JPH0948997A - Liquid bleach composition - Google Patents

Abstract

(57) Abstract: A two-component liquid bleaching composition having a high bleaching detergency even if it is not used in combination with a detergent. SOLUTION: Hydrogen peroxide, a nonionic surfactant, at least one selected from an amphoteric surfactant and a cationic surfactant, and a bleaching activator represented by the general formula (1). A two-pack type liquid bleaching composition comprising an agent A containing a specific amount of the above and an agent B containing an alkaline agent. Embedded image [R ¹ is an alkyl or alkenyl group having 5 to 19 carbon atoms, Z is —SO ₃ M or —COOM, and M is a cation. ]

Description

Detailed Description of the Invention

[0001]

The present invention relates to liquid bleach compositions. More specifically, it relates to a two-pack type liquid bleach composition having a high bleaching detergency even if it is not used in combination with a detergent.

[0002]

2. Description of the Related Art Bleaching agents are classified into chlorine-based bleaching agents and oxygen-based bleaching agents. However, chlorine-based bleaching agents are limited in the fibers that can be used, cannot be used in colors and patterns, and have a unique odor. Therefore, oxygen-based bleaching agents which do not have these drawbacks have been remarkably popular recently. Among these oxygen bleaching agents, sodium percarbonate and sodium perborate are used as powder bleaching agents, and hydrogen peroxide is used as a liquid oxygen bleaching agent. However, the liquid oxygen bleaching agent has a lower bleaching power than the chlorine bleaching agent, and its improvement is required.

In order to make up for the above drawbacks of liquid oxygen bleaching agents, research has been conducted on liquid bleaching agents containing bleach activators and organic peroxy acids. For example, JP-A-62-2
Japanese Patent No. 30897 discloses a liquid bleaching composition in which particles of a bleaching activator which produces an organic peracid are dispersed in an acidic aqueous solution containing hydrogen peroxide. Also, Japanese Patent Application Laid-Open
-70593 discloses a fluid aqueous liquid detergent composition having a substantially water-insoluble organic peroxy acid. Furthermore, the present inventors have disclosed a liquid bleach composition in which a specific surfactant and a bleach activator are combined in JP-A-6-207196 and JP-A-7-82591.

However, although these bleaching compositions can obtain a high bleaching detergency when used in combination with a detergent, there is a problem that satisfactory performance cannot be obtained when used alone. Therefore, an object of the present invention is to provide a liquid bleaching composition which has improved the above-mentioned drawbacks.

[0005]

Means for Solving the Problems As a result of intensive studies for solving the above-mentioned problems, the present inventors have achieved the above-mentioned object by combining a specific agent containing a bleach activator and a specific agent containing an alkaline component. The inventors have found that the above can be achieved, and have completed the present invention. That is, the present invention, the following (a-1) component 0.5 ~ 10 wt%, (a-2) component
0.5 to 30% by weight, 0.1 to 20% by weight of component (a-3), and (a-
4) A two-component type liquid bleaching composition comprising agent A containing 0.1 to 10% by weight of components and agent B containing 0.005 to 20% by weight of alkali agents. (a-1) hydrogen peroxide (a-2) nonionic surfactant (a-3) at least one selected from amphoteric surfactants and cationic surfactants (a-4) general formula (1 ) Bleach activator represented by

[0006]

Embedded image

[Wherein R ¹ is a straight-chain or branched-chain carbon atom having 5 to 5 carbon atoms]
19 represents an alkyl group or an alkenyl group, and Z is -SO ₃ M
Or-indicates COOM. M is an organic or inorganic cation. ]

[0008]

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

[Agent A] The agent A of the present invention comprises the component (a-1), the component (a
-2) The component, the component (a-3), and the component (a-4) are contained as essential components.

[Component (a-1)] Used in the agent A of the present invention
The component (a-1) is hydrogen peroxide.

[Component (a-2)] Used in the agent A of the present invention
The component (a-2) is a nonionic surfactant, and in particular the general formula
The nonionic surfactant represented by (2) is preferably used.

