JP2609996B2 - 1-halopiperidine derivative - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a 1-halopiperidine derivative, and more particularly to the above-mentioned compound which is suitably used for bleaching fibers, clothing and the like, and particularly for washing and bleaching textile products.

[0002]

2. Description of the Related Art Conventionally, bleaching agents such as hypochlorite, powdered salad, hydrogen peroxide, adducts of hydrogen peroxide such as sodium percarbonate, persulfates, isocyanuric hydrochloride and organic peroxides have been used. Are used. Among these compounds, hydrogen peroxide and hydrogen peroxide adducts have little discoloration and discoloration of the color pattern, so as a bleach for clothing,
In other words, it is widely used to bleach and remove stains and dark spots caused by tea, fruit juice, cosmetics, etc. attached to clothing. However, these compounds generally have a problem that the bleaching effect is low at low temperatures.

In order to solve the above problems, various methods have been proposed for adding various activators to perform effective bleaching at a low temperature. For example, a method of promoting the decomposition of hydrogen peroxide using a heavy metal such as iron, manganese or cobalt and a complex such as EDTA as an activator (US Pat. No. 315)
664), carboxylic anhydrides (US Pat. No. 23624)
No. 01), N-acylated product (JP-B-38-10165)
And the like, a method using a compound which reacts with hydrogen peroxide in a bleaching bath to produce peracetic acid is known. However, the method using a heavy metal complex has a low activation effect,
A sufficient low temperature bleaching effect cannot be obtained. Further, although the method of adding a peracetic acid-generating compound has a high activating effect, when removing stains such as tea and fruit juice, the oxidizing action of oxygen-active species in the bath is too high, and at the same time, clothing of color and pattern is used. There is a disadvantage in that the dyestuff present thereon is also oxidized and eventually causes a discoloration phenomenon.

On the other hand, one of the N-halosulfonamide derivatives
It is known that paratoluenesulfochlorosodium amide is used for desizing and bleaching and refining of fibers (Japanese Patent Laid-Open No. 49-110979). Also, a method for stabilizing a halogen ion-generating compound, specifically hypochlorite, halogenated isocyanurate, etc., to be added to a detergent composition using the sulfonamide derivative (JP-A-61-1)
No. 4299) has been proposed. However, even if these techniques are used, it is not possible to obtain a bleaching agent which has an excellent bleaching effect at a low temperature and does not cause discoloration to a colored pattern.

[0005]

Accordingly, the present invention can be used for a bleaching composition which exhibits an excellent bleaching effect even at a low temperature and which causes little discoloration to a color pattern. It is intended to provide a compound that can be used.

[0006]

The present invention has been made based on the finding that the use of a 1-halopiperidine derivative having a specific structure can achieve the above object efficiently. That is, the present invention provides a compound represented by the general formula [I]:

[0007]

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In the formula, R _{1 to} R ₄ are alkyl groups, and R ₅ and R ₆ are hydrogen, which may be the same or different. And R ₁ and R ₂ or R ₃ and R ₄ together with the carbon atom to which they are attached

[0009]

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May be formed. X ₁ is halogen, Z is

[0011]

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And a group represented by Here, Y is an alkoxyl group, a carboxyl group, -CONH ₂ , -OP (O) (OR ₈ ) Cl,
-NR ₉ R _10, or ^{_{-N + R 11 R 12 R 13}} · A - with a group represented, R ₈ is an alkyl group or phenyl group having 1 to 16 carbon atoms, R ₉ and R ₁₀ are also the same May be 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, and R ₁₁ and R ₁₂ are the same or different and are C _m H
Indicates _{2m + 1,} R ₁₃ represents a hydrogen atom or a C _m H _{2m + 1, m} is 1 to 4, A ^- is an anion residue. And a compound that is a 1-halopiperidine derivative represented by｝. Preferred among the compounds of the general formula [I] of the present invention are those wherein Y is an alkoxyl group, -NR ₉ R ₁₀ or -N ⁺ R ₁₁
A compound represented by R ₁₂ R ₁₃ .A ⁻ , wherein M ₁ is an alkali metal.

The compound represented by the above general formula [I] can be produced, for example, by the following method.

That is, an amine compound (= NH) as a raw material is dissolved in an inert solvent, and a halogenating agent and then, if necessary, solid carbonic acid are added to obtain an objective N-halogen compound (= NX). Can be manufactured.

The inert solvent used is not particularly limited as long as it is not involved in the reaction, but preferably includes water, alcohol, or a mixed solvent of halogenated hydrocarbon and water.

