JPH09188895A - Liquid bleaching agent composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a liq. oxygen-based bleaching agent compsn. which hardly undergoes a change in viscosity with a change in temp. and does not undergo the decomposition of hydrogen peroxide during storage. SOLUTION: This compsn. contains hydrogen peroxide, 0.1-30wt.% nonionic surfactant (a) having an HLB determined by the Davis method of 5-12, and 0.1-30wt.% nonionic surfactant (b) having an HLB determined by the Davis method of 4.3-10 and lower than that of the surfactant (a) by 0.2-1.5 in a wt. ratio of the surfactant (a), to the surfactant (b) of (100:1)-(1:100).

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a liquid bleaching composition, and more particularly to a liquid bleaching composition having little change in viscosity with temperature and excellent stability of hydrogen peroxide. It is a thing.

[0002]

BACKGROUND OF THE INVENTION Bleaching agents are classified into chlorine-based bleaching agents and oxygen-based bleaching agents. However, chlorine-based bleaching agents cannot be used for colors and patterns because of the limited fibers that can be used. In addition, the oxygen-based bleaching agent, which does not have these drawbacks, has recently been remarkably popular because it has a unique odor. Of these oxygen-based bleaching agents, sodium percarbonate and sodium perborate are used as powder bleaching agents, and hydrogen peroxide is used as a liquid oxygen-based bleaching agent. It is especially preferred because it is easy to apply.

By the way, when a liquid oxygen bleaching agent is directly applied to clothes, the viscosity of the liquid affects the ease of use, and therefore a method of controlling the viscosity has been studied. WO94 / 114
No. 74 discloses a method for controlling viscosity by using two kinds of nonionic surfactants. Also, USP49
No. 00469 discloses a method of controlling viscosity by blending a fatty acid. However, these methods have a problem in that the viscosity remarkably changes with a change in temperature, which makes it difficult to use in actual use. Further, in a system without hydrogen peroxide, USP 4648987 discloses a method of controlling viscosity by using two kinds of nonionic surfactants and xanthan gum. However, when these methods are applied to a system in which hydrogen peroxide is present, there is a problem that hydrogen peroxide is significantly decomposed during storage.

Accordingly, it is an object of the present invention to provide a liquid oxygen bleaching agent which has a small change in viscosity with respect to a change in temperature and which does not decompose hydrogen peroxide during storage.

[0005]

Means for Solving the Problems As a result of intensive studies for solving the above-mentioned problems, the present inventors have found that at least two specific nonionic surfactants are blended in a specific combination in a specific ratio. As a result, they have found that the above problems can be solved, and completed the present invention.

That is, the present invention is based on hydrogen peroxide, (a) at least one nonionic surfactant having an HLB of 5 to 12 determined by Davis 'method, and (b) determined by Davis' method. HLB of 4.3 to 10 and at least one nonionic surfactant smaller than HLB of the nonionic surfactant of (a) by 0.2 to 1.5, and the content of the nonionic surfactant of (a). Is 0.1 to 30% by weight, the content of the nonionic surfactant (b) is 0.1 to 30% by weight, and the blended weight of the nonionic surfactant (a) and the nonionic surfactant (b). The ratio is (a)
/ (B) = 100/1 to 1/100, to provide a liquid bleaching composition.

HLB by the method of Mr. Davis is "Surfactant: Physical properties / application / chemical ecology", 7th edition, page 24,
Defined in Fumio Kitahara, Yasukatsu Ooi, Shigeo Hayano, Ichiro Hara, published by Kodansha Scientific (issued in 1990).

[0008]

Embodiments of the present invention will be described below in detail.

The liquid oxygen bleach currently available on the market is
The viscosity at 20 ° C. was low, and when such a liquid oxygen bleaching agent was applied to clothing, it flowed before it permeated into the fibers and the effect of application and washing could not be fully exerted. Viscosity is 3 cp to 100 c in order to fully exert the coating cleaning effect.
p, preferably 3 to 50 cp, and more preferably 3 to 40 cp is good, and such viscosity can be achieved to some extent by adding a surfactant such as a nonionic surfactant. However, such a liquid oxygen-based bleaching composition has a problem in that when the temperature is changed from 10 ° C. to 40 ° C., the viscosity remarkably changes and the usability deteriorates. Therefore, a liquid bleaching composition having a viscosity at 10 to 40 ° C. of 3 cp to 100 cp and a viscosity change rate of ± 20% or less when the temperature changes by 10 ° C. in this temperature range is desired. Here, the rate of change in viscosity is a value represented by the following formula.

