Classifications

• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/395—Bleaching agents
  • C11D3/3951—Bleaching agents combined with specific additives
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/16—Organic compounds
  • C11D3/26—Organic compounds containing nitrogen
  • C11D3/28—Heterocyclic compounds containing nitrogen in the ring
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/16—Organic compounds
  • C11D3/26—Organic compounds containing nitrogen
  • C11D3/30—Amines; Substituted amines ; Quaternized amines
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/39—Organic or inorganic per-compounds
  • C11D3/3942—Inorganic per-compounds
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/395—Bleaching agents
  • C11D3/3955—Organic bleaching agents

Definitions

• the present invention relates to a bleaching composition and a bleaching detergent composition which are suitable for bleaching fibers and clothes, particularly for washing and bleaching fibrous products.
• Examples of such methods include a method in which a complex comprising EDTA and a heavy metal such as iron, manganese or cobalt is used as an activator to promote the decomposition of hydrogen peroxide (U.S. Patent No.315664) and a method in which a compound which produces peracetic acid when reacted with hydrogen peroxide in a bleaching bath, i.e., carboxylic acid anhydride (U.S. Patent No.2362401) or an N - acylated compound (Japanese Patent Publication No.10165 1 1963) is used.
• the method using a heavy metal complex has a low activation efficiency and cannot provide a sufficient effect concerning bleaching at low temperatures.
• the method employing the addition of a peracetic acid-producing compound exhibits a high activation efficiency, but has disadvantages in that, when stains such as tea or fruit juice stains are removed, the oxidative effect of the active oxygen species contained in the bath is too high and thus the dyes and coloring matters present on colored and patterned clothes are simultaneously oxidized, resulting in changes in color.
• Hydroxyl radicals (*OH) and singlet oxygen C02) are known as active oxygen species which are released from peroxide compounds and exhibit bleaching effects.
• the present inventors have found that, of these species, .OH has problems from the user's point of view in that it has a very high oxidative effect and exhibits a high bleaching effect on both the coloring matters of stains and also dyes, resulting in changes in the colors of colored and patterned clothes.
• '0 2 exhibits a mild oxidative effect as compared with .OH and a low bleaching effect on dye coloring matters, but has a sufficiently high bleaching effect on the coloring matters as stains.
• the present invention provides a bleaching composition comprising:
• the component (A) used in the present invention is a compound which releases hydrogen peroxide in an aqueous solution.
• the hydrogen peroxide addition compounds include percarbonates, perborates, perphosphates and hydrogen peroxide addition compounds of urea.
• such salts include sodium salts, potassium salts, lithium salts, and calcium salts. Among these compounds, sodium percarbonate or sodium perborate or sodium perphosphates is preferably used.
• the heterocyclic hindered amine compound (B-1) used as the component (B) in the present invention is preferably a compound having the following General Formula [I] or a salt thereof: (wherein R, to R 4 each donate a lower alkyl group and may be the same as or different from each other, or R, and R 2 or R 3 and R 4 may be bonded to each other to form a 5-membered or 6 - membered alicyclic ring (i.e., cyclopentyl or cyclohexyl group) involving the carbon atoms to which they are bonded, and X donates a divalent organic residue).
• R, to R 4 each donate a lower alkyl group and may be the same as or different from each other, or R, and R 2 or R 3 and R 4 may be bonded to each other to form a 5-membered or 6 - membered alicyclic ring (i.e., cyclopentyl or cyclohexyl group) involving
• the lower alkyl groups include those having 1 to 4 carbon atoms, (i.e., methyl, ethyl, propyl, butyl or isobutyl group) preferably methyl group.
• Examples of the divalent organic residues include -(CH 2 )a-, -CH 2 CH 2 -, -CONH-, -CH 2 CONHCH 2 - and -CH 2 -Y-CH 2 -.
• Y is the same as that in General Formula [II] which will be given below.
• the alkali metals in the above-described formula include litium, sodium and potassium.
