JP2010138269A - Liquid bleaching detergent composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an aqueous bleaching detergent composition that is stably preserved in a dissolved state of phthalimide percarboxylic acid for a long period of time even under an aqueous condition and develops high bleaching performance in use. <P>SOLUTION: The liquid bleaching detergent composition comprises (a) a specific phthalimide percarboxylic acid, (b) a polyoxyethylene alkyl ether type nonionic surfactant having an HLB (Griffin method) of 10.5-17.5, (c) an anionic surfactant and water and has the mass ratio of (b)/[(b)+(c)] of 1/1-2/3 and pH of 2-5.5 at 20°C. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a liquid bleach detergent composition.

Phthalimide percarboxylic acid has strong oxidizing power and is expected to be used as a bleach base (Patent Documents 1 and 2). However, the investigation of blending such a compound as a component of a liquid bleach composition has not yet been sufficiently conducted. This is because such compounds generally have very low solubility in aqueous compositions, and even if they can be dissolved in aqueous compositions, the stability is very low. Therefore, as a technique for blending phthalimidopercarboxylic acid into the liquid bleach composition, it can be blended in a non-aqueous (anhydrous) composition or in a suspended or dispersed state in an aqueous composition. (Patent Documents 3 and 4).
European Patent Application No. 325288 European Patent Application No. 349940 US Pat. No. 6,844,305 US Pat. No. 4,981,606

  Conventional non-aqueous detergent compositions containing phthalimido percarboxylic acid or aqueous detergent compositions containing phthalimido percarboxylic acid in a suspended or dispersed state are water (especially low-temperature water). ) Is difficult to dissolve, and sufficient bleaching performance cannot be exhibited. Moreover, since it is necessary to contain various organic solvents in high concentration, the non-aqueous cleaning composition is expensive and has a problem in terms of safety. So far, a liquid bleach detergent composition containing phthalimido percarboxylic acid has not been found to improve such a problem.

  An object of the present invention is to provide an aqueous bleaching detergent composition that can be stably stored for a long time in a state in which phthalimidopercarboxylic acid is dissolved even under aqueous conditions, and exhibits high bleaching performance when used. is there.

  In the present invention, (a) phthalimidopercarboxylic acid represented by the following general formula (1) [hereinafter referred to as component (a)], (b) HLB (Griffin method) is 10.5 to 17.5. 3 to 30% by mass of a certain polyoxyethylene alkyl ether type nonionic surfactant (hereinafter referred to as component (b)), (c) an anionic surfactant (hereinafter referred to as component (c)) 0 to 10% by mass, And the mass ratio of the component (b) and the component (c) is 1/1 to 2/3 as (b) component / [(b) component + (c) component] at 20 ° C. The present invention relates to a liquid bleach detergent composition having a pH of 2.0 to 5.5.

[Wherein, n represents an integer of 1 to 15, and M represents a hydrogen atom, an alkali metal atom or an alkaline earth metal atom. ]

  ADVANTAGE OF THE INVENTION According to this invention, the liquid bleach detergent composition which can be stably stored over a long period in the state which melt | dissolved phthalimide percarboxylic acid, and expresses high bleaching performance at the time of use is obtained.

[(A) component]
The component (a) phthalimidopercarboxylic acid is a compound represented by the above general formula (1). Among them, n in the general formula (1) is preferably 3 to 13, more preferably 3 to 10, especially. Preferably it is 5. A compound in which M is a hydrogen atom is particularly preferred because of its particularly good stability and biodegradability.

  One reason why the component (a) of the present invention can exist stably in the composition is that the component (a) is efficiently incorporated into the phase formed by the component (b). It is believed that there is.

  From the viewpoint of improving the stability of the component (a) and the liquid feeling as a product, the liquid bleaching detergent composition of the present invention contains 0.01 to 1.0% by mass of the component (a), preferably 0.01. -0.8 mass%, More preferably, it contains 0.02-0.7 mass%.

[Component (b)]
The liquid bleach detergent composition of the present invention contains a nonionic surfactant having an HLB (Griffin method) of 10.5 to 17.5 as the component (b). The HLB is preferably 10.5 to 16.5.

