.

Next, the present invention will be described with reference to examples, but the present invention is not limited thereto.

[Production example]

Next, production examples of some of the activators used in the present invention are particularly preferable.

Production Example 1 1-chloro-4- [N, N-bis (2-hydroxyethyl) amino] -2,2,6,6-tetramethylpiperidine 4- [N, N-bis (2-hydroxyethyl) amino ]
Was dissolved 2,2,6,6-tetramethylpiperidine 3.82g dichloromethane 30 ml, in a mixed solvent of H ₂ O 10 ml, stirring under ice cooling, calcium high I B chloride (calcium hypochlorite)
1.85 g was added slowly. Next, 0.85 g of solid carbonic acid was added, and the mixture was stirred at 0 ° C. for 15 minutes and further at room temperature for 1 hour. After completion of the reaction, extraction was performed with dichloromethane, and the organic layer was dried over sodium sulfate. An oily substance obtained by distilling dichloromethane off the organic layer was subjected to silica gel column chromatography [eluent: ethyl acetate: triethylamine = 30: 1].
After that, the product was recrystallized from a mixed solvent of hexane-ether (10: 1) to obtain the desired product as crystals having a melting point of 54-56 ° C.

Further, the corresponding amine compound was subjected to the same reaction as above, and the obtained crude product was purified by column chromatography, and if necessary, distilled and recrystallized to obtain the following target compound.

1-chloro-4- [N- (2-hydroxyethyl) -methylamino] -2,2,6,6-tetramethylpiperidine mp.37
~ 39 ° C 1-chloro-4- [N- (2,3-dihydroxypropyl) -methylamino] -2,2,6,6-tetramethylpiperidine mp.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 mp. 55 to 57 ° C 3- (N-chloro-Nt-butylamino) -1,2-propanediol mp.72 to 73.5 ° C Production Example 2 1-chloro-4- [N, N- From bis (sodiumoxycarbonylmethyl) amino] -2,2,6,6-tetramethylpiperidine 4- [N, N-bis (ethoxycarbonylmethyl) amino] -2,2,6,6-tetramethylpiperidine Production example 1
1-chloro-4- [N, N-bis (ethoxycarbonylmethyl) amino] -2,2,6,6-tetramethylpiperidine 3.41 g and sodium hydroxide 0.78 g obtained in the same reaction as in 30 ml of ethanol It was dissolved and stirred at room temperature for 15 hours. The resulting insoluble matter is collected by filtration, washed with ethanol and then with diethyl ether, and then dried under reduced pressure to absorb infrared characteristics at 1598 cm ^-1 , 1428 cm ^-1. The desired product was obtained as crystals having.

Production Example 3 Trimethyl- (1-chloro-2,2,6,6-tetramethyl-
4-piperidine) ammonium paratoluene sulfonate 1-chloro-4-obtained from 4-dimethylamino-2,2,6,6-tetramethylpiperidine in the same manner as in Production Example 1
Dimethylamino-2,2,6,6-tetramethylpiperidine 1.7
9 g and 1.57 g of methyl paratoluene sulfonate were dissolved in 16 ml of methanol and stirred at room temperature for 15 hours. After the reaction,
The crystals obtained by distilling off methanol were purified by reprecipitation in a system of methanol-diethyl ether, and the decomposition points 202 to 204
The desired product was obtained as crystals at ℃.

〔Example〕

The methods for producing the contaminated cloth and the dyed cloth, the bleaching effect, and the measurement method for the degree of discoloration and fading performed in Examples and Comparative Examples of the present invention are shown below.

Preparation of contaminated cloth 20g of black tea is put in water 1 and boiled for 5 minutes, and a cotton broad cloth (pretreated cloth,
20 × 30 cm) 10 pieces were put and dyed while boiling for 30 minutes. Then, the contaminated cloth was squeezed, air-dried, cut into a size of 5 × 5 cm, and subjected to a bleaching test.

Preparation of dyeing cloth 450ml of water, 0.75g of dye (CINo.Roactive Red-21) and 13.5g of anhydrous sodium sulfate were dissolved and put into 3 pieces of purified cotton broad cloth (20 × 30cm), and kept at 60 ℃ for 20 minutes. After that, 9 g of sodium carbonate was added, and the mixture was kept at 60 ° C. for 60 minutes. After that, it is washed with water, washed with 0.1% acetic acid aqueous solution, and further boiled with 0.2% anionic surfactant aqueous solution for 5 minutes,
It was washed with water, dried, cut into a size of 5 × 5 cm, and subjected to a discoloration / fading test.