[0010]

[Equation 1]

As a result of intensive investigations by the present inventors in order to obtain such a liquid oxygen bleaching composition, at least two nonionic surfactants having a specific HLB as described above are combined in a specific combination. It could be achieved by using it.

That is, the nonionic surfactant used in the present invention has (a) HLB of 5 to 1 obtained by the method of Davis.
2, preferably 5-10, more preferably 5-8, at least one nonionic surfactant (hereinafter abbreviated as nonionic surfactant (a)), and (b) determined by the method of Davis. HLB is 4.3 to 10, preferably 4.3 to 8, more preferably 4.5 to 7, and 0.2 to 1.5, preferably 0.5 to 1.5, more preferably HLB of the nonionic surfactant (a).
It is selected from at least one small nonionic surfactant (hereinafter abbreviated as nonionic surfactant (b)) of 0.7 to 1.5.

Nonionic surfactant (a) used in the present invention
The nonionic surfactant (b) is preferably a nonionic surfactant represented by the general formula (I).

R ^1- (OA) _n -OX (I) [In the formula, R ¹ is a linear alkyl group having 6 to 20 carbon atoms, preferably 8 to 18 carbon atoms, more preferably 8 to 14 carbon atoms, and A 1 is Carbon number 2
To 3 are linear or branched alkylene groups, preferably ethylene groups, and n is 2 to 20, preferably 2 to 15, more preferably 3 showing the average number of moles of alkylene oxide added.
Is a number of 15 to 15, and X is H or an alkyl group having 1 to 5 carbon atoms, preferably H or a methyl group. Where R ¹ ,
n and X are 5 in the above HLB for the nonionic surfactant (a).
~ 12, nonionic surfactant (b) has HLB of 4.3 ~
10 and 0.2-1. From the HLB of nonionic surfactant (a).
5 Selected to be smaller. As a more specific example, the combination of compounds shown in Table 1 is preferable.

[0015]

[Table 1]

The content of hydrogen peroxide in the liquid bleach composition of the present invention is 0.1 to 10% by weight, preferably 0.5 to 10% by weight, more preferably 1 to 6% by weight. When the content of hydrogen peroxide is 0.1 to 10% by weight, sufficient bleaching performance and excellent storage stability can be obtained.

The content of the nonionic surfactant (a) in the liquid bleach composition of the present invention is 0.1 to 30% by weight, preferably 0.5 to 20% by weight, more preferably 0.5 to 10% by weight. Content of the nonionic surfactant (b) is 0.1 to 30% by weight, preferably 0.1 to 10% by weight, more preferably 0.1 to 10% by weight.
5% by weight. Further, the blending weight ratio of the nonionic surfactant (a) and the nonionic surfactant (b) is (a) / (b) = 100.
/ 1 to 1/100, preferably 100/1 to 1/5, and more preferably 100/1 to 1/1. Nonionic surfactant
If the content of (a) is less than 0.1% by weight, sufficient bleaching performance cannot be obtained, and if it exceeds 30% by weight, the viscosity is remarkably increased and it becomes difficult to handle. Further, if the content of the nonionic surfactant (b) is less than 0.1% by weight, the viscosity remarkably changes with temperature change, and if it exceeds 30% by weight, the viscosity remarkably increases and it becomes difficult to handle. Further, the blending weight ratio (a) / (b) of the nonionic surfactant (a) and the nonionic surfactant (b) is 100/1 to
If it deviates from the range of 1/100, the viscosity changes remarkably with temperature changes, which causes a problem that it becomes difficult to handle.

Further, the liquid bleach composition of the present invention comprises
A bleach activator can be added as the component (c).
The compounding amount is 0 to 20% by weight, preferably 0.1% in the composition.
˜10% by weight, more preferably 0.1 to 5% by weight.
When the blending amount of the component (d) is 20% by weight or less, the bleaching performance can be improved without decolorizing the colored pattern, which is preferable.

Examples of the bleach activator include O-acetylated compounds represented by glucose pentaacetate, N-acylated compounds represented by tetraacetylethylenediamine, and acid anhydrides represented by maleic anhydride. In addition, alkanoyloxybenzenesulfonates exemplified in JP-B-63-12520 and JP-A-6-316700, and JP-A-63-2339.
69, JP-A-63-31566, JP-A-6
Examples thereof include a bleach activator which reacts with hydrogen peroxide to produce an organic peracid having a quaternary ammonium group, as disclosed in JP-A-4-68347 and JP-A-1-190654. . Among these bleach activators, the compound represented by the general formula (II) is preferable.