(B) As a component, the nonionic surfactant represented by General formula (2) is mentioned.
_{^{R 2 -O [(EO) a}} / (PO) b] -H (2)
[Wherein R ² represents an alkyl group or an alkenyl group having 10 to 18 carbon atoms, preferably 12 to 14 carbon atoms. EO is an ethyleneoxy group and PO is a propyleneoxy group. a is an average addition mole number of EO and is a number of 0 to 40, b is an average addition mole number of PO and is a number of 0 to 20, and a case where both a and b are 0 is excluded. Preferably a is a number of 5 to 30, more preferably 5 to 25, preferably b is a number of 0 to 10, more preferably 0 to 8, particularly preferably 0 to 6. ]

  In the general formula (2), EO and PO may be arranged in any form of a random copolymer or a block copolymer.

  The nonionic surfactant represented by the general formula (2) includes a polyoxyethylene alkyl ether type nonionic surfactant and a polyoxyalkylene alkyl ether type nonionic interface having an oxyethylene group and an oxypropylene group. An active agent is mentioned, These can also use both 2 types together.

Specific examples of the polyoxyethylene alkyl ether type nonionic surfactant include, but are not limited to, compounds represented by the following general formula.
C ₁₂ H ₂₅ -O (C ₂ H ₄ O) _a1 -H (a1 = 5-29, HLB = 10.8-17.5)
C ₁₄ H ₂₉ -O (C ₂ H ₄ O) _a2 -H (a2 = 6-34, HLB = 11.0-17.5)
C ₁₂ H ₂₅ -O (C ₂ H ₄ O) _a3 (C ₃ H ₆ O) _b1 (C ₂ H ₄ O) _a4 -H (a3 + b1 + a4 = 4 to 29, HLB = 10.8 to 17.5)

As an example of the nonionic surfactant of the general formula (2), polyoxyethylene lauryl ether (oxyethylene average addition mole number 5 to 20, HLB 10.8 to 16.5), polyoxyethylene myristyl ether (oxyethylene average) molar number of addition _{6~20, HLB11.0~16.1), C 12 H} 25 O- (C 2 H 4 O) 7 - (C 3 H 6 O) 2 - (C 2 H 4 O) 4 -H (HLB15.8). The nonionic surfactant as component (b) can be blended as a mixture of two or more.

  From the viewpoint of improving the storage stability of the component (a) and the bleaching property, the liquid bleach detergent composition of the present invention contains 3 to 30% by mass, preferably 4 to 25% by mass of the component (b). Preferably it contains 5-25 mass%.

[Component (c)]
Moreover, the liquid bleach cleaning composition of this invention can contain an anionic surfactant as surfactant from a viewpoint of a cleaning performance improvement. Examples of the anionic surfactant include alkyl having 10 to 18 carbon atoms or alkenyl group having alkenyl group or alkenylbenzene sulfonate, polyoxyalkylene (average number of added alkylene oxide of 0.5 to 5) alkyl (10 carbon atoms). -18) Ether sulfate ester, alkyl (C10-16) sulfate ester, α-olefin (C8-18) sulfonate, α-sulfo fatty acid salt (C10-16) or α-sulfo Fatty acid (10 to 16 carbon atoms) lower alkyl (1 to 3 carbon atoms) ester salt and the like.

As the alkylbenzene sulfonate, any of those generally circulated in the detergent surfactant market can be used as long as the alkyl group has 10 to 18 carbon atoms, for example, manufactured by Kao Corporation. Neoperex F25, Dobs 102 manufactured by Shell, etc. can be used. Industrially, alkylbenzene widely distributed as a detergent raw material can be obtained by sulfonation using an oxidizing agent such as chlorosulfonic acid or sulfurous acid gas. As for carbon number of an alkyl group, 10-14 are preferable. The polyoxyalkylene alkyl ether sulfate is an average of 0 per molecule of ethylene oxide in a linear or branched primary alcohol or linear secondary alcohol having 10 to 18 carbon atoms, preferably 10 to 16 carbon atoms. 0.5-5 mol can be added, and this can be obtained by sulfation using the method described in JP-A-9-137188, for example. The alkyl sulfate salt is obtained by sulfonating a linear or branched primary alcohol or linear secondary alcohol having 10 to 16 carbon atoms, preferably 10 to 14 with SO ₃ or chlorosulfonic acid, and neutralizing. it can. The α- olefin sulfonate, an α- alkene having 8 to 18 carbon atoms and sulfonated with SO _3, can be obtained through the hydration / neutralization, a compound hydroxyl group in the hydrocarbon group is present not A mixture of compounds in which a saturated bond is present. In addition, as the α-sulfo fatty acid lower alkyl ester salt, the alkyl group preferably has 10 to 16 carbon atoms, and methyl ester or ethyl ester is preferable from the viewpoint of washing effect. As the salt of the component (c), sodium salt, potassium salt, magnesium salt, calcium salt, alkanolamine salt, and ammonium salt are preferable, and sodium salt, potassium salt, and magnesium salt are preferable from the viewpoint of cleaning effect.

