JP2002080895A - Liquid bleaching agent composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a liquid bleaching agent composition which has the viscosity suitable for the application onto stain and dirt and also the excellent bleaching and washing power. SOLUTION: The liquid bleaching agent composition contains (a) hydrogen peroxide, (b) 0.1-10 wt.% of a compound having in the molecule at least one of 8-20C alkyl or alkenyl groups and at least one of polyoxyalkylene chains (the alkyle) groups have the number of carbons of 2-4) and also having a weight- average molecular weight of 2,500-50,000, and (c) 0.01-10 wt.% of a polyalkylene glycol ((e alkylene group has the number of carbons of 2-4), with a weight ratio of (c)/(b) being of 0.001-10.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a thickened liquid bleaching composition, and more particularly to a liquid bleaching composition having a viscosity suitable for application to stain stains and excellent bleaching detergency.

[0002]

2. Description of the Related Art A liquid bleach containing hydrogen peroxide as a main base has the advantages that it can be used for coloring of textiles such as clothing, can be applied directly to dirt, and can be washed as it is with a detergent for clothing. Used at home, preferred. On the other hand, when a liquid bleach is used for absorbent articles such as textiles, the liquid bleach remains on the surface, so that a sufficient bleaching power for stains can be exhibited. Attempts have also been made to increase the viscosity of the liquid bleach from a work point of view.

In general, as a method for increasing the viscosity of an aqueous solution, a polymer thickener such as an acrylic acid polymer, xanthan gum or polyvinyl alcohol, or a clay material such as smectite can be used. Since hydrogen-based liquid bleach is prepared in consideration of stability and acidic, it shows sufficient stability in acidity and is economically excellent,
Furthermore, it is difficult to obtain a sufficient thickening effect without causing turbidity in appearance.

[0004] For example, it is difficult to thicken an acrylic polymer with an acidic polymer, and if a sugar-based thickener such as xanthan gum is blended, the viscosity after storage decreases. Also,
When polyvinyl alcohol is used, it is necessary to mix it in a large amount, so that it is difficult to effectively increase the viscosity. Clay materials may accelerate the decomposition of hydrogen peroxide itself.

In order to solve these problems, Japanese Patent Laid-Open No.
JP-A-193399 proposes a compounding system containing a phenol compound for viscosity stability in addition to a polymer thickener, and JP-A-10-72598 discloses a polyol such as a saccharide and boron. Although systems containing compounds have been proposed, these liquid bleach compositions are uneconomical because special viscosity stabilizers must be incorporated.

[0006] On the other hand, the present applicant has found that a specific polyoxyalkylene derivative is effective for thickening in a hydrogen peroxide blended system, and has disclosed it in Japanese Patent Application Laid-Open No. H10-130693. However, an oxygen-based liquid bleach having stronger bleaching performance is desired.

[0007]

SUMMARY OF THE INVENTION Accordingly, it is an object of the present invention to provide a liquid bleach composition having sufficient viscosity and excellent bleaching power.

[0008]

According to the present invention, there are provided (a) hydrogen peroxide (hereinafter referred to as "component (a)") and (b) at least one alkyl or alkenyl group having 8 to 20 carbon atoms in a molecule. And a compound having at least one polyoxyalkylene chain (alkylene group having 2 to 4 carbon atoms) and a weight average molecular weight of 2,500 to 50,000 [hereinafter, referred to as
(Referred to as component (b)) 0.1 to 10% by weight, and (c) a polyalkylene glycol (the alkylene group has 2 to 2 carbon atoms).
4) [Hereinafter referred to as component (c)] 0.01 to 10% by weight
And (c) / (b) is 0.001 to 10 in weight ratio.
A liquid bleach composition.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION The liquid bleach composition of the present invention contains hydrogen peroxide as component (a), preferably from 0.1 to 10%.
% By weight, more preferably 1 to 6% by weight.