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

The reaction temperature is from 0 ° C. to room temperature, and the time required for the reaction is from 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 off the solvent from the extract. Further, if necessary, it is purified by, for example, column chromatography, distillation and recrystallization. The ammonium salt is obtained by the N
It is produced by dissolving a halogen compound in an inert solvent and reacting with an acid or an ester thereof.

The inert solvent is not particularly limited as long as it does not participate in the reaction, but is preferably an alcohol such as methanol or ethanol. 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) 1-chloro-4- [N- (2-hydroxyethyl)
Methylamino] -2,2,6,6-tetramethylpiperidine:

[0019]

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2) 1-Chloro-4- [N- (2.3dihydroxypropyl) methylamino] -2.2.6.6-
Tetramethylpiperidine:

[0021]

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

[0023]

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4) 1-chloro-4- [N- (2.3-dihydroxypropyl) butylamino] -2.2.6.6
-Tetramethylpiperidine:

[0025]

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5) 1-chloro-4- [N, N-bis (2
-Hydroxyethyl) amino] -2,2,6,6-tetramethylpiperidine:

[0027]

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6) 1-chloro-4- [N- (2-hydroxyethyl) -N- (2.3dihydroxypropyl) amino] -2,2,6,6-tetramethylpiperidine:

[0029]

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7) 1-chloro-4- [N-acetyl-N
-Methylamino] -2,2,6,6-tetramethylpiperidine:

[0031]

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8) 1-chloro-4- [N-acetyl-N
-Butylamino] -2,2,6,6-tetramethylpiperidine:

[0033]

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9) Trimethyl- (1-chloro-2.2.2.
6,6-tetramethyl-4-piperidyl) ammonium paratoluenesulfonate:

[0035]

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10) Dimethyl- (1-chloro-2.2.2 ·
6,6-tetramethyl-4-piperidyl) ammonium chloride:

[0037]

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11) Dimethyl- (1-chloro-2.2.2.
6,6-tetramethyl-4-piperidyl) ammonium acetate:

[0039]

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12) Spiro [4.5] -8-chloro-2
-Hydroxymethyl-7.7.9.9-tetramethyl-
8-aza-1,4-dioxadecane:

[0041]

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13) 1-chloro-4-methoxy-2.2
* 6,6-tetramethylpiperidine:

[0043]

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14) 1-chloro-4- [N, N-bis (sodiumoxycarbonylmethyl) amino] -2.2
* 6,6-tetramethylpiperidine:

[0045]

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1-chloro-piperidine derivatives such as 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- [N- ( 2-hydroxyethyl) methylamino] 2,2,6,6-tetramethylpiperidine, 1-chloro-4- [N- (2,3-dihydroxypropyl) methylamino] -2,2,6,6-tetra Methylpiperidine, 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. Among them, particularly preferred is 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, -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.

These compounds are characterized in that they have a bulky chemical structural part near the N-halo-amino group as shown in the above specific examples.

When the compound of the present invention is used as an activator, the activator is used in an amount of 0.05 to 4.0 with respect to 1 mol of hydrogen peroxide produced from the hydrogen peroxide or the hydrogen peroxide adduct.
Mole, preferably 0.1 to 1.5 mole. Hydrogen peroxide adducts that can be combined with the compounds of the present invention are compounds that release hydrogen peroxide in a water bath, and include hydrogen peroxide adducts of percarbonate, perborate, perphosphate, and urea. And the like. In addition, as said salt, a sodium salt, a potassium salt, a lithium salt, a calcium salt, etc. are illustrated. Of these, sodium percarbonate and sodium perborate are preferably used.

When the compound of the present invention is used as a bleaching agent composition, it is dissolved in an amount of 0.01 g or more, preferably 0.1 g or more, particularly preferably 1 g or more, per 100 g of a 0.01% aqueous solution of hydrogen peroxide. It is better to use one. The compound of the present invention can be used as a bleach as it is or as a bleaching agent by adding a conventional component as a bleaching composition in combination with hydrogen peroxide and / or a hydrogen peroxide adduct. At this time, if a surfactant such as polyoxyethylene nonyl phenyl ether (average oxyethylene chain length P = 5 to 30) is added in an amount of 1 to 5%, penetration of the bleaching component into clothing in water is promoted. It is preferable because it can improve the stain removal effect.