R ² -X- (AO) _m -Y (2) [wherein R ² is a linear or branched alkyl group having 6 to 22, preferably 8 to 18 and more preferably 10 to 18 carbon atoms. Represents a group or an alkenyl group, or has a straight or branched chain total carbon number of 1 to
18 represents an aryl group which may be substituted with preferably 6 to 18 alkyl groups. X represents an -O- group or a -COO- group, preferably an -O- group. A is a straight or branched chain carbon number 2-3
Of the alkylene group, and m A's may be the same or different. Y represents H or an alkyl group having 1 to 3 carbon atoms. m is a number of 3 to 50, preferably 3 to 20, more preferably 4 to 15, which represents the average number of moles of alkylene oxide added. In the general formula (2), the A group represents an ethylene group or a propylene group (preferably a branched propylene group), but these may be polymerized in a block type or a random type. More specifically, the nonionic surfactants shown in Table 1 can be mentioned.

[0013]

[Table 1]

[Component (a-3)] Used in the agent A of the present invention
The component (a-3) is at least one selected from amphoteric surfactants and cationic surfactants. As the amphoteric surfactant, sulfobetaine or carbobetaine represented by the general formula (3) is preferably used.

[0015]

Embedded image

[Wherein at least one of R ³ , R ⁴ and R ⁵ represents a linear or branched C 6-20, preferably C 8-18 alkyl or alkenyl group, the rest having 1 carbon ~ 5,
It is preferably an alkyl group of 1 to 3 or a hydroxyalkyl group. R ⁶ represents an alkylene group which may be substituted with a hydroxyl group and has 1 to 6 carbon atoms, preferably 1 to 3 carbon atoms, and T ⁻ represents —COO ⁻ or —SO ₃ ^— , preferably —SO ₃
^- show the. Specific examples of the more preferable amphoteric surfactant include the following compounds.

[0017]

[Chemical 6]

As the cationic surfactant, a compound represented by the general formula
The quaternary ammonium salt represented by (4) is preferably used.

[0019]

[Chemical 7]

[Wherein R ⁷ , R ⁸ , R ⁹ and R ¹⁰ are at least 1
One is a straight or branched chain having 6 to 20 carbon atoms, preferably 8 to 18 carbon atoms
Represents an alkyl group or an alkenyl group, and the rest has 1 carbon
~ 3 alkyl groups or hydroxyalkyl groups are shown. L ⁻ represents an organic or inorganic anion group. Specific examples of these quaternary ammonium salts include the following compounds.

[0021]

Embedded image

[Wherein, h is a number of 6 to 20, preferably 8 to 18, g and d are the same or different and are 6 to 20, preferably 8]
To 18 are shown, R ¹¹ is an alkyl group having 1 to 3 carbon atoms or a hydroxyalkyl group, Q ⁻ is Cl ⁻ , a halogen ion such as Br ⁻ , CH ₃ SO ₄ ^— , CH ₃ CH ₂ SO ₄ ^- alkyl sulfates ions such, or ^{_{C 11 H 23 COO -, CH}} 3 COO - shows the fatty acid, such as an ion. Among these, dioctyl dimethyl ammonium salt, didecyl dimethyl ammonium salt, didodecyl dimethyl ammonium salt, dodecyl trimethyl ammonium salt, tetradecyl trimethyl ammonium salt, and hexadecyl trimethyl ammonium salt are particularly preferable.

Among the above amphoteric surfactants or cationic surfactants, cationic surfactants are preferred.

[Component (a-4)] Used in the agent A of the present invention
The component (a-4) is a bleaching activator represented by the general formula (1). In the general formula (1), Z represents —SO ₃ M or —COOM, and the organic or inorganic cation represented by M is an alkali metal such as Na or K, ammonium, or C 3
~ 15, preferably 7-15 alkylammonium, monoethanolammonium, diethanolammonium,
Examples thereof include triethanol ammonium, and alkali metals are particularly preferable. Specific examples of the bleach activator used in the present invention include the following compounds.

