JPH08295897A - Liquid bleach composition - Google Patents

Abstract

PURPOSE: To provide a liquid bleaching composition which does not require the combination with an alkaline detergent and shows a high bleaching effect against oil stain as well as tea stain when it is applied and washed. CONSTITUTION: This composition consists of (A) 0.5-10wt.% of H2 O2 or an inorganic peroxide which forms H2 O2 in aqueous solution, (B) 3-30wt.% of a nonionic surfactant of 5-12 HLB value according to Davies' method and (C) 0.001-20wt.% of a lipophilic compound having at least a 6-22 C alkyl, an alkenyl or an aryl group and at least one hydrophilic group in the molecule and having a HLB value of less than 5 where the weight ratio of (C)/(B) is set to 0.001-1.0.

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 a high bleaching power in coating and washing and particularly useful for bleaching textiles.

[0002]

BACKGROUND OF THE INVENTION Bleaching agents are classified into chlorine-based bleaching agents and oxygen-based bleaching agents, but chlorine-based bleaching agents are limited in the fibers that can be used. Oxygen-based bleaching agents, which do not have these drawbacks, have recently become extremely popular because they cannot be used and have a characteristic 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 particularly preferred because it can be applied directly to the skin.

The liquid oxygen bleaching agent is usually stored under acidic conditions from the viewpoint of the stability of hydrogen peroxide, and when it is actually used, it can be effectively treated by mixing it with an alkaline detergent or the like and setting it under alkaline conditions. Is bleached. This is generated under alkaline conditions although the bleaching power of hydrogen peroxide itself is relatively low
This is because -OOH ions have high bleaching power. For this reason, when applying liquid oxygen bleach to textiles,
An effective bleaching power could not be obtained unless it was used in combination with an alkaline detergent or the like.

In order to compensate for these drawbacks, various surfactants have been added to the liquid bleaching composition to enhance the bleaching power. For example, JP-A-3-17194 discloses a liquid bleaching composition containing a nonionic surfactant and an anionic surfactant. In addition, JP-A-4-213
No. 400 discloses a liquid bleach composition containing an anionic or nonionic surfactant and glutaric acid, polyethylene glycol or the like. However, if the liquid oxygen-based bleaching agent containing these surfactants is used for application cleaning without being used in combination with an alkaline detergent, it is effective for cleaning oil stains, etc. However, it has a drawback that it does not show a bleaching effect for stains requiring the bleaching power of. Further, when a large amount of a surfactant is blended, the viscosity of the liquid bleaching agent composition remarkably increases, which makes it difficult to handle.

An object of the present invention is to provide a liquid bleaching composition which does not need to be used in combination with an alkaline detergent and exhibits high bleaching power not only on oil stains but also on black tea stains when applied and washed. is there.

[0006]

In order to solve the above problems, the present inventors have made earnest studies and, as a result, have found that the above objects can be achieved by combining extremely selected components, and the present invention has been made. completed. That is, the present invention is as follows:
It contains 0.5 to 10% by weight of component (a), 3 to 30% by weight of component (b) and 0.001 to 20% by weight of component (c), and contains (c) component and (b)
The weight ratio of the components is [(c) component] / [(b) component] = 0.001 ~
A liquid bleaching composition characterized in that it is 1.0.

(A) Component: H ₂ O ₂ or an inorganic peroxide that generates H ₂ O ₂ in an aqueous solution (b) Component: Nonionic surfactant having an HLB of 5 to 12 by the method of Davies (c ) Component: HLB according to the method of Davies, which has at least one alkyl group, alkenyl group or aryl group having 6 to 22 carbon atoms and at least one hydrophilic group in the molecule.
A lipophilic compound having a value of less than 5

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION Embodiments of the present invention will be described in detail below.

[Component (a)] In the present invention, as the component (a), H ₂ O ₂ or an inorganic peroxide capable of generating H ₂ O ₂ in an aqueous solution is used. Examples of inorganic peroxides that generate H ₂ O ₂ in an aqueous solution include sodium percarbonate and sodium perborate.

