JPH093020A - N-halogenated hindered amine compound - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject new compound exhibiting an excellent bleaching effect at low temperature, little in the discoloration and fading of color-patterned products, and capable of being suitable used for washing and bleaching fiber products. SOLUTION: A compound of the formula [R24 is OH, a halogen, a group of the formula: C(Cn H2n+1 )3 ((n is 1-9), a group of the formula: Cn H2n OH, a group of the formula: CH2 -C(Cn H2n+1 )3 , a group of the formula: Cn H2n+1 (OH)2 a group of the formula: (C2 H4 O)n H, a group of the formula: Cn H2n COOH, a group of the formula: Cn H2n COOR26 (R26 is a 1-9C alkyl), a group of the formula: Cn H2n -SO3 M2 (M2 is H, an alkali metal), a group of the formula: Cn H2n OSO3 M2 , a group of the formula: Cn H2n PO3 M2 , a group of the formula: Cn H2n CN; X2 is a halogen]. For example, 3-(N-chloro-N-cyclohexylamino)-1-2,propanediol. The exemplified compound is obtained by gradually adding calcium hypochlorite to 3-(N-cyclohexylamino)-1,2-propanediol, adding a solid carbonic acid under stirring, and subsequently isolating and purifying the reaction product.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to N-halo hindered amine compounds, and more particularly to the above compounds which are preferably used for bleaching fibers, clothes and the like, especially 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]

Therefore, the present invention can be used for a bleaching composition or the like which exhibits an excellent bleaching effect even at a low temperature and hardly causes discoloration or fading of a color pattern. It is intended to provide a compound.

[0006]

The present invention was made based on the finding that the above problems can be efficiently achieved by using a halohindered amine compound having a specific structure. That is, the present invention provides a compound represented by the general formula [I]:

[0007]

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(Where R is_{twenty four}Is -OH, -F, -Cl, -Br,
-I, -C- (C_nH_{2n + 1})_Three, -C_nH_2nOH, -CH_Two-C- (C_nH
_{2n + 1})_Three, -C_nH_2n-1(OH)_Two,-(C_TwoH_FourO)_nH, -C_nH_2nCOO
H, -C _nH_2nCOOR₂₆(R₂₆Is C₁~ C₉Alkyl group), -C_nH
_2n-SO_ThreeM_Two, C_nH_2nOSO_ThreeM_Two, C_nH_2nPO_ThreeM_TwoOr -C_nH
_2nIt is a group represented by CN, and n is an integer of 1 to 9. M
_TwoIs H or alkali metal, X_TwoRepresents halogen. )
A N-halo hindered amine compound represented by
You. Preferred compounds of the general formula [I] of the present invention
Is R_{twenty four}Is C_nH_2n-1(OH)_Two(N is an integer of 1 to 9
And X_TwoIs a compound in which is halogen.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION As the compound represented by the above general formula [I], the following compounds are preferable. 1) 3- (N-chloro-N-cyclohexylamino)-
1,2-propanediol:

[0010]

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These compounds are characterized by having a bulky chemical structure portion near the N-haloamino 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 mol, preferably 0 to 1 mol of hydrogen peroxide generated from hydrogen peroxide or a hydrogen peroxide adduct. .1 to 1.5
It is desirable to use it so that it becomes a mole. Hydrogen peroxide adducts that can be combined with the compounds of the invention include
It is a compound that releases hydrogen peroxide in a water bath, and examples thereof include percarbonates, perborates, perphosphates, and hydrogen peroxide adducts of urea. 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 0.01 g or more, preferably 0.1 g or more, particularly preferably 1 g or more with respect to 100 g of a 0.01% aqueous hydrogen peroxide solution. 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 agent composition using the compound 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 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 bleaching agent in which the compound of the present invention is combined with hydrogen peroxide and / or a hydrogen peroxide adduct is added to an enzyme-containing detergent, an effect of removing stains such as proteins due to the enzyme effect on the object to be washed is added. , You can get an excellent bleaching effect. 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.

As the above-mentioned anionic surfactant, a linear alkylbenzene sulfonate having an alkyl group having 9 to 15 carbon atoms (C), an alkyl sulfate (especially 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.

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 change as in the case of using a conventional activator. Since it does not cause discoloration, it is extremely suitable for washing at home. 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.

[0019]

EXAMPLES Reference 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.

Example 1 3- (N-chloro-N-cyclohexylamino) -1,
2-Propanediol The corresponding amine compound was reacted in the same manner as in Reference Example 1,
The obtained crude product was purified by column chromatography, and if necessary, distillation and recrystallization to obtain the target compound (mp. 55 to 57 ° C).

Claims (2)

[Claims] 1. A compound represented by the general formula [I]:(Where R_{twenty four}Is -OH, -F, -Cl, -Br, -I, -C- (C_n
H_{2n + 1})_Three, -C_nH_2nOH, -CH_Two-C- (C_nH_{2n + 1})_Three, -C_n
H_2n-1(OH)_Two,-(C_TwoH_FourO)_nH, -C_nH_2nCOOH, -C _nH_2nCO
OR₂₆(R₂₆Is C₁~ C₉Alkyl group), -C_nH_2n-SO_ThreeM_Two, C
_nH_2nOSO_ThreeM_Two, C_nH_2nPO_ThreeM_TwoOr -C_nH_2nIndicated by CN
And n is an integer of 1 to 9. M_TwoIs H or
Lucari Metal, X_TwoRepresents halogen. N- represented by)
Halo hindered amine compounds. 2. The compound according to claim 1, wherein R ₂₄ is C _n H _2n-1 (OH) ₂ (n is an integer of 1 to 9) and X ₂ is halogen.