In the present invention, at least one alkyl group or alkenyl group having 8 to 20 carbon atoms, preferably 10 to 20 carbon atoms, particularly preferably 12 to 20 carbon atoms, is preferably used as component (b). And has 2 to 2 carbon atoms
A compound having at least one polyoxyalkylene chain, preferably at least one polyoxyethylene chain, having a weight average molecular weight of 2,500 to 50,000 is used. In the present invention, the component (b) has an average of 50 to 5 repeating units of the oxyalkylene group.
00 is preferable, and specifically, the following general formula (I)
Are preferred, the compounds having a weight average molecular weight of 2,500 to 50,000 represented by R ¹ -X - _{^{[(R 2 O) m - (}} CO) p -R 3 ] _n (I) wherein, R ¹ is 8 to 20 carbon atoms, preferably 10 to 2
0, particularly preferably an alkyl or alkenyl group having 12 to 20, and R ² is an alkylene group having 2 or 3 carbon atoms, preferably an ethylene group. X represents any of O, COO, N, and CON, and when X is O or COO, n = 1, X
Is N or CON, n = 2. m is 50-50
0, preferably 50 to 300, particularly preferably 100 to
200, p is 0 or 1, R ³ is hydrogen atom, carbon number 1
And represents an alkyl group having from 20 to 20 or an alkenyl group having from 8 to 20 carbon atoms. ].

The weight average molecular weight of the component (b) is determined by using polyethylene glycol obtained by using a mixture of 10% by volume of acrylonitrile and 90% by volume of 0.1 mmol / l phosphate buffer (pH 2.0) as an eluent. It is measured by gel permeation chromatography as a standard.

More preferred examples of the component (b) include Emanone 3199 (polyoxyethylene monostearate, molecular weight 7000) and Emanone 32 manufactured by Kao Corporation.
99 (polyoxyethylene distearate, molecular weight 85
00), Emulgen 2200 (polyoxyethylene cetyl ether, molecular weight 7000), Emulgen 3200
(Polyoxyethylene stearyl ether, molecular weight 61
00), bissurf S (addition reaction product of emulgen 3200 and vinylcyclohexene diepoxide, molecular weight 10,000 to 20,000), bissurf CT (addition reaction product of emulgen 2200 and vinylcyclohexene diepoxide, molecular weight 20,000 to 30,000) And the like.

The liquid bleaching composition of the present invention contains component (b) in an amount of 0.1 to 10% by weight, preferably 0.1 to 8% by weight, more preferably 1 to 6% by weight from the viewpoint of a thickening effect. %contains.

The liquid bleach composition of the present invention contains, as the component (c), a polyalkylene glycol (alkylene group having 2 to 4 carbon atoms), and a compound represented by the formula (II) is particularly preferable. . HO- (AO) _j -H (II) wherein AO is an oxyalkylene group, and A represents a linear or branched alkylene group having 2 to 3 carbon atoms, preferably an ethylene group. j represents a number having an average value of 3 to 500, preferably 50 to 300, particularly preferably 100 to 200. ].

The liquid bleach composition of the present invention contains component (c) in an amount of from 0.01 to 10% by weight, preferably from 0.01 to 10% by weight, in order to obtain a suitable viscosity and to prevent the composition from separating or becoming cloudy during storage. It contains 0.01 to 5% by weight.

In the present invention, the weight ratio of the component (b) to the component (c) in the composition is as follows: component (c) / (b)
Component = 0.001 to 10, preferably 0.005 to 5. Within this range, it is possible to obtain a composition having a sufficient thickening effect and a liquid that does not separate or become cloudy at high temperatures.

[0017] The liquid bleach composition of the present invention comprises at least one selected from anionic surfactants, cationic surfactants and nonionic surfactants other than the compound of the general formula (1).
It is preferable to contain a seed from the viewpoint of the cleaning effect.