[Component (b)] In the present invention, a nonionic surfactant having an HLB of 5 to 12, preferably 5 to 11, and more preferably 5.5 to 10 according to the method of Davies is used as the component (b). It (b) Component H by Davies' method
When LB is lower than 5, sufficient bleaching performance cannot be obtained,
If it is higher than 12, problems such as increase in viscosity of the composition and separation of blended components tend to occur.

HLB by the method of Davies is "Surfactant: Physical Properties, Applied and Chemical Ecology", 7th edition , page 24, Fumio Kitahara, Yasukatsu Ooi, Shigeo Hayano, Ichiro Hara, Kodansha Scientific. Issuance (issued in 1990).

Examples of the nonionic surfactant preferable as the component (b) include nonionic surfactants represented by the general formula (I). R ¹ X (AO) _m Y (I) [In the formula, R ^{1 represents a} linear or branched alkyl group or an alkenyl group having 6 to 22 carbon atoms, or the total number of linear or branched carbon atoms is 1 The alkyl group of -18 represents an aryl group which may be substituted. X: represents an -O- group or a -COO- group. A: Shows a linear or branched alkylene group having 2 to 3 carbon atoms. Y: H or an alkyl group having 1 to 3 carbon atoms is shown. m: 3 to 50 showing the average number of moles of alkylene oxide added
Number of. However, in this case, R ¹ , X, A, Y and m
Are selected so that the HLB according to Davies' method is 5-12. In the general formula (I), the A group represents an ethylene group or a propylene group (preferably a branched propylene group), which may be added in a block type or may be added in a random type. . More specifically, the nonionic surfactants shown in Table 1 can be mentioned.

[0013]

[Table 1]

[Component (c)] In the present invention, the component (c) has at least one alkyl group, alkenyl group or aryl group having 6 to 22 carbon atoms and at least one hydrophilic group in the molecule. However, lipophilic compounds having an HLB of less than 5, preferably less than 4, and more preferably less than 3 according to the method of Davies are used. When the HLB of the component (c) is 5 or more, good bleaching performance cannot be obtained, and the composition tends to separate in the composition.

The hydrophilic group in this case means the above-mentioned "Surfactant: Physical properties / application / chemical ecology", 7th edition , page 24, table
Say what is listed in 1.13. Among these hydrophilic groups, carboxyl group (-COOH), hydroxyl group (-OH), ester group or tertiary amine group or acid salt of the group is preferable, and aliphatic alcohol having -COOH or -OH group or Aliphatic carboxylic acids are more preferred.

As the preferred lipophilic compound of the component (c),
For example, the compound represented by the general formula (II) may be mentioned. R ² Z (II) [In the formula, R ^{2 represents a} linear or branched alkyl group or alkenyl group having 6 to 22 carbon atoms, or a linear or branched alkyl group having 1 to 18 carbon atoms in total. Represents an optionally substituted aryl group. Z: Indicates -OH or -COOH. More specifically, the lipophilic compounds shown in Table 2 can be mentioned.

[0017]

[Table 2]

[Liquid Bleaching Agent Composition] In the liquid bleaching agent composition of the present invention, the component (a) is 0.5 to 10% by weight in the composition,
Preferably 1-10% by weight, more preferably 1-6% by weight
Be compounded. The component (b) is blended in an amount of 3 to 30% by weight, preferably 3 to 20% by weight, more preferably 5 to 20% by weight. Further, the component (c) is 0.001 to 20% by weight, preferably 0.
The amount is 01 to 10% by weight, more preferably 0.01 to 5% by weight. The weight ratio of the component (c) and the component (b) is [(c) component] / [(b) component] = 0.001 to 1.0, preferably 0.01 to
1.0, more preferably 0.01 to 0.5.