Bleaching test method (i) Bleaching agent composition A predetermined amount of hydrogen peroxide or a hydrogen peroxide adduct and an activator was dissolved in 200 ml of water at 25 ° C. Then, five pieces of black tea-contaminated cloth were added to this bath, bleaching treatment was performed for 30 minutes, washed with water and dried to obtain a bleached cloth. The reflectance of the above pre-treated cloth, black tea-contaminated cloth and bleached cloth is measured by a photoelectric reflectometer (ELREPHO Ca
(manufactured by rl Zeiss), and the bleaching rate (%) was determined by the following formula (12).

(Ii) Bleaching detergent composition The bleaching detergent is added to water at 25 ° C and a hardness of 3 ° DH at a concentration of 0.8.
%, And the tea-contaminated cloth was immersed in this at a bath ratio of 50 and left for 30 minutes. Then, add a cotton knit clean cloth and water with a hardness of 3 ° DH at 25 ° C and wash with 30 times the bath concentration.
Adjusted to 15%, Terg-O-Tometer (made by USTesting)
Was used for 10 minutes at 120 rpm. The test cloth thus treated was subjected to dehydration for 1 minute in a washing machine, overflow rinsing for 1 minute, and dehydration for 1 minute, and then dried by ironing to obtain a bleached cloth.

The reflectance of each of the pretreated cloth, the black tea-contaminated cloth and the bleached cloth was measured using a photoelectric reflectometer (manufactured by ELREPHO Carl Zeiss), and the bleaching rate was calculated by the following formula (12).

When the bleaching rate is improved by 5% in this test, the improvement of the whiteness can be visually discerned, and the improvement of the bleaching effect is recognized in practical use.

Discoloration test method (i) Bleaching agent composition A bleaching bath similar to the bleaching test was prepared, 2 sheets of dyeing cloth were added to this bath, bleaching treatment was carried out for 30 minutes, washing with water and air-drying followed by lightness of the dyeing cloth. , Hue color difference meter (DICOM N
D504DE type) and the discoloration degree ΔE was calculated according to the following equation (13).

However, ΔL: change in lightness of the dyed cloth before and after bleaching Δa: Δb; change of hue before and after bleaching of the dyed cloth (a, the larger the numerical value, the stronger the red color; the smaller the numerical value, the stronger the green color. The larger the value is, the stronger the yellow is, and the smaller the value is, the stronger the blue is.) When the discoloration degree ΔE is 10 or more in this test, it can be visually discerned that the discoloration has occurred, and the discoloration is large in practical use. Is recognized.

(Ii) In the case of a bleaching detergent composition Fix the four corners of the dyed cloth to the frame with pins. 0.5 g of the bleaching detergent of each of Examples and Comparative Examples is sprinkled on each of the cloths, water is further sprayed on the cloth, and the cloth is left for 15 minutes, washed with water and air-dried. The condition of the dried fabric was evaluated according to the following criteria, and the degree of discoloration was examined.

3 points: The part in contact with the bleaching detergent is significantly discolored and faded,
Many spots are observed.

2 points: The portion in contact with the bleaching detergent is discolored and discolored, and spot-like ones are clearly observed.

1 point: A portion in contact with the bleaching detergent is slightly discolored and fading, and spots are slightly observed.

0 point: The part in contact with the bleaching detergent does not discolor at all,
No spots are observed.

Example 1 Sodium peroxide was used as a hydrogen peroxide adduct, and various 1-chloro-nitrogen-containing heteroalicyclic compounds were used as activators, and a bleaching test and a discoloration / fading test were conducted according to the methods described above. . The total concentration of hydrogen peroxide generated from sodium percarbonate and the activator was 3.7 × 10 ^-2 mol /, and the ratio of the amounts was set to the ratio shown in Table-1. Table 1 summarizes the obtained results.

As is clear from Table 1, when the activator which is a comparative example is not used (No. 1), when an organochlorine compound having a large hydrolysis equilibrium constant is used as the activator (No. 17-1)
9) When tetraacetylglycoluril (TAGU), which is a peracetic acid producing compound, is used as an activator (No. 2
In 0), it can be seen that excellent performance cannot be obtained for both due to low bleaching rate and large discoloration. On the other hand, according to the product of the present invention, the bleaching rate is high, and the discoloration and fading of the dye is small.