The bleaching composition using the compound of the present invention can be added as a bleaching effect-imparting component to a granular detergent. That is, 0.1 to 30% by weight of hydrogen peroxide and / or hydrogen peroxide adduct, 0.1 to 30% by weight of the compound of the present invention, anionic surfactant, nonionic surfactant and amphoteric surfactant At least one surfactant selected
It is suitably used as a bleaching detergent composition containing 0.1 to 50% and common components such as zeolite, alkali builder, fragrance and coloring matter.

When a bleach in which the compound of the present invention is combined with hydrogen peroxide and / or an adduct of hydrogen peroxide is added to an enzyme-containing detergent, an effect of removing stains such as proteins due to an enzyme effect on the object to be washed is added. Excellent bleaching effect can be obtained. Alkaline proteases often used in the industry are known to be inactivated by active chlorine,
It is hard to say that the compound of the present invention is preferable for an enzyme when used alone, but it has been found that, in combination with hydrogen peroxide, the compound of the present invention has almost no adverse effect on the enzymatic effect and still has a sufficient bleaching effect. It was.

Examples of the anionic surfactant include linear alkylbenzene sulfonates and alkyl sulfates having 9 to 15 carbon atoms (C) in the alkyl group (particularly, C ₁₀ to C ₁₀ ).
C _22), olefin sulfonates (especially C ₁₀ ~C _24),
Alkane and (or) hydroxyalkane sulfonates (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 -C ₂₀ alkyl group and 1 to 10, preferably one or a mixture of two or more of such 2-4 with ethylene oxide units) and soaps (especially C ₁₂ -C ₂₀₎ and the like.

Nonionic surfactants include ethylene oxide and propylene oxide (typically 5 to 30).
Unit) and an aliphatic or aromatic alcohol or an aliphatic amine or amide. Of these, for the aliphatic compounds, the hydrophobic aliphatic moiety is C
Those having a chain length of ₈ -C _12, which alkyl aromatic group having a chain length of C ₆ -C ₁₂ are preferred for the aromatic compound. As the amphoteric surfactant, the aliphatic moiety is linear or branched, and one substituent is C _{8 to} C ₁₈ ,
And water-soluble derivatives of aliphatic quaternary ammonium, phosphonium and sulfonium cationic compounds having an anionic water-soluble group, particularly a sulfonate group at one end, such as alkyl-hydroxy-propane-sulfonate and alkyl-dimethyl-ammonium-hydroxy. -Propane-sulfonate.

Examples of the washing builder include sodium sulfate, sodium carbonate, sodium silicate, sodium pyrophosphate, sodium tripolyphosphate, nitrilotriacetic acid and its water-soluble salts, sodium ethylenediaminetetraacetate, and various aluminosilicates such as zeolite A And so on. Representative examples of the enzyme include proteases such as Alcalase, Esperase and Savinase from Novo and alkaline cellulase. The bleaching operation consists of dissolving or dispersing the composition in water and dipping the textile fabric therein. The amount of bleach used at that time can be appropriately selected depending on the desired degree of bleaching.
The bleaching temperature of 20 to 40 ° C. is sufficient, but may be higher.

[0055]

When the compound of the present invention is used in a bleaching composition, an excellent bleaching effect can be obtained at a relatively low temperature, and at the same time, a color pattern as in the case of using a conventional activator is obtained. It is very suitable for washing at ordinary households and the like because it does not cause discoloration. Further, when the compound of the present invention is used in a bleaching composition, not only does not cause discoloration of the color and pattern, but also bleaching can be performed while reducing the embrittlement of woven fibers and pulp fibers. It is also suitable for bleaching in the paper making process. Therefore, the compound of the present invention is used not only for a wide range of applications but also as a bleaching agent, especially 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 to these examples.

[0056]

EXAMPLE 1 1-Chloro-4- [N, N-bis (2-hydroxyethyl) amino] -2,2,6,6-tetramethylpiperidine 4- [N, N-bis (2- Hydroxyethyl) amino]
3.82 g of -2,2,6,6-tetramethylpiperidine
Was dissolved in a mixed solvent of 30 ml of dichloromethane and 10 ml of H ₂ O, and while stirring under ice cooling, 1.85 g of calcium hibochloride (salax powder) was gradually added. 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. The oily substance obtained by distilling off dichloromethane from the organic layer was subjected to silica gel column chromatography [eluent; ethyl acetate: triethylamine = 30: 1], and then extracted from a mixed solvent of hexane-ether (10: 1). By recrystallization, the target product was obtained as crystals having a melting point of 54 to 56 ° C.