[0025]

Embedded image

[B Agent] The B agent of the present invention contains an alkaline agent as an essential component. As the alkaline agent, hydroxides or carbonates of alkali metals or alkaline earth metals are preferably used. Specifically, NaOH, KOH, Mg (OH)
₂ , hydroxides such as Ca (OH) ₂ , Na ₂ CO ₃ , K ₂ CO ₃ , MgCO
₃ , carbonates such as CaCO ₃ , especially NaOH, KOH
, Na ₂ CO ₃ and K ₂ CO ₃ are preferred.

[Liquid Bleaching Agent Composition] The agent A in the liquid bleaching agent composition of the present invention contains 0.5 to 10% by weight, preferably 1 to 10% by weight, more preferably 1 to 10% by weight of the component (a-1). 6% by weight, (a
-2) 0.5 to 30% by weight of components, preferably 1 to 20% by weight,
More preferably 1 to 10 wt%, component (a-3) 0.1 to 20 wt%, preferably 0.5 to 10 wt%, more preferably 1.0
~ 10 wt%, component (a-4) 0.1 ~ 10 wt%, preferably
0.1 to 5% by weight, more preferably 0.1 to 3% by weight. The agent B of the present invention contains an alkaline agent in an amount of 0.005 to 20% by weight, preferably 0.01 to 10% by weight. When the amount of the component (a-1) in the agent A of the present invention is less than 0.5% by weight, sufficient bleaching performance cannot be obtained, and when it exceeds 10% by weight, the storage stability of hydrogen peroxide is significantly reduced. If the content of the component (a-2) is less than 0.5% by weight, sufficient bleaching performance cannot be obtained, and if it exceeds 30% by weight, the viscosity increases and handling becomes difficult. (a
-3) When the content of the component is less than 0.1% by weight, sufficient bleaching performance cannot be obtained, and when it exceeds 20% by weight, the viscosity of the composition increases and it becomes difficult to handle. When the content of the component (a-4) is less than 0.1% by weight, sufficient bleaching performance cannot be obtained, and when it exceeds 10% by weight, it is difficult to dissolve in the composition and the appearance is significantly impaired. If the amount of the alkaline agent in the agent B of the present invention is less than 0.005% by weight or more than 20% by weight, sufficient bleaching performance cannot be obtained.

In the liquid bleaching composition of the present invention, the mixing ratio of agent A and agent B is agent A / agent B (weight ratio) = 1/10.
0 to 50/1 is preferable, and 1/20 to 50/1 is more preferable.
It is. Sufficient bleaching power cannot be obtained when the ratio of A agent / B agent is outside the range of 1/100 to 50/1.

[Arbitrary Ingredient] The composition of the present invention comprises the agent A (a-
The components (1) to (a-4) and the agent (B) contain the component (b-1) as an essential component, but other components may be added. 0.005 to 5.0% by weight of a sequestering agent may be added as an optional component to either or both of the agents A and B of the present invention. The following compounds are mentioned as a sequestering agent.

(1) Phosphoric acid compounds such as phytic acid or alkali metal salts or alkanolamine salts 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. 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. Further, the agent B of the present invention may contain 0.1 to 30% by weight of at least one selected from anionic surfactants and nonionic surfactants as an optional component. As the nonionic surfactant, the compounds represented by the general formula (2) are preferable, and more specific examples include the compounds shown in Table 1 above. Also,
The nonionic surfactant compounded in the agent B may be the same as or different from the component (a-2) compounded in the agent A. Examples of the anionic surfactant blended with the agent B include alkylbenzene sulfonates, alkyl or alkenyl ether sulfates, olefin sulfonates, alkane sulfonates, saturated or unsaturated fatty acid salts, alkyl or alkenyl ether carboxylates. ,
Examples include α-sulfo fatty acid salts and α-sulfo fatty acid esters. Of these, alkylbenzene sulfonates are particularly preferred.