Example 2 The results of a bleaching test carried out in the same manner as in Example 1 except that the following 1-chloro-nitrogen-containing heterocyclic compound was used as the activator of the component (B) are summarized in Table-2. .

As is clear from Table-2, when no activator is used (No.1) and when only activator is used (No.10)
Compared with the above, a combination of both according to the present invention (No. 2 ~
It can be seen that No. 9) has an excellent bleaching rate and a low degree of discoloration.

Example 3 The same bleaching test as in Example 1 was carried out except that various N-chloro type organic chlorine compounds were used as activators.
The results are summarized in Table-3.

As is clear from Table 3, it is understood that a higher bleaching rate can be obtained by the product of the present invention in which the activator is used in combination, as compared with the case where the activator is not used (No. 1) which is a comparative example.
In addition, when used alone as an activator (No. 9) and when amines having no hindered amine structure were used as activators (Nos. 23 to 25), tetraacetylglycoluril, a peracetic acid-producing compound, was used. When (TAGU) is used as an activator (No.26), and when an activator with a hypohalous acid formation hydrolysis constant of 2.5 × 10 ^-5 is used (No.2)
It can be seen that when 7) is used, the bleaching rate is low, and the discoloration and fading is large, so that excellent effects cannot be obtained for both properties. On the other hand, according to the product of the present invention, the bleaching rate can be maintained high and the discoloration and fading of the dye is small.

 Table 4 shows the hydrolysis constants of the compounds used in Example 3.

Example 4 A granular detergent having the following composition (Table 5), sodium perborate monohydrate as a hydrogen peroxide adduct, and 1-chloronitrogen-containing heteroalicyclic compound as an activator were powder-mixed and The bleaching detergent compositions of Sample Nos. 1 to 7 shown in -6 were prepared and subjected to a bleaching test and a discoloration test. The obtained results are summarized in Table-6.

Example 5 A bleaching detergent composition was prepared in the same manner as in Example 4 except that the activators shown in Table 7 were used instead of the activators used in Example 4, and a bleaching test was conducted. The results are summarized in Table-7.

Example 6 A granular detergent having the following composition (Tables 8 and 9) was prepared, and sodium perborate monohydrate and 1-chloro-4-hydroxy-2,2,6,6-tetramethyl as an activator were prepared. A bleaching detergent composition containing 5% each of piperidine was prepared, and a bleaching test and a discoloration test were conducted.

Table-8 Ingredients Amount (%) LAS-Na 7.0 Fat alcohol ethoxylate ^{* 1} 2.5 Sodium soap ^{* 2} 2.5 Sodium tripolyphosphate 36 Sodium silicate 6 Ethylenediamine tetraacetate (EDTA) 0.1 Tinopearl CBS-X 0.2 Carboxymethylcellulose sodium 0.5 Water 8 Sodium sulphate balance * 1) Aliphatic alcohol ethoxylate with C16-18 and EO = 7 * 2) Aliphatic soap sodium salt with C16-18 Table-9 Ingredients (%) LAS-Na12AS-Na5AES -Na ^{* 1} 5 Zeolite (4A type) 12 Sodium silicate 15 Sodium carbonate 3 Chinopearl CBS-X 0.2 Water 5 Sodium sulphate remaining * 1) Sodium alkyl ether sulphate with C12 to C15 and EO = 3 Table-8, Granules of 9 When the hydrogen peroxide adduct / activator of the present invention was added to the detergent base, it showed the same excellent bleaching performance and discoloration as in the case of No. 3 in Table-6.

Example 7 A bleaching detergent composition was prepared in the same manner as in Examples 4 and 6 except that sodium percarbonate was used as the hydrogen peroxide adduct, and a bleaching test and a discoloration test were conducted. Excellent effect was obtained.