Further, the corresponding amine compound was subjected to the same reaction as described above, and the obtained crude product was purified by column chromatography and, if necessary, distillation and recrystallization 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)

Example 2 1-chloro-4- [N, N-bis (sodiumoxycarbonylmethyl) amino] -2,2,6,6-tetramethylpiperidine 4- [N, N-bis (ethoxycarbonyl) Methyl) amino] -2,2,6,6-tetramethylpiperidine, obtained by the same reaction as in Example 1, 1-chloro-4- [N, N-
Bis (ethoxycarbonylmethyl) amino] -2,2
Dissolve 3.41 g of 6,6-tetramethylpiperidine and 0.78 g of sodium hydroxide in 30 ml of ethanol, and add 1
Stir for 5 hours. The resulting insoluble matter was collected by filtration, washed with ethanol and then with diethyl ether, and dried under reduced pressure to obtain infrared characteristic absorptions of 1,598 cm ^-1 and 1,428 cm.
^{-1 -} to obtain the desired product as crystals having a (-COO absorption).

Example 3 Trimethyl- (1-chloro-2,2,6,6-tetramethyl-4-piperidyl) ammonium paratoluenesulfonate Prepared from 4-dimethylamino-2,2,6,6-tetramethylpiperidine 1-chloro- obtained by the same reaction as in Example 1
1.79 g of 4-dimethylamino-2,2,6,6-tetramethylpiperidine and methyl paratoluenesulfonate 1.
57 g was dissolved in 16 ml of methanol and stirred at room temperature for 15 hours. After completion of the reaction, the crystals obtained by distilling off methanol were purified by reprecipitation in a methanol-diethyl ether system to obtain the desired product as crystals having a decomposition point of 202 to 204 ° C.

[0061]

[Reference example] Each of the contaminated cloths performed in the reference example of the present invention,
The method for preparing the dyed cloth and the method for measuring the bleaching effect and the degree of discoloration are shown below. Preparation of contaminated cloth 20 g of black tea is put in 1 liter of water and boiled for 5 minutes. 10 pieces of cotton broad cloth (pre-treated cloth, 20 × 30 cm) which has been glued and purified is added to the liquid from which the black pigment is extracted, and boiled for 30 minutes Dyed. Next, squeeze the stained cloth and air-dry for 5
It was cut into a size of × 5 cm and subjected to a bleaching test.

Preparation of Dyeing Cloth 0.75 g of dye (CINo. Roactive Red-21) in 450 ml of water
And 13.5 g of anhydrous sodium sulfate were dissolved and glued. Three pieces of cotton broad cloth (20 × 30 cm) which had been purified were inserted and kept at 60 ° C. for 20 minutes, and 9 g of sodium carbonate was added.
Hold at 0 ° C. for 60 minutes. Thereafter, it was washed with water, washed with a 0.1% acetic acid aqueous solution, further boiled with a 0.2% aqueous anionic surfactant solution for 5 minutes, washed with water, dried, cut into a size of 5 × 5 cm, and subjected to a discoloration test. .

Bleaching Test Method (i) In the case of bleaching composition A predetermined amount of hydrogen peroxide or an adduct of hydrogen peroxide and an activator was dissolved in 200 ml of water at 25 ° C. Then 5 tea stained cloths were added to this bath and bleached for 30 minutes.
It was washed with water and dried to obtain a bleached cloth. The reflectivity of the pre-treated cloth, black tea-contaminated cloth and bleached cloth can be measured using a photoelectric reflectometer (ELREPHO
Carl Zeiss) using the following formula
The bleaching rate (%) was determined by (12).

(Ii) In the case of a bleaching detergent composition The bleaching detergent is dissolved in water having a concentration of 25 ° C. and a hardness of 3 ° DH at a concentration of 0.2.
8%, and a black stained cloth was soaked in the bath at a ratio of 50 times and left for 30 minutes. After that, a clean cloth of cotton knit and water having a hardness of 3 ° DH at 25 ° C. were added thereto, and the bath ratio was 30.
Adjust the detergent concentration to 0.15% and use Terg-O-Tometer (USTe
Washing was performed for 10 minutes at a rotation speed of 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 reflectivity of the pre-treated cloth, the black tea-contaminated cloth and the bleach-treated cloth was measured using a photoelectric reflectometer (ELREPHO Carl Zeiss).
And the bleaching ratio was determined by the following equation (12).