Examples of the anionic surfactant include alkyl benzene sulfonate, alkyl or alkenyl sulfate, alkyl or alkenyl ether sulfate, α-olefin sulfonate, saturated or unsaturated fatty acid salt, and N-acyl amino acid type. Examples thereof include a surfactant, an alkyl or alkenyl ether carboxylate, an amino acid type surfactant, and an alkyl or alkenyl phosphate ester salt. Among them, the alkyl group has 8 to 2 carbon atoms.
Alkyl benzene sulfonates are particularly preferred. The liquid bleach composition of the present invention contains 0 to 30% by weight, preferably 0.1% by weight of an anionic surfactant from the viewpoint of the bleaching and washing effect.
It is preferably contained in an amount of from 20 to 20% by weight, particularly preferably from 0.1 to 10% by weight.

Examples of the cationic surfactant include quaternary ammonium salts and the like.
The compound (I) is preferred from the viewpoint of the bleaching and washing effect.

[0020]

Embedded image

Wherein R ^{4 to} R ⁷ are at least one, preferably one of them, an alkyl group having 8 to 18 carbon atoms, preferably 8 to 16 carbon atoms, and the rest having 1 to 3 carbon atoms. It is an alkyl group or a hydroxyalkyl group. Y ⁻ represents an anionic group, preferably a sulfate ion, a phosphate ion, an alkylsulfate ion having 1 to 3 carbon atoms and an alkyl group having 6 to 6 carbon atoms which may be substituted with an alkyl group, on the storage stability of hydrogen peroxide. 12 arylsulfonic acid ions, having 1 to 1 carbon atoms
2 fatty acid ions. ].

The liquid bleach composition of the present invention preferably contains a cationic surfactant in an amount of 0 to 5% by weight, more preferably 0.05 to 3% by weight.

The liquid bleaching composition of the present invention preferably contains the component (b), especially a nonionic surfactant other than the general formula (I), from the viewpoint of the bleaching washing effect and the storage stability. The compound represented by the general formula (IV) is preferred. _{^{R 8 - (OB) k -OH}} (IV) wherein, R ⁸ is 6 to 20 carbon atoms, preferably 8 to 18,
More preferably, it is a straight-chain or branched-chain alkyl group having 8 to 14 carbon atoms, B is a straight-chain or branched-chain alkylene group having 2 to 3 carbon atoms, preferably an ethylene group, and k is an average addition mole of alkylene oxide. It indicates a number, and is a number of 2 to 20, preferably 3 to 15, and more preferably 5 to 10. ].

The liquid bleaching composition of the present invention contains 0.05 to 30% by weight, more preferably 0.1 to 20% by weight, especially 0.1 to 15% by weight of a nonionic surfactant other than the component (b). It is preferred to contain.

The liquid bleach composition of the present invention preferably contains a bleach activator from the viewpoint of bleaching performance. As the bleach activator used in the present invention, a compound represented by the general formula (V) is preferable.

[0026]

Embedded image

[Wherein R ⁹ represents a linear or branched alkyl or alkenyl group having 5 to 17 carbon atoms;
Is -SO ₃ M or indicates -COOM, M represents a cation hydrogen atom or an organic or inorganic. ].

As an example of the compound represented by formula (V), those described on page 6 of JP-A-10-130693 can be mentioned.

The liquid bleach composition of the present invention contains 0.01 to 10% by weight, more preferably 0.05 to 5% by weight of a bleach activator,
In particular, it is preferable to contain 0.1 to 3% by weight.