• the aliphatic, aromatic and araliphatic acyl groups include a lower aliphatic acyl group (i.e., formyl, acetyl, propionyl butyryl or isobutyryl), benzoyl, toluoyl and phenylacetyl groups.
• the substituted or unsubstituted carbamoyl groups include a carbamoyl group and a mono or di-lower alkyl carbamoyl group, preferably N-methylcarbamoyl group.
• the alkyl groups R 10 include methyl and ethyl groups and the aryl groups R 10 include phenyl and tolyl group.
• Preferred heterocylic hindered amines of the present invention are those having formula [II] wherein R is hydrogen or methyl, Y is >CH 2 -, >CH-OR s (in which R 5 is hydrogen or lower alkyl), (in which both of R 6 and R 7 are hydrogen, or R 6 is hydrogen or lower alkyl and R 7 is lower aliphatic acyl, carbamoyl.
• R s is hydrogen, lower alkyl, lower aliphatic acyl, carbamoyl, or mono- or di-lower alkyl carbamoyl) or (in which Rs is as defined above and Rs is methyl or ethyl).
• J.P Japanese Patent Publication for Opposition Purpose
• acylic hindered amine compounds (B-2) used as the components (B) of the present invention are those having the following General Formula [III] or salts thereof: wherein R 11 , R 12 and R 13 each donate -COOR 15 , in which R 15 is an alkyl group having 1 to 9 carbon atoms i.e., methyl, ethyl, propyl.
• n is an integer of 1 to 9 and R 14 donates -H, -C n H 2n+1 , in which R 16 is an alkyl group having 1 to 9 carbon atoms defined above n is an integer of 1 to 9, and M 2 is H or an alkali metal defined above).
• Preferred acylic hindered amines of the present invention are those having formula [III] wherein each of R 11 , R 12 and R 13 is -C n H 2n+1 or -C n H 2n OH (in which n is 1 - 4) and R 14 is H, -C n H 2n+1 , -CnH2nOH, -CH 2 CH(OH)CH 2 0H or -C n H 2n+1 SO 3 M 2 (in which n is 1 - 4 and M 2 is H or alkali metal).
• These compounds (B-1) and (B-2) have a characteristic chemical structure in which a tertiary carbon atom is adjacent to an amino group.
• Examples of the amine salts of the above General Formula [I] to [III] include salts of inorganic acids such as hydrochloric acid, sulfuric acid and phosphoric acid and organic acids such as acetic acid, propionic acid, benzoic acid and p-toluenesulfonic acid.
• the component (C) used in the present invention may be any compound capable of forming a hypohalogenous acid ion upon dissolution in water to form ions or upon hydrolysis.
• the halogen of the hypohalogenous acid is preferably chlorine or bromine.
• the compounds as the component (C) include, for example, sodium N-chloro-p-toluenesulfonamide (chloramine T), sodium N-chlorobenzenesulfonamide (chloramine B), N-chlorosulfonamide, sodium N-cyclohexyl-N-chlorosulfonamide, N,N-dichlorosulfamoylben- zoic acid, N,N-dichloro-p-tolunesulfonamide (dichloramine T), N,N-dichlorobenzenesulfonamide, N-chlorosaccharin, N-chloromethanesulfonamide, N-chlorosulfa
• the present invention is characterized by using the above-described components (A), (B) and (C) in combination.
• excellent bleaching power and prevention of changes in color can be achieved.
• the three components can be used in any ratio, it is preferred for obtaining an improved effect to use 0.05 to 4 mol, preferably 0.1 to 1.5 mol, of the component (B) and 0.05 to 4 mol, preferably 0.1 to 1.5 mol, of the component (C) per mol of hydrogen peroxide as the component (A) or hydrogen peroxide formed from the hydrogen peroxide addition compound.
• the component (A) is used in an amount of 50 to 99% by weight (hereinafter referred to as "%"), preferably 60 to 95%, the component (B) is used in an amount of 0.5 to 40%, preferably 2.0 to 30%, and the component (C) is used in an amount of 0.5 to 40%. preferably 2.0 to 30%.
• the components (A) to (C) used in the present invention can be granulated or surface-treated to control the dissolution velocity thereof depending on their use. An excellent effect can be obtained also when the component (A) is added after the addition of the components (B) and (C).
• the bleaching composition of the present invention can be employed as it is or can be used as a bleaching agent in a mixture with conventionally-used components.
• the bleaching composition of the present invention can be added as a bleaching effect- imparting component to granular detergent.
• the bleaching composition can be desirably used as a bleaching-detergent composition containing 0.1 to 30% by weight of the component (A), 0.1 to 30% by weight of the component (B), 0.1 to 30% by weight of the component (C) and 0.1 to 50% of at least one surfactant selected from the group comprising anionic surfactants, nonionic surfactants, and ampholytic surfactants, as well as conventionally-used components such as zeolite, an alkali builder, a perfume, and a dyestuff.