  In the liquid bleach detergent composition of the present invention, from the viewpoint of improving the storage stability of the component (a), the content of the component (c) is 0 to 10% by mass, and further 0 to 5% by mass in the composition. Is preferred. The mass ratio of the component (b) and the component (c) is 1/1 to 2/3, preferably 1/1 to 4 as (b) component / [(b) component + (c) component]. / 5. Moreover, in the surfactant component, the ratio of the component (b) is 80% by mass or more, preferably 80 to 100% by mass, particularly preferably 90 to 100% by mass.

[Component (d)]
The liquid bleach cleaning composition of the present invention preferably contains a metal sequestering agent as the component (d) from the viewpoint of improving the stability of the component (a). As the metal sequestering agent, a phosphonic acid type is preferably used. Specific examples thereof include ethane-1,1-diphosphonic acid, ethane-1,1,2-triphosphonic acid salt, 1-hydroxyethane-1,1-diphosphonic acid, ethanehydroxy-1,1,2-triphosphonic acid. And organic phosphonic acid derivatives such as ethane-1,2-dicarboxy-1,2-diphosphonic acid, methanehydroxyphosphonic acid, nitrilotrimethylenephosphonic acid, and ethylenediaminetetrakismethylenephosphonic acid. These can be used alone or in combination of two or more. Of these, 1-hydroxyethane-1,1-diphosphonic acid, ethylenediaminetetrakismethylenephosphonic acid and the like are preferable. (D) Content of a component is 0.01-0.5 mass% in a composition, Furthermore, 0.05-0.3 mass% is preferable.

[(E) component]
The liquid bleach detergent composition of the present invention may contain at least one organic solvent as the component (e) from the viewpoint of improving the liquid feel of the product. Specific examples of the component (e) include an organic solvent represented by the following general formula (3), an ester organic solvent (for example, methyl acetate, ethyl acetate, methyl propionate, etc.), a ketone organic solvent (for example, acetone). , Diethyl ketone, methyl ethyl ketone, diisopropyl ketone, methyl isobutyl ketone, methyl isopropyl ketone, etc.) and ether organic solvents (dioxane, tetrahydrofuran, triethylene glycol dimethyl ether, etc.).
R ³ —O— (AO) _p —H (3)
(Wherein, R ³ represents a hydrogen atom, a linear or branched alkyl group having 1 to 6 carbon atoms, phenyl or benzyl, A is shows a linear or branched alkylene group having 2 to 4 carbon atoms And p A may be the same or different, and p is a number of 0 to 5 indicating the average number of moles of alkylene oxide added.

  Specific examples of the compound represented by the general formula (3) include alcohols such as ethanol, propanol and butanol, ethylene glycol, propylene glycol, trimethylene glycol, polyethylene glycol (p in formula (3) up to 5). ), Glycols such as butyl diglycol, diethylene glycol and triethylene glycol, and polyalkylene glycol alkyl ethers such as diethylene glycol butyl ether and triethylene glycol phenyl ether.

  As the component (e), an organic solvent containing two sites having a hydroxy group is preferable, and ethylene glycol, propylene glycol, trimethylene glycol, polyethylene glycol (p in Formula (3) up to 5), and An organic solvent selected from butyl diglycol is more preferable, and an organic solvent selected from propylene glycol and butyl diglycol is particularly preferable.

  From the viewpoint of improving the storage stability of the component (a), the liquid bleach cleaner composition of the present invention is preferably 0.1 to 10% by mass, more preferably 0.1 to 7% by mass, More preferably 0.1 to 5% by mass is contained.