Further, it is preferable to add a sequestering agent to the bleaching composition of the present invention from the viewpoints of storage stability and bleaching washing effect. Examples of the sequestering agent used in the present invention include (1) a phosphoric acid compound such as phytic acid or an alkali metal salt or an alkanolamine salt thereof, (2) ethane-1,1-diphosphonic acid, ethane-1, 1,2-triphosphonic acid, ethane-1-hydroxy-1,1-diphosphonic acid and derivatives thereof, ethanehydroxy-1,1,2-triphosphonic acid, ethane-1,2
-Phosphonic acids such as -dicarboxy-1,2-diphosphonic acid and methanehydroxyphosphonic acid or alkali metal salts or alkanolamine salts thereof, (3) 2-phosphonobutane-1,2-dicarboxylic acid, 1-phosphonobutane-2, Phosphonocarboxylic acids such as 3,4-tricarboxylic acid and α-methylphosphonosuccinic acid or alkali metal salts or alkanolamine salts thereof, (4) amino acids such as aspartic acid, glutamic acid and glycine, or alkali metal salts thereof or Alkanolamine salts,
(5) Aminopolyacetic acids such as nitrilotriacetic acid, iminodiacetic acid, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, glycol etherdiaminetetraacetic acid, hydroxyethyliminodiacetic acid, triethylenetetraaminehexaacetic acid, diencoric acid, and alkali metal salts thereof. Or alkanolamine salts, (6) diglycolic acid, oxydisuccinic acid, carboxymethyloxysuccinic acid, citric acid, lactic acid, tartaric acid, oxalic acid, malic acid, oxydisuccinic acid, gluconic acid, carboxymethylsuccinic acid, carboxymethyltartaric acid, etc. (7) an alkali metal salt or an alkanolamine salt of aluminosilicate represented by zeolite A, (8) an aminopoly (methylene phosphonic acid) or An alkali metal salt or an alkanolamine salt, or a polyethylene polyamine (methylene phosphonic acid) or alkali metal salts or alkanolamine salts, and the like are preferable.

Among them, the above (2), (5),
At least one selected from the group consisting of (6) and (8)
Species are preferred, and at least one selected from the group consisting of the above (2) is more preferred.

The liquid bleach composition of the present invention preferably contains 0.01 to 5% by weight, particularly 0.1 to 1.5% by weight of a sequestering agent.

It is preferable to use a fragrance in the liquid bleach composition of the present invention in order to increase the commercial value. As fragrances, fragrances conventionally incorporated in detergents, for example,
The fragrance described in 3-101496 can be used. Of course, the perfume components to be blended and, if necessary, the blending ratio and blending amount are taken into account so as not to be deteriorated by other detergent components.

The liquid bleaching composition of the present invention may contain a hydrotrope for the purpose of stabilizing the liquid at low temperatures and improving freeze-recoverability and preventing liquid separation at high temperatures. No problem. As such a hydrotrope, generally, a short-chain alkylbenzene sulfonate represented by toluene sulfonate, xylene sulfonate, etc., ethanol, ethylene glycol, propylene glycol, hexylene glycol, glycerin, etc. Typical examples include alcohols and polyhydric alcohols. The hydrotrope can be added in an amount of about 0 to 10% by weight in the liquid bleach composition of the present invention.

The liquid bleach composition of the present invention may further contain various compounds. For example,
Phosphoric acid known as a stabilizer for hydrogen peroxide, barbituric acid, uric acid, acetanilide, aminopolycarboxylic acids represented by oxyquinoline and phenacetin, and DL-α-tocopherol, gallic acid derivatives,
Butylated hydroxyanisole (BHA), 2,6-di-tert-butyl-4-methylphenol (BHT) and the like can be added. The amount of these stabilizers depends on the concentration of hydrogen peroxide, but it is usually about 0 to 5% by weight, preferably 0.01 to 3% by weight, in the composition of the present invention.

Further, the liquid bleach composition of the present invention may contain a substance known as a discoloration inhibitor. Such substances include phenylalanine, histidine,
Amino acids and amino acid salts such as lysine, tyrosine and methionine, and amino or imide compounds such as hydroxyiminodiacetic acid, and also one or more copolymers of monomers copolymerizable with acrylonitrile and acrylonitrile having a quaternary ammonium group And so on.
Although amino acids have optical isomers, optical isomers do not participate in the effects of the present invention. Therefore, it is also possible to use chemically synthesized amino acids.