• the bleaching composition of the present invention when added to an enzyme- containing detergent, the effect concerning the removal of stains such as proteins is obtained by the enzyme effect acting on an article to be washed, whereby an excellent bleaching effect can be obtained.
• alkali protease which is widely used in the industry related to this invention, is known to be inactivated by active chlorine, it is difficult to say that the activator used in the present invention is preferable for an enzyme if it is used singly.
• a system of the present invention in which the activator composition of (B) and (C) is used in combination with hydrogen peroxide has only a slightly adverse influence upon an enzyme and shows an adequate bleaching effect.
• anionic surfactants include linear alkylbenzenesulfonates in which the alkyl has 9 to 15 carbon atoms (C), alkylsulfates (particularly C 10 to C 22 ), olefin sulfonates (particularly C 10 to C 24 ), alkane and/or hydroxyalkane sulfonates (particularly C 10 to C24), alkylphenoxy ether sulfates (particularly having C s to C 12 alkyl groups and 1 to 10 ethylene oxide units), alkyl ether sulfates (particularly, having C 10 to C 20 alkyl groups and 1 to 10, preferably, 2 to 4, ethylene oxide units), and mixtures of one or more kinds of soap (particularly C 12 to C 20 ).
• nonionic surfactants include the addition products of ethylene oxide or propylene oxide (typically 5 to 30 units) with aliphatic or aromatic alcohols or aliphatic amines or amides.
• aliphatic compounds preferably have C s to C 12 chains in the hydrophobic aliphatic portions thereof, and aromatic compounds preferably have alkyl aromatic groups having C s to C, 2 chains.
• ampholytic surfactants include water-soluble derivatives of aliphatic quaternary ammonium, phosphonium, and sulfonium cationic compounds in each of which the aliphatic portion is a linear or branched chain, one substituent is Cs to Cis, and an anionic water-soluble group, particulary a sulfonate group, is present at one end, such as alkyl hydroxypropanesulfonates and alkyl dimethylammonium- hydroxypropanesulfonates.
• detergent builders include sodium sulfate, sodium carbonate, sodium silicate, sodium pyrophosphate, sodium tripolyphosphate, nitrilotriacetic acid and water-soluble salts thereof, sodium ethylenediaminetetraacetate, and various aluminosilicates such as Zeolite A.
• the bleaching-detergent composition contains a builder in an amount of 5 to 90% by weight.
• Typical examples of enzymes include protease such as alkalase produced by Novo Corp., esperase, and sabinase and alkali cellulase.
• the bleaching-detergent composition may contain an enzyme in an amount of 0.01 to 10% by weight.
• the bleaching operation comprises dissolving or dispersing the composition in water and immersing textile fabrics in the solution.
• the amount of bleaching agent used can be suitably selected according to the desired degree of bleaching.
• a temperature within the range of 20 to 40° C is sufficient for bleaching, but one higher than 40 C may of course be employed.
• the present invention can obtain an excellent bleaching effect at a relatively low temperature and is extremely suitable for domestic washing because it produces not discoloration of colored and patterned clothes, as experienced when conventional activators are used.
• the present invention is not only free from any tendency to cause discoloration of colored and patterned clothes but is also capable of bleaching textile fibers or pulp fibers while at the same time reducing embrittlement, it is suitable for bleaching industrial threads and fabrics and for bleaching in paper-making processes.
• the bleaching composition of the present invention is suitable also for the bleaching and deterging artificial teeth stained with sordes such as nicotine.
• the bleaching composition of the present invention can be widely used, and is also suitable for use as a bleaching agent for clothes.
• This bleaching composition is also useful as an additive for various detergents.
• Predetermined amounts of hydrogen peroxide or a hydrogen peroxide addition product and an activator were dissolved in 200 ml of water at 25° C.
• Five pieces of cloth stained with black tea were placed in this water bath and then subjected to bleaching treatment for 30 minutes.