Example 8 A bleaching detergent composition was prepared in the same manner as in Example 5 except that sodium perborate monohydrate was changed to sodium percarbonate, and N-chloro-t-butylamine was used as an activator. When the test was conducted, the same effect as No. 1 of Example 5 was obtained.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display location D06L 3/02 // C07D 211/08 211/12 211/44 211/58 211/62 223/04 223/10 243/08 508 295/22 Z 491/113 7019-4C

Claims (9)

[Claims] 1. A nitrogen-containing heteroalicyclic compound in which (A) hydrogen peroxide and / or a hydrogen peroxide additive, and (B) a hydrogen atom of a secondary amino group in the heterocycle is substituted with a halogen atom, Or a non-heterocyclic N-halo-hindered amine compound having a hydrohalous acid formation hydrolysis equilibrium constant of 1 × 10 ^{−10 to} 5
A bleaching composition comprising at least one activator in the range of ^{x10 -6} (25 ° C). 2. The bleaching composition according to claim 1, wherein the activator of component (B) is a 1-halopiperidine derivative. 3. The activator of component (B) is represented by the general formula [I]: (In the formula, R _{1 to} R ₆ are hydrogen or an alkyl group, and these may be the same or different. Further, R ₁ and R ₂ or R ₃ and
R ₄ together with their attached carbon atom May be formed. X ₁ is halogen, Z is Is a group represented by. Here, Y is an alkoxyl group, a hydroxyl group, a carboxyl group, R ₈ is an alkyl group having 1 to 16 carbon atoms or a phenyl group, R ₉ and R ₁₀ may be the same or different, C _m H _{2m + 1} , C _m H _2m OH, C _m H _2m-1 (OH) ₂ , C _m H _2m COOM
₁ (M ₁ is H or an alkali metal) or a lower alkanoyl group, R ₁₁ and R ₁₂ are the same or different, and are C _m H
_{2m + 1} or C _m H _2m OH, R ₁₃ is a hydrogen atom or C _m H
_{2m + 1} , m is 1 to 4, and A ⁻ is an anion residue). The bleaching composition according to claim 1, which is a 1-halopiperidine derivative represented by the formula (1). 4. The 1-halopiperidine derivative is a hindered type, wherein R _{1 to} R ₄ in the general formula [I] are alkyl groups, R ₅ and R ₆ are hydrogen, and Z is The bleaching composition according to claim (3), which is a group represented by: 5. The 1-halopiperidine derivative is a hindered type, wherein R _{1 to} R ₄ in the general formula [I] are methyl groups, R ₅ and
R ₆ is hydrogen, X ₁ is chlorine, Z is And Y is a hydroxyl group, a lower alkoxy group, Or The bleaching composition according to claim (3), which is a group represented by 6. The component (B) activator is a 1-halomorpholine derivative, a 1-halohexamethyleneimine derivative, 1-
1 selected from the group of halodiazacycloheptanone derivatives
Claim (1) which is a mixture of two or more species
The bleaching composition according to the item. 7. The non-heterocyclic N-halo-hindered amine compound of component (B) has the general formula [II] or [III]: (In the formula, R ₂₁ , R ₂₂ , and R ₂₃ are -COOH and -C, respectively.
_{n H 2n + 1, -C n} H 2n + 1) 3, -C n H 2n OH, -CH 2 -CC n H
_{2n + 1) 3, -C n} H 2n COOH, -OC n H 2n + 1 or -COOR ₂₅ (R ₂₅
Is a C _1-9 alkyl group), and n is 1
Is an integer from 9 to 9. R ₂₄ is -H, -OH, -F, -C
_{l, -Br, -I, -C n} H 2n + 1, -CC n H 2n + 1) 3, -C n H
_{2n OH, -CH 2 -CC n H} 2n + 1) 3, -C n H 2n-1 (OH) 2,
_{(C 2 H 4 O) n} H, -C n H 2n COOH, -C n H 2n COOR 26 (R 26 is C
_{Alkyl) -C n H 2n -SO 3 M} 2 of _1~9, -C _n H _2n OSO
₃ M ₂ , C _n H _2n PO ₃ M ₂ or a group represented by —C _n H _2n CN,
Is an integer of 1-9. M ₂ is H or alkali metal, X ₂
Represents halogen. ) The bleaching composition according to claim (1), which is a compound represented by the formula (1). 8. The bleaching composition according to claim 1, wherein the content of the component (A) is 50 to 99.5% by weight and the content of the component (B) is 50 to 0.5% by weight. 9. (A) 0.1 to 30% by weight of hydrogen peroxide and / or hydrogen peroxide adduct, (B) Nitrogen-containing complex fat in which the hydrogen atom of the secondary amino group in the heterocycle is substituted with a halogen atom. A cyclic compound or a non-heterocyclic N-halo-hindered amine compound, which has a hydrohalous acid formation hydrolysis equilibrium constant of 1 × 10 ^{−10 to} 5 × 1.
At least one activator in the range of 0 ^-6 (25 ° C) 0.1
A bleaching detergent composition containing about 30% by weight.