In the liquid bleach composition of the present invention, Tinopal CBS (manufactured by Ciba Specialty Chemicals) and Tinopearl SWN (Ciba) are used as fluorescent whitening agents in order to increase the bleaching effect on white fiber. 0-5% by weight of a fluorescent whitening agent such as a specialty chemicals, or a color index fluorescent whitening agent 28, 40, 61 or 71 may be added.

Further, the liquid bleach composition of the present invention further comprises a coloring agent such as a dye or a pigment, a fragrance, a bactericide, an ultraviolet absorber, an inorganic electrolyte (for example, NaCl, Na ₂ SO ₄ ,
CaCl ₂ ) and various other small amounts of additives (0 to 0, respectively)
(About 2% by weight). As the dye, an acid dye having hydrogen peroxide property in an acidic solution is particularly preferable.

From the viewpoint of storage stability of hydrogen peroxide, the liquid bleach composition of the present invention has a pH at 20 ° C. of 7 or less,
In particular, it is preferably 2 to 6. To adjust the pH, use an inorganic acid such as sulfuric acid or phosphoric acid, or an organic acid such as toluenesulfonic acid or benzenesulfonic acid, or use the above-described sequestering agent or anionic surfactant It is advisable to add it in the form or to adjust it with a caustic such as sodium hydroxide or potassium hydroxide as needed.

The liquid bleach composition of the present invention is applied directly to clothing, and immediately or after leaving for a predetermined time, for example, 5 to 30 minutes, and then washed with a washing machine or the like. It is used in such a method that clothes are immersed in an aqueous solution in which a substance is dissolved.

The liquid bleaching composition of the present invention can be used in combination with a conventionally known clothing detergent.

[0042]

According to the present invention, it is possible to provide a liquid bleaching composition which more effectively realizes a suitable viscosity at the time of use for coating and has an excellent bleaching and detergency for all stains and stains. .

[0043]

EXAMPLES Liquid bleach compositions having the compositions shown in Tables 1 to 3 were prepared using hydrogen peroxide and the following b-1 to f-1.

(B) Ingredients b-1: Emulgen 2200 (manufactured by Kao Corporation, polyoxyethylene cetyl ether, molecular weight 7000) b-2: Bissurf CT (manufactured by Kao Corporation, Emulgen 2200 and vinylcyclohexenedi) B'-1: Xanthan gum (manufactured by Aldrich) (c) component-c-1: Polyethylene glycol (average degree of condensation 30)
0) · c-2: Polyethylene glycol (average degree of condensation 35) (Other Components) · d-1: alkylbenzene sulfonate sodium _{· d-2: C 12 H} 25 O (C 2 H 4 O) 6 -H · _{d-3: C 12 H 25} O (C 2 H 4 O) 8 -H · d-4: N- tetradecyl -N, N-dimethyl ammonium methyl sulfate

[0045]

Embedded image

F-1: phosphonic acid chelating agent (Dequest 2010, manufactured by Monsanto Japan Limited).

With respect to the obtained liquid bleaching composition, the viscosity, the bleaching performance at the time of application and the storage stability were examined by the following methods.

(Measurement of Viscosity)
was placed in a 20 ° C. constant temperature bath for 30 minutes, and the viscosity was measured using a B-type viscometer (model BM) manufactured by Tokyo Keiki Co., Ltd. (Rotor No. 1).
1, 60 r / min)).

(Evaluation of bleaching performance) Mud dirt Two pairs of socks worn by an 8-year-old boy for one day (Gunze Co., Ltd.)
, Support & clean, cotton, acrylic, polyester, polyurethane), apply 5 mL of the liquid bleaching agent shown in Table 2, and after 5 minutes, add a commercially available weak alkaline detergent (Attack, Kao Corporation, 0.0667%) The washing was performed using a washing machine standard course (National washing machine NA-F60E). After dehydration and natural drying, 10 trained panelists (3
5 males of the 0-year-old and 5 females of the 30-year-old) were evaluated according to the following criteria, and the average score was obtained. Table 2 shows the results. 1; dirt has been removed to a satisfactory level 2; slight dirt remains 3; dirt remains 4; considerable dirt remains ・ Lar oil dirt Each of 4 dirt oil stained cloths prepared as follows , Table 2
1 ml of the liquid bleach composition shown in Table 1 was applied, and after 5 minutes, the commercially available weak alkaline detergent solution (concentration: 0.0833)
(% By weight) and washed with a tergotometer using 1 L. After being sufficiently rinsed with tap water, it was dried and the bleaching ratio was calculated by the following equation.