• the cloths were then washed with water and dried to obtain bleached cloths.
• the degree of reflection of each of the pretreated cloth, black tea-stained cloth, and bleached cloth was measured by using a photoelectric reflection meter (ELREPHO produced by Carl Zeiss Co., Ltd.) and the bleaching ratio (%) thereof was obtained by the equation (3) described below.
• a bleaching-detergent composition was added to water with a hardness of 3 DH at 25° C so that the concentration became 0.8%, and a cloth stained with black tea was immersed in the water bath in a bath ratio of 50 times and then allowed to stand for 30 minutes.
• a clean cotton knitted cloth and water with a hardness of 3° DH at 25° C were then added to the water bath and the bath ratio and the concentration of the detergent composition were adjusted to be 30 times and 0.15%, respectively, followed by washing with a Terg-0-Tometer (produced by U.S. Testing Co., Ltd.) for 10 minutes at 120 rpm.
• the pieces of test cloth treated in the above-described manner were dehydrated for 1 minute, rinsed with overflowing water for 1 minute. and dehydrated for 1 minute in turn with a washing machine, and then dried by ironing to obtain bleached cloths.
• a bleaching bath the same as that used in the bleaching test was prepared and two pieces of dyed cloth were then added into the bath, followed by bleaching treatment for 30 minutes.
• the cloths were then washed with water and dried with air, and the lightness and shade thereof were measured by using a differential colorimeter (DICOM ND504DE model produced by Nihon Denshoku-kogyo Co., Ltd.).
• the degree of discoloration E was determined by the following equation (4): wherein AL : change in lightness before and after the bleaching of the cloths.
• Aa, Ab change in shade before and after the bleaching of the cloths.
• a piece of dyed cloth was fixed at the four corners in a frame by using pins.
• 0.5 g of each of the bleaching-detergent compositions of Examples and Comparative Examples was sprinkled over this cloth, and water was then sprayed thereon. After being allowed to stand for 15 minutes, the cloth was washed with water and then dried with air. After drying, the state of the cloth was evaluated on the basis of the criteria described below for the purpose of measuring the degree of discoloration.
• the bleaching and discoloration tests were performed by using hydrogen peroxide or sodium percarbonate as the component (A) in combination with an amine compound and a compound capable of forming a hypohalogenous acid ion in the solution.
• the results obtained are summarized in Table 1.
• component (A) 0 or 1 x 10- 2 mol,1 (in terms of H 2 O 2 )
• component (B) 0 or 1 x 10- 2 mol
• % component (C) 0 or 1 x 10- 2 mol/l %
• a granular detergent having the composition shown in Table 3 was mixed with sodium perborate monohydrate as the hydrogen peroxide addition compound, chloramine T and/or sodium dichloroisocyanurate as the chlorine-containing compound and 4-hydroxy-2,2,6,6-tetramethylpiperidine and/or t-butylaminoethanol as the amine to give a powdery bleaching detergent composition shown in Table 4.
• the composition was subjected to the bleaching and discoloration tests.
• the sodium perborate monohydrate used had its dissolution velocity delayed by granulation.
• Granular detergents having compositions shown in Tables 5 and 6 were prepared. Sodium perborate monohydrate, 4-hydroxy-2,2,6,6-tetramethylpiperidine as the specified amine and chloramine T as the chlorine-containing compound were added each in an amount of 5% to the compositions to give bleaching detergent compositions, which were then subjected to the bleaching test and discoloration test.
• Bleaching-detergent compositions were formed in the same manner as that of Example 4 except that sodium percarbonate was used as the hydrogen peroxide addition compound. The compositions were subjected to the bleaching and discoloration tests to obtain the results similar to those of Example 4.

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• Chemical & Material Sciences (AREA)
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• Oil, Petroleum & Natural Gas (AREA)
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Cited By (7)

Citations (5)

• 1988
  • 1988-11-04 EP EP88118440A patent/EP0315204A3/de not_active Ceased

Patent Citations (5)

Non-Patent Citations (3)

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