Further, the agent B may contain 0.1 to 10% by weight of a polymer of unsaturated carboxylic acid. Specific examples of the unsaturated carboxylic acid include acrylic acid, methacrylic acid, fumaric acid, maleic acid, 2-hydroxyacrylic acid, itaconic acid, aconitic acid, citraconic acid and the like. These may be homopolymers or copolymers of two or more kinds of unsaturated carboxylic acids. Further, the molecular weight of these polymers is preferably 200 to 100,000, and 500 to
50,000 is more preferable.

Further, the agent A of the present invention uses an inorganic acid such as sulfuric acid or phosphoric acid or an organic acid such as toluene sulfonic acid or benzene sulfonic acid, and may also contain sodium hydroxide or potassium hydroxide if necessary. It is preferable to adjust the pH to 1-6, preferably 1-5 using such caustic.

[0033]

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 7 and Comparative Examples 1 to 4 Hydrogen peroxide was used as the component (a-1) and the following (a-2) was used as the component (a-2).
-2-1) to (a-2-3) and (a-3) as the following components (a-3-1) to (a
-3-3), (a-4) below as a component (a-4-1), (a-4-2), as a sequestering agent (c-1) below, NaOH or Na as an alkaline agent
₂ CO ₃ and other optional components are used, and the composition A shown in Table 2 is used.
Agent, agent B having the composition shown in Table 3 was prepared, and these
The agent and the agent B were blended in the ratios shown in Table 4 to prepare a liquid bleach composition. For comparison, a liquid bleaching composition having the composition shown in Table 5 was prepared. The bleaching performance of each of the obtained liquid bleaching agent compositions was measured by the following method.
The results are shown in Tables 4 and 5. (a-2) Component C ₁₂ H ₂₅ O (C ₂ H ₄ O) ₁₀ -H (a-2-1) C ₁₀ H ₂₁ O (C ₂ H ₄ O) ₆ -CH ₃ (a-2-2 ) C ₁₁ H ₂₃ COO (C ₂ H ₄ O) ₁₅ -H (a-2-3)

[0035]

Embedded image

[0036]

Embedded image

[0037]

[Chemical 12]

<Method of measuring bleaching performance> Regarding the bleaching agent composition of the present invention, the amounts of the agents A and B shown in Table 4 were put into a tub containing 2 liters of tap water and uniformly dissolved. 5 pieces of black tea-contaminated cloths prepared as above were added. After being left for 30 minutes, the tea-contaminated cloth was rinsed with tap water and dried, and the bleaching rate was calculated by the following formula. For comparison products, see Table 5
25 g of the liquid bleaching composition having the composition shown in the above was used and bleached in the same manner.

-Bleaching rate of black tea-contaminated cloth

[0040]

[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 80 g of Nitto black tea (yellow package) is boiled in 3 liters of ion-exchanged water for about 15 minutes, and then rubbed with de-squeezed cotton, soaking cotton cloth # 2003 in this solution for about 15 minutes. Boiled for a minute. It was removed from the heat as it was, left to stand for about 2 hours, naturally dried, washed with water until the washing liquid did not become colored, dehydrated, pressed, and made into a test piece of 10 cm × 10 cm, which was used in the experiment.

[0042]

[Table 2]

[0043]

[Table 3]

[0044]

[Table 4]

[0045]

[Table 5]

Comparative Examples 5 to 8 Liquid bleaching compositions having the compositions shown in Table 6 were prepared. The bleaching performance of the obtained liquid bleaching agent composition was measured in the same manner as in Example 1 immediately after preparation and after storage at room temperature for 3 days. The residual rate of the bleaching activator after storage at room temperature for 3 days was measured by high performance liquid chromatography. Table 6 shows the results.