In this test, when the bleaching ratio is improved by 5%, the improvement in the whiteness can be visually discriminated, and the improvement in the bleaching effect is practically recognized. Discoloration and discoloration test method (i) In the case of a bleaching composition Prepare a bleach bath similar to the bleach test, add two dyed cloths to this bath, perform bleaching treatment for 30 minutes, wash with water, air-dry, and then lightness of the dyed cloth. Color difference meter (DICO manufactured by Nippon Denshoku Industries Co., Ltd.)
M ND 504DE), and the degree of discoloration ΔE was determined according to the following equation (13). ^{△ E = √ (△ L 2} + △ a 2 + △ b 2) ···· (13) where, △ L; bleaching before and after the brightness change of the dyed fabric △ a: △ b; 〃 hue 〃 (a is (The larger the value, the stronger the red, the smaller the value, the stronger the green, and the larger the value, the stronger the yellow, and the smaller the value, the stronger the blue.)

In this test, when the degree of discoloration ΔE is 5 or more,
It can be visually determined that discoloration has occurred, and it is recognized that the discoloration is large in practical use. (ii) In the case of the bleaching detergent composition The four corners of the dyed cloth are fixed to the frame using pins. 0.5 g of the bleaching detergents of Examples and Comparative Examples were respectively sprinkled on the cloth, and further sprayed with water, and allowed to stand for 15 minutes.
Rinse and air dry. 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: The portion in contact with the bleaching detergent slightly discolored and slightly spotted. 0 point: The part in contact with the bleaching detergent does not discolor at all,
No spots are observed.

REFERENCE EXAMPLE 1 Sodium percarbonate was used as a hydrogen peroxide adduct, and various 1-chloro nitrogen-containing heteroalicyclic compounds of the present invention were used as activators. A discoloration test was performed. The total concentration of hydrogen peroxide generated from sodium percarbonate and the activator was 3.7 × 10 ^-2 mol / l, and the ratio between the amounts was as shown in Table 1. Table 1 summarizes the obtained results.

[Table 1] Table 1 ─────────────────────────────────── Test activator bleaching / fading agent Activator / Peroxide white △ E No Hydrogen rate (-) (Molar ratio) (%) ─────────────────────────── ──────── Comparative example 1 ────── 0/100 34 1.0 ──────────────────────────── ─────── 21-Chloro-4- [N- (2-hydroxyethyl 50/50 66 2) methylamino] -2,2,6,6-tetramethylpiperidine 31-chloro- 4- [N-2,3-dihydroxy 〃 65 2 propyl) methylamino] -2,2,6,6-tetramethylpiperidine light 4 1-chloro-4 [N, N-bis (2-hydroxy 〃67 2 Ciethyl) amino] -2,2,6,6-tetramethylpiperidine 51-chloro-4- [N- (2,3-dihydroxy 〃503propyl) butylamino ] -2,2,6,6-Tetramethylpiperidine 6 trimethyl- (1-chloro-2,2,6,6-tetra67-2-tramethyl-4-piperidyl) ammonium paratoluenesulfonate 71-chloro-4 -Methoxy-2,2,6,6- te 601 tramethylpiperidine 8 spiro [4,5] -8-chloro-2-hydroxy 601 cismethyl-7,7,9,9-tetramethyl-8 -Aza-1,4-dioxadecane 91-chloro-4- [N, N-bis (sodium オ 46 1 oxycarbonylmethyl) amino] -2,2,6,6-tetramethylpiperidine ──────場合 As is clear from Table 1, when no activator is used (No.1) As compared with those using the compound of the present invention (N
o.2 to No.9) show excellent bleaching ratio and low discoloration degree.

Claims (2)

(57) [Claims] 1. A compound of the general formula [I]: Wherein R _{1 to} R ₄ are an alkyl group, R ₅ and R ₆ are hydrogen,
These may be the same or different. And R ₁ and R ₂ or R ₃ and R ₄ together with the carbon atom to which they are attached May be formed. X ₁ is halogen, Z is Is a group represented by Wherein Y is an alkoxyl group, a carboxyl _{group, -CONH 2, -OP (O)} (OR 8) Cl, -NR 9 R 10, or ^{_{-N + R 11 R 12 R 13}} · A - , a group represented by 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, and C _m H _{2m + 1} , C _m H _2m O
H, 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, and R ₁₁ and R ₁₂ are the same or different and C _m H _{2m +1} and R ₁₃
Represents a hydrogen atom or a C _m H _{2m + 1, m} is 1 to 4, A ^-
Is an anionic residue. A compound which is a 1-halopiperidine derivative represented by｝. 2. Y is an alkoxyl group, -NR ₉ R ₁₀ or -N ⁺
_{R 11 R 12 R 13 · A} - with a group represented, M ₁ is an alkali metal, A compound according to claim 1.