[0050]

(Equation 1)

The reflectance is ND manufactured by Nippon Denshoku Industries Co., Ltd.
It was measured using a 460 nm filter with R-101DP. In addition, as for the contaminated oil cloth, 0.3 mL of oil oil manufactured by SUBY FOOD CO., LTD.
cm) and dried naturally for 3 hours to provide a test cloth for the experiment.

(Evaluation of Storage Stability) The liquid bleach composition of Table 3 was placed in a 100 mL screw tube, and the appearance after storage at 40 ° C. for one month was visually evaluated according to the following criteria. ：: uniform and transparent ×: one of separation, cloudiness, and precipitation is observed

[0053]

[Table 1]

[0054]

[Table 2]

[0055]

[Table 3]

(Note) The pH was adjusted using a 0.1N aqueous sulfuric acid solution or a 0.1N aqueous sodium hydroxide solution.

First, regarding the effect of viscosity, Examples 1 and 2 in Table 1 were used.
According to the result, if the total blending amount of the component (b) and the component (c) is the same, the viscosity of Example 1 is higher, so that the combination of the component (b) and the component (c) It is considered that the thickening effect is higher than the use of component b) alone.

Table 2 shows the results of the bleaching effect. Example 5 shows a combination system of the component (b) and the component (c), Example 6 shows a system using the component (b) alone, and Example 7 shows a system using the component (c) alone. From this, it is considered that the bleaching performance is improved when the component (c) is used in combination with the component (b) rather than when the component (b) is used alone.

According to the results of Examples 8 and 9 in Table 3, the component (c) alone did not provide a thickening effect, and from the results of Examples 10 and 11, storage exceeded (c) / (b) = 10. It can be seen that the stability decreases.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C11D 17/04 C11D 17/04 17/08 17/08 (72) Inventor Muneo Aoyagi 1334 Minato, Wakayama City, Wakayama Prefecture 4H003 AB19 AC08 AE05 BA12 BA21 DA01 DA03 EB09 EB24 EB34 EB46 ED02 EE04 FA30 FA43 FA44

Claims (3)

[Claims] (1) hydrogen peroxide; (b) at least one alkyl or alkenyl group having 8 to 20 carbon atoms in a molecule; and a polyoxyalkylene chain (alkylene group having 2 to 4 carbon atoms). And at least one compound having a weight average molecular weight of 2,500 to 50,000
% By weight and (c) 0.01 to 10% by weight of a polyalkylene glycol (alkylene group having 2 to 4 carbon atoms), and (c) / (b) is 0.001 to 10 in weight ratio. Liquid bleach composition. 2. The liquid bleach composition according to claim 1, wherein (b) is a compound of the following general formula (I). R ¹ -X-[(R ² O) _m- (CO) _p -R ³ ] _n (I) wherein R ¹ is an alkyl or alkenyl group having 8 to 20 carbon atoms, and R ² is ² carbon atoms. Or 3 alkylene groups.
X represents any of O, COO, N, and CON, and X represents O
Or, in the case of COO, n = 1, and when X is N or CON, n = 2. m is 50 to 500, p is 0 or 1, R ³
Is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms or 8 carbon atoms.
Represents up to 20 alkenyl groups. ] 3. A viscosity at 20 ° C. of 10 to 600 mP.
The liquid bleach composition according to claim 1 or 2, which is a · s.