In this case, the component (a) is 0.5% by weight.
If it is less than 10% by weight, sufficient bleaching performance cannot be obtained, and if it exceeds 10% by weight, the storage stability of the composition is significantly reduced. Further, if the content of the component (b) is less than 3% by weight, sufficient bleaching performance cannot be obtained, and if it exceeds 30% by weight, the viscosity increases and handling becomes difficult. Further, if the content of the component (c) is less than 0.001% by weight, sufficient bleaching performance cannot be obtained, and if it exceeds 20% by weight, the composition becomes cloudy and the appearance is remarkably deteriorated. Also,
If the weight ratio of the (c) component to the (b) component [(c) component] / [(b) component] is less than 0.001, sufficient bleaching performance cannot be obtained and 1.0
If it exceeds the range, inconveniences such as clouding and separation of the solution occur.

In the present invention, by satisfying the above conditions, a liquid bleaching agent having a high bleaching power in coating and washing can be obtained. 20 of the liquid bleach composition of the present invention
The viscosity at ° C is 300 cp or less, preferably 200 cp or less,
More preferably, it is 100 cp or less. If the viscosity exceeds 300 cp, it becomes difficult to handle.

Further, the liquid bleach composition of the present invention comprises
A sequestering agent can be added as the component (d). As the sequestering agent, (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-
Diphosphonic acid, phosphonic acid such as methanehydroxyphosphonic acid, or their alkali metal salts or alkanolamine salts (3) 2-phosphonobutane-1,2-dicarboxylic acid, 1-phosphonobutane-2,3,4-tricarboxylic acid, α- Phosphonocarboxylic acids such as methylphosphonosuccinic acid or their alkali metal salts or alkanolamine salts (4) Aspartic acid, glutamic acid, amino acids such as glycine or their alkali metal salts or alkanolamine salts (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. Among these, at least one selected from the group consisting of (2), (5), (6) and (7) is preferable, and at least one selected from the group consisting of (2) is more preferable. The amount of such a sequestering agent is 0.0005 to 5% by weight, preferably 0.01 to 1% by weight, based on the liquid bleaching composition of the present invention.

In the present invention, in addition to the above components, at least one selected from anionic surfactants and cationic surfactants.
Seeds can be incorporated. Specific examples thereof 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. , Α-sulfo fatty acid salts or α-sulfo fatty acid esters, quaternary ammonium salts, and the like.

In the present invention, a bleaching activator may be further added. 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. Japanese Examined Patent Publication No. 63-12520 and Japanese Unexamined Patent Publication No. Hei 6
No. 316700, alkanoyloxybenzene sulfonates, and JP-A-63-23396.
9, JP-A-63-31566, JP-A-64
Examples include bleach activators which react with hydrogen peroxide to produce an organic peracid having a quaternary ammonium group, as disclosed in JP-A-68347 and JP-A-1-190654.

The liquid bleaching composition of the present invention may contain known components which are usually added in addition to the above components. For example, as the builder, a water-soluble inorganic builder such as sulfate, carbonate, bicarbonate, silicate or phosphate can be used. Further, known magnesium sulfate, magnesium silicate, magnesium chloride, magnesium silicate, magnesium oxide, magnesium hydroxide, and other magnesium salts and silicates such as sodium silicate are used as stabilizers for peroxides or hydrogen peroxide adducts. be able to. Further, if necessary, anti-redeposition agents such as carboxymethyl cellulose, polyvinylpyrrolidone, and polyethylene glycol can be added.

The liquid bleach composition of the present invention basically comprises the above-mentioned components (a) to (c), or (a) to (d),
Although it is dissolved or dispersed in water, a hydrotrope agent may be added for the purpose of improving the stability of liquid at low temperature and the freeze-restoration property, or preventing the liquid separation at high temperature. As such a hydrotrope, generally, a short-chain alkylbenzene sulfonate represented by toluene sulfonate, xylene sulfonate, etc.,
Examples thereof include alcohols represented by ethanol, ethylene glycol, propylene glycol, hexylene glycol, glycerin, and the like, and polyhydric alcohols. The hydrotrope can be incorporated in the liquid bleaching composition of the present invention in an amount of about 0 to 30% by weight.