[0047]

[Table 6]

As is apparent from Table 6, a one-pack type liquid bleach composition containing an alkali agent (Comparative Examples 5 and 6).
The bleaching performance immediately after production is equivalent to that of the bleaching agent composition of the present invention, but the bleaching activator is decomposed with time with alkali, and the bleaching activator is completely decomposed after 3 days. It can be seen that is decreasing.

[0049]

The bleaching composition of the present invention is a two-pack type liquid bleaching composition having high bleaching performance and excellent storage stability. According to the present invention, high bleaching is possible without using it together with a detergent. A liquid bleach composition having strength can be provided.

Claims (9)

[Claims] 1. The following component (a-1) is 0.5 to 10% by weight, (a-
2) A agent containing 0.5 to 30% by weight of component, 0.1 to 20% by weight of component (a-3), and 0.1 to 10% by weight of component (a-4),
A two-component type liquid bleaching composition comprising agent B containing 0.005 to 20% by weight of an alkaline agent. (a-1) hydrogen peroxide (a-2) nonionic surfactant (a-3) at least one selected from amphoteric surfactants and cationic surfactants (a-4) general formula (1 ) A bleaching activator represented by [In the formula, R ¹ represents a linear or branched alkyl group or alkenyl group having 5 to 19 carbon atoms, and Z represents -SO ₃ M or -COOM. M is an organic or inorganic cation. ] 2. The two-component liquid bleaching composition according to claim 1, wherein the alkaline agent is a hydroxide or carbonate of an alkali metal or an alkaline earth metal. 3. The agent B comprises at least one selected from anionic surfactants and nonionic surfactants.
The two-component liquid bleaching composition according to claim 1 or 2, containing 0.1 to 30% by weight. 4. The agent B is a polymer of unsaturated carboxylic acid.
The two-component liquid bleaching composition according to any one of claims 1 to 3, which contains 0.1 to 10% by weight. 5. Either or both of agent A and agent B,
A metal sequestering agent is contained in an amount of 0.005 to 5.0% by weight.
The two-component liquid bleaching composition according to any one of 1. 6. The two-pack type liquid bleach composition according to claim 1, wherein the nonionic surfactant is a compound represented by the general formula (2). R ² -X- (AO) _m -Y (2) [In the formula, R ² represents a linear or branched alkyl group having 6 to 22 carbon atoms or an alkenyl group, or a total of linear or branched chains. An aryl group which may be substituted with an alkyl group having 1 to 18 carbon atoms is shown. X represents an -O- group or a -COO- group. A represents a linear or branched alkylene group having 2 to 3 carbon atoms, and m A's may be the same or different. Y represents H or an alkyl group having 1 to 3 carbon atoms. m is a number of 3 to 50 indicating the average number of moles of alkylene oxide added. ] 7. The amphoteric surfactant is sulfobetaine or carbobetaine represented by the general formula (3).
The two-component liquid bleaching composition according to any one of 1. Embedded image [In the formula, at least one of R ³ , R ⁴ , and R ⁵ represents a linear or branched alkyl group or alkenyl group having 6 to 20 carbon atoms,
The rest represents an alkyl group having 1 to 5 carbon atoms or a hydroxyalkyl group. R ⁶ represents an alkylene group having 1 to 6 carbon atoms which may be substituted with a hydroxyl group, and T ⁻
It is -COO ^- or -SO ₃ ^- shows the. ] 8. The two-pack type liquid bleach composition according to claim 1, wherein the cationic surfactant is a quaternary ammonium salt represented by the general formula (4). Embedded image [In the formula, at least one of R ⁷ , R ⁸ , R ⁹ , and R ¹⁰ represents a linear or branched alkyl group or alkenyl group having 6 to 20 carbon atoms, and the rest are alkyl groups having 1 to 3 carbon atoms or A hydroxyalkyl group is shown. L ⁻ represents an organic or inorganic anion group. ] 9. The compounding ratio of the agent A and the agent B is agent A / agent B.
(Weight ratio) = 1/100 to 50/1 The two-pack type liquid bleaching composition according to any one of claims 1 to 8.