[0020]

Embedded image

[In the formula, R ² is a straight or branched chain having 5 to 5 carbon atoms.
19 represents an alkyl group or an alkenyl group, and Y represents —SO ₃ M or —COOM. Here, M represents H or a cation such as an alkali metal or an alkaline earth metal. ] The following compounds are mentioned as these specific examples.

[0022]

Embedded image

Further, the liquid bleach composition of the present invention comprises
As component (d), at least one selected from anionic surfactants and cationic surfactants can be blended. The blending amount of the component (d) is 0 to 10% by weight, preferably 0.
The amount is 01 to 5% by weight, more preferably 0.05 to 5% by weight.
When the compounding amount of the component (d) is 10% by weight or less, there is no increase in the viscosity of the composition and it is preferable from the viewpoint of easy handling.

Specific examples of the anionic surfactant and the cationic surfactant include alkylbenzene sulfonates, alkyl or alkenyl ether sulfates, alkyl or alkenyl sulfates, olefin sulfonates, alkane sulfonates, saturated or unsaturated. Fatty acid salts, alkyl or alkenyl ether carboxylates,
Examples include α-sulfo fatty acid salts or α-sulfo fatty acid esters, quaternary ammonium salts and the like. Among these, alkylbenzene sulfonates (where the average carbon number of the alkyl group is preferably 12) are preferable as the anionic surfactant, and the compound represented by the general formula (III) is preferable as the cationic surfactant.

[0025]

Embedded image

[In the formula, R ¹¹ , R ¹² , R ¹³ and R ¹⁴ : at least one of these groups represents a linear or branched alkyl group or alkenyl group having 6 to 20 carbon atoms, and the remaining The group represents an alkyl group having 1 to 3 carbon atoms or a hydroxyalkyl group. L ⁻ : Indicates an anionic group. Examples of L ⁻ in the general formula (III) include a halogen anion, an alkylsulfate anion, and a fatty acid anion. As specific examples of these, the following general formula (III-
The compound represented by 1) or (III-2) is mentioned.

[0027]

Embedded image

[In the formula, R ^{11-1 represents a} linear or branched alkyl group having 6 to 20 carbon atoms. R ^12-1 : Shows an alkyl group having 1 to 3 carbon atoms. L ^1- : a halogen anion, an alkyl sulfate (wherein the alkyl group has 1 to 3 carbon atoms) anion or a fatty acid anion. ]

[0029]

[Chemical 6]

[In the formula, R ^11-1 , R ^12-1 , L ^1- : has the above meaning. R ^14-1 : a linear or branched alkyl group having 6 to 20 carbon atoms is shown. Further, the liquid bleaching composition of the present invention may contain a sequestering agent as the component (e). Examples of the sequestering agent 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 its derivatives, ethanehydroxy-1,1,2-
Triphosphonic acid, ethane-1,2-dicarboxy-1,2-
Phosphonic acid such as diphosphonic acid, methanehydroxyphosphonic acid or an alkali metal salt or alkanolamine salt thereof (3) 2-phosphonobutane-1,2-dicarboxylic acid, 1-phosphonobutane-2,3,4-tricarboxylic acid, α- Phosphonocarboxylic acids such as methylphosphonosuccinic acid or alkali metal salts or alkanolamine salts thereof (4) aspartic acid, glutamic acid, amino acids such as glycine or alkali metal salts or alkanolamine salts thereof (5) nitrilotriacetic acid, Iminodiacetic acid, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, glycol etherdiaminetetraacetic acid, hydroxyethyliminodiacetic acid,
Aminopolyacetic acid such as triethylenetetramine hexaacetic acid and diencoric acid or their alkali metal salts or alkanolamine salts (6) Diglycolic acid, oxydisuccinic acid, carboxymethyloxysuccinic acid, citric acid, lactic acid, tartaric acid, oxalic acid, malic acid , Oxydisuccinic acid, gluconic acid, carboxymethyl succinic acid, carboxymethyl tartaric acid, and other organic acids, or their alkali metal salts or alkanolamine salts (7) Alkali metal salts of aluminosilicate represented by zeolite A or alkanolamine salts (8) ) Aminopoly (methylenephosphonic acid) or its alkali metal salt or alkanolamine salt, or polyethylenepolyamine poly (methylenephosphonic acid) or its alkali metal salt or alkanolamine salt. Of these, at least one selected from the group consisting of the above (2), (5), (6) and (7) is preferred, and at least one selected from the group consisting of the above (2) is more preferred. The amount of such a sequestering agent is desirably 0.0005 to 5% by weight, preferably 0.01 to 1% by weight, based on the liquid bleaching composition of the present invention.