The liquid bleaching composition of the present invention may further contain various compounds. For example,
Phosphoric acid, which is known as a stabilizer of hydrogen peroxide, barbituric acid, uric acid, acetanilide, aminopolycarboxylic acids represented by oxyquinoline and phenacetin, and DL-α-tocopherol, gallic acid derivative, butyl Hydroxyanisole (BHA), 2,6-
Di-tert-butyl-4-methylphenol (BHT) and the like can be added. The addition 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,
Amino acids and amino acid salts such as lysine, tyrosine, methionine, and amino or imide compounds such as hydroxyiminodiacetic acid, and one or more of acrylonitrile and acrylonitrile having a quaternary ammonium group and a copolymerizable monomer Copolymers and the like. Although amino acids have optical isomers, the optical isomers do not participate in the effect of the present invention. Therefore, it is also possible to use chemically synthesized amino acids. Further, the liquid bleaching composition of the present invention, as a fluorescent whitening agent in order to increase the bleaching effect on white fiber, Tinopearl (T
inopal) CBS [manufactured by Ciba-Geigy],
Optical brighteners such as Chino Pearl SWN (manufactured by Ciba Geigy) and color index optical brighteners 28, 40, 61, 71 may be added in an amount of 0 to 5% by weight.

Further, the liquid bleaching composition of the present invention may contain a thickener in an amount of 0 to 20% by weight for the purpose of increasing the viscosity of the composition and improving the usability. As the thickener, generally, a polyacrylic acid salt, a maleic acid acrylic acid copolymer, a carboxymethylcellulose derivative, a synthetic polymer such as methylcellulose or hydroxymethylcellulose, a natural polymer such as xanthan gum, guar gum, or kerzan, montmorillonite, or veegum. Water-swelling clay minerals such as are used.

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

The pH of the liquid bleach composition of the present invention is preferably 6 or less, more preferably 3.5 or less. To adjust the pH, use inorganic acids such as sulfuric acid and phosphoric acid, organic acids such as toluenesulfonic acid and benzenesulfonic acid, or use the above-mentioned sequestering agents and anionic surfactants in acid form. It is advisable to add it by using the above method or adjust it with a caustic alkali such as sodium hydroxide or potassium hydroxide if necessary. Further, the liquid bleaching composition of the present invention can also be used as a mixture with a conventionally known clothing detergent.

[0031]

According to the present invention, there is provided a liquid bleaching composition which does not need to be used in combination with an alkaline detergent and exhibits high bleaching power not only on oil stains but also on black tea stains when applied and washed. be able to.

[0032]

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

Examples 1 to 8 and Comparative Examples 1 to 5 H ₂ O ₂ as the component (a) and the following compound (b-1) as the component (b)
~ (B-5), the following compounds as the component (c) (c-1) ~ (c-4),
The following compounds (d-1) are used as the component (d), and the following compounds (b'-1) to (b'-3) are used as the other components, and the liquid bleaching agent composition is shown in Table 3 and Table 4, respectively. The thing was prepared. The bleaching performance of each of the obtained liquid bleaching compositions was measured by the following method, and the viscosity at 20 ° C. was measured by a B-type viscometer manufactured by Tokyo Keiki Co., Ltd. The results are shown in Tables 3 and 4. The blending composition shown in Table 3 and Table 4 was 0.5
The pH was adjusted to 2 with an aqueous solution of N-sulfuric acid.

(B) Component C ₁₂ H ₂₅ O (CH ₂ CH ₂ O) ₁₀ H (b-1) HLB 6.50 C ₁₈ H ₃₇ O (CH ₂ CH ₂ O) ₃₅ H (b-2) HLB 11.90 C ₁₀ H ₂₁ O (CH ₂ CH ₂ O) ₆ CH ₃ (b-3) HLB 5.06 C ₁₁ H ₂₃ COO (CH ₂ CH ₂ O) ₁₅ H (b-4) HLB 9.13 C ₁₅ H ₃₁ COO (CH ₂ CH ₂ O) ₁₀ CH ₃ (b-5) HLB 5.10 (c) Component C ₁₂ H ₂₅ OH (c-1) HLB 3.20 C ₁₆ H ₃₃ OH (c-2) HLB 1.30 C ₁₁ H ₂₃ COOH (c- 3) HLB 3.88 C ₁₇ H ₃₅ COOH (c-4) HLB 1.03 (d) component

[0035]

Embedded image

Other components C ₁₂ H ₂₅ O (CH ₂ CH ₂ O) ₄ H (b'-1) HLB 4.50 C ₁₀ H ₂₁ O (CH ₂ CH ₂ O) ₃ CH ₃ (b'-2) HLB 4.07 C ₁₇ H ₃₅ COO (CH ₂ CH ₂ O) ₃₅ H (b'-3) HLB 12.89 <Measuring method of bleaching performance> 5 tea-contaminated cloths prepared as follows are shown in Table 3 and Table 4, respectively. Liquid bleach composition
0.5 ml each was applied. After leaving it for 10 minutes, it was rinsed with tap water, dried and the bleaching rate was calculated by the following formula. Bleaching rate of tea-contaminated cloth

[0037]

[Equation 1]

The reflectance is NDR-101 manufactured by Nippon Denshoku Industries Co., Ltd.
Measured with DP using a 460 nm 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.

[0039]

[Table 3]

[0040]

[Table 4]

(Note) * 1; Linear alkyl (average carbon number 12)
Sodium benzene sulfonate

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Takaomi Himo 1334 Minato Minato, Wakayama City, Wakayama Prefecture Kao Co., Ltd. (72) Inventor Kasumi Maeda 1334 Minato Minato, Wakayama City, Wakayama Lab.

Claims (5)

[Claims] 1. The following component (a) is contained in an amount of 0.5 to 10% by weight, the component (b) is included in an amount of 3 to 30% by weight, and the component (c) is included in an amount of 0.001 to 20% by weight, and the components (c) and (b) are included. The weight ratio of [(c) component] /
[Component (b)] = 0.001 to 1.0 A liquid bleaching composition. (a) Component: H ₂ O ₂ or an inorganic peroxide that generates H ₂ O ₂ in an aqueous solution (b) Component: Nonionic surfactant having an HLB of 5 to 12 by the method of Davies (c) Component: HLB according to the method of Davies, which has at least one alkyl group, alkenyl group or aryl group having 6 to 22 carbon atoms and at least one hydrophilic group in the molecule.
A lipophilic compound having a value of less than 5 2. The liquid bleaching composition according to claim 1, wherein the component (b) is a nonionic surfactant represented by the general formula (I). R ¹ X (AO) _m Y (I) [In the formula, R ^{1 represents a} linear or branched alkyl group or an alkenyl group having 6 to 22 carbon atoms, or the total number of linear or branched carbon atoms is 1 The alkyl group of -18 represents an aryl group which may be substituted. X: represents an -O- group or a -COO- group. A: Shows a linear or branched alkylene group having 2 to 3 carbon atoms. Y: H or an alkyl group having 1 to 3 carbon atoms is shown. m: 3 to 50 showing the average number of moles of alkylene oxide added
Number of. However, in this case, R ¹ , X, A, Y and m
Are selected so that the HLB according to Davies' method is 5-12. ] 3. The liquid bleach composition according to claim 1, wherein the component (c) is a lipophilic compound represented by the general formula (II). R ² Z (II) [In the formula, R ^{2 represents a} linear or branched alkyl group or alkenyl group having 6 to 22 carbon atoms, or a linear or branched alkyl group having 1 to 18 carbon atoms in total. Represents an optionally substituted aryl group. Z: Indicates -OH or -COOH. ] 4. The liquid bleaching composition according to claim 1, further comprising a sequestering agent as the component (d). 5. The liquid bleach composition according to claim 1, which has a viscosity at 20 ° C. of 300 cp or less.