The liquid bleach composition of the present invention may contain known components which are usually added in addition to the above components. For example, water-soluble inorganic builders such as sulfates, carbonates, bicarbonates, silicates and phosphates can be used as builders. In addition, as a stabilizer for peroxides or hydrogen peroxide adducts, known magnesium sulfate, magnesium silicate, magnesium chloride, magnesium silicofluoride, magnesium oxide, magnesium salts such as magnesium hydroxide, and silicates such as sodium silicate are used. be able to. Further, if necessary, a redeposition inhibitor such as carboxymethylcellulose, polyvinylpyrrolidone, or polyethylene glycol can be added.

The liquid bleach composition of the present invention basically comprises hydrogen peroxide, nonionic surfactants (a) and (b), or hydrogen peroxide, nonionic surfactants (a) and ( b) Further, the above-mentioned components (c) to (e) are dissolved or dispersed in water, but the stabilization of the liquid at low temperature and the freeze-restoration property are improved, and the liquid separation at high temperature is performed. A hydrotrope agent may be added for the purpose of prevention. 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. Representative examples include alcohols and polyhydric alcohols. The hydrotrope can be added in an amount of about 0 to 30% 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, barbituric acid, uric acid, acetanilide, aminopolycarboxylic acids represented by oxyquinoline, phenacetin and the like, and DL-α-tocopherol, gallic acid derivatives, butyl known as hydrogen peroxide stabilizers 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 an anti-fading agent. Such substances include phenylalanine, histidine,
Lysine, tyrosine, amino acids such as methionine and amino acid salts, and amino or imide compounds such as hydroxyiminodiacetic acid, and acrylonitrile and one or two or more monomers copolymerizable with acrylonitrile having a quaternary ammonium group And copolymers. 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 addition, the liquid bleach composition of the present invention contains Tinopearl (T) as a fluorescent whitening agent to increase the bleaching effect on white fiber.
inopal) CBS (manufactured by Ciba-Geigy),
A fluorescent whitening agent such as Tinopearl SWN (manufactured by Ciba Geigy) or a color index fluorescent whitening agent 28, 40, 61, 71 may be added in an amount of 0 to 5% by weight.

Further, a thickener can be added to the liquid bleaching composition of the present invention in an amount of 0 to 20% by weight for the purpose of increasing the viscosity of the composition and improving usability. As the thickener, generally, polyacrylates, acrylic acid-maleic acid copolymer, carboxymethylcellulose derivatives, methylcellulose, synthetic polymers such as hydroxymethylcellulose, natural polymers such as xanthan gum, guar gum, kelzan, montmorillonite, veegum Water-swellable clay minerals are used.

Further, the liquid bleaching composition of the present invention further comprises coloring agents such as dyes and pigments, fragrances, bactericides, ultraviolet absorbers and inorganic electrolytes (eg NaCl, Na ₂ SO ₄ , CaCl ₂ ).
, Etc., can be added in appropriate amounts (each about 0 to about 2% by weight). As the dye, an acid dye having hydrogen peroxide resistance in an acidic solution is particularly preferable. In addition, in the composition of the present invention, in order to improve the bleaching performance, conventionally known enzymes (cellulase, amylase, protease, lipase, etc.) can be added as necessary.

The pH of the liquid bleaching composition of the present invention is desirably 6 or less, preferably 3.5 or less. In order 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 metal-sequestering agent or anionic surfactant in an acid form. Or, if necessary, by using a caustic such as sodium hydroxide or potassium hydroxide. Further, the liquid bleach composition of the present invention can be used by mixing with a conventionally known clothing detergent.

[0038]

INDUSTRIAL APPLICABILITY According to the present invention, it is possible to provide a liquid bleaching composition which has a small change in viscosity with temperature and has a high bleaching effect in coating cleaning.

[0039]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples.

Examples 1 to 6 and Comparative Examples 1 to 6 Hydrogen peroxide, nonionic surfactants (a) and (b) selected from the nonionic surfactants 1 to 8 shown in Table 2, c) As a bleach activator of the following components (c-1) ~ (c-2)
The following (d-1) to (d-2) are used as the anionic or cationic surfactant of the component (d), and the following (e-1) is used as the sequestering agent of the component (e). A liquid bleach composition having the composition shown in Table 3 and Table 4 was prepared. The compositions in Tables 3 and 4 were adjusted to pH 2 with 0.5N sulfuric acid aqueous solution.

[0041]

[Table 2]

Note) *: Obtained by the method of Mr. Davis.

[0043]

Embedded image

The bleaching performance of the obtained liquid bleaching composition was measured by the following method, and the viscosity at each temperature was measured using a B-type viscometer manufactured by Tokyo Keiki Co., Ltd. (model BM). The results are shown in Tables 3 and 4.

<Measurement of Bleaching Performance> 0.5 ml of the liquid bleaching agent composition shown in Tables 3 and 4 was applied to 5 pieces of black tea-contaminated cloths prepared as described below, and immediately the commercially available weak alkaline detergent solution (concentration) : 0.0833%) 1 liter was used for washing with a tergotometer. After sufficiently rinsing with tap water, it was dried and the bleaching rate was calculated by the following formula.

[0046]

[Equation 2]

The reflectance is NDR-101DP manufactured by Nippon Denshoku Industries Co., Ltd.
At 460 nm using a filter. (Preparation of black tea contaminated cloth) Nitto black tea (yellow package) 80
After being boiled with 3 liters of ion-exchanged water for about 15 minutes, it was rubbed with desizing-exposed cotton, and a cotton cloth # 2003 was dipped in this solution and boiled for about 15 minutes. Remove from heat as it is, about 2
After leaving it for about an hour, it was naturally dried, washed with water until the washing liquid was not colored, dehydrated, pressed, and made into a test piece of 10 cm × 10 cm, which was used for the experiment.

[0048]

[Table 3]

[0049]

[Table 4]

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Muneo Aoyagi 1334 Minato, Wakayama City, Wakayama Pref.

Claims (7)

[Claims] 1. Hydrogen peroxide, (a) at least one nonionic surfactant having an HLB of 5 to 12 determined by Davis's method, and (b) HLB determined by Davis's method.
Of 4.3 to 10 and 0.2 to 1.5 smaller than the HLB of the nonionic surfactant of (a) at least one of the nonionic surfactants.
And the content of nonionic surfactant (a) is
0.1 to 30% by weight, the content of (b) nonionic surfactant is
0.1 to 30% by weight, the blending weight ratio of the nonionic surfactant (a) to the nonionic surfactant (b) is (a) / (b) = 100.
The liquid bleaching composition is characterized in that it is from 1/1 to 1/100. 2. The liquid bleach composition according to claim 1, wherein the nonionic surfactant (a) and the nonionic surfactant (b) are nonionic surfactants represented by the general formula (I). Stuff. R ^1- (OA) _n -OX (I) [In the formula, R ¹ is a linear alkyl group having 6 to 20 carbon atoms, and
Is a linear or branched alkylene group having 2 to 3 carbon atoms,
n is the average number of moles of alkylene oxide added 2 to
The number is 20, and X is H or an alkyl group having 1 to 5 carbon atoms. However, R ¹ , n and X are such that the nonionic surfactant of (a) has an HLB of 5 to 12 and the nonionic surfactant of (b) has an HLB of 4.3 to 10 and a nonionic surfactant of (a) It is selected to be 0.2-1.5 smaller than the HLB of the ionic surfactant. ] 3. The liquid bleaching according to claim 1, wherein the viscosity at 10 to 40 ° C. is 3 cp to 100 cp, and the rate of change in viscosity when the temperature changes by 10 ° C. in this temperature range is ± 20% or less. Agent composition. 4. The liquid bleaching composition according to claim 1, which further contains a bleaching activator as the component (c). 5. The liquid bleaching composition according to claim 4, wherein the bleaching activator is a compound represented by the general formula (II). Embedded image [In the formula, R ² represents a linear or branched alkyl group or alkenyl group having 5 to 19 carbon atoms, and Y represents -SO ₃ M or -COOM. Here, M represents H or a cation. ] 6. The method according to claim 1, further comprising an anionic surfactant or a cationic surfactant as the component (d).
A liquid bleaching composition according to any one of the preceding claims. 7. The liquid bleaching composition according to claim 1, further comprising a sequestering agent as the component (e).