[Component (f)]
The liquid bleach detergent composition of the present invention may contain hydrogen peroxide as the component (f) from the viewpoint of improving the bleaching performance. The content of the component (f) is preferably 0.1 to 6% by mass, more preferably 0.5 to 5% by mass, and still more preferably 1 to 4.5% by mass in the liquid bleach detergent composition. More preferably, it is 1-3 mass%. In such a range, an excellent bleaching effect can be obtained.

[Radical trapping agent]
The liquid bleach cleaning composition of the present invention may contain a radical trapping agent from the viewpoint of improving the stability of hydrogen peroxide. As the radical trapping agent, phenol-based compounds, that is, derivatives having phenolic OH groups, derivatives thereof such as ester derivatives and ether derivatives thereof are preferable. Preferable examples include dimethoxyphenol, catechol, hydroquinone, methoxyphenol, dibutylhydroxytoluene (BHT) and the like.

[Other ingredients]
In addition, the liquid bleach detergent composition of the present invention may contain optional components such as hydrotropes, silicones, bactericides, enzymes, fragrances, and fluorescent dyes. The liquid bleach detergent composition of the present invention contains water, and usually the balance of the composition is water.

  As a fragrance | flavor, the fragrance | flavor as described in paragraph [0007]-[0022] of Unexamined-Japanese-Patent No. 2003-213295 can be used, for example.

  As the fluorescent dye, for example, a fluorescent dye described in JP-A No. 2004-308070 can be used.

[PH]
The liquid bleach detergent composition of the present invention has a pH at 20 ° C. of 2 to 5.5, preferably 2.5 to 5, and more preferably 2.5 to 4.5. Within this range, the stability of the component (a) can be improved, and excellent bleach washing performance can be exhibited.

  PH adjusting agents for adjusting to such pH include inorganic acids such as hydrochloric acid and sulfuric acid, or acid agents such as organic acids such as citric acid, succinic acid, malic acid, fumaric acid, tartaric acid, malonic acid and maleic acid. Or alkali agents such as sodium hydroxide, potassium hydroxide, ammonia and derivatives thereof, amine salts (monoethanolamine, diethanolamine, triethanolamine, etc.), sodium carbonate, potassium carbonate and the like can be used alone or in combination. . Among these, it is particularly preferable to use an inorganic acid selected from hydrochloric acid and sulfuric acid, or an inorganic base selected from sodium hydroxide and potassium hydroxide.

  The appearance of the liquid bleach detergent composition of the present invention is preferably transparent and uniform. Here, the term “transparent and uniform” means that a quartz cell having an optical path length of 10 mm of the measurement cell is used, and when ion-exchanged water is put into a symmetrical cell, the light transmittance at a wavelength of 660 nm is 30% or more. This means that generation cannot be confirmed. The viscosity of the liquid bleach detergent composition of the present invention is preferably 5 to 250 mPa · s at 20 ° C. from the viewpoint of ease of use during coating.

  In addition, the viscosity of this invention is measured as follows. To the B-type viscometer manufactured by Tokyo Keiki Co., Ltd., the rotor No. Prepare the one with 1 Place the sample in a tall beaker, set the sample adjusted to 20 ° C. in a constant temperature bath at 20 ° C. on the viscometer, set the rotation speed of the rotor to 60 rpm, and measure the viscosity 60 seconds after starting the rotation of the present invention. Viscosity.

  The liquid bleach detergent composition of the present invention is suitable for textile products such as clothing and bedding.

Examples 1-13 and Comparative Examples 1-8
Liquid bleach detergent compositions having the compositions shown in Table 1 were prepared, and the pH, storage stability of component (a), bleaching performance and liquid feeling were evaluated by the following methods. The results are shown in Table 1. The pH of the composition was adjusted with sodium hydroxide. Each composition had a viscosity at 20 ° C. of 5 to 150 mPa · s.

[PH]
The pH of the liquid bleach detergent composition at 20 ° C. was measured using a pH meter F52 manufactured by Horiba, Ltd. and a pH electrode 6367-S004.

[Storage stability of component (a)]
80 g of the liquid bleach detergent composition was placed in a 100 mL glass sample bottle and stored at 30 ° C. for 4 weeks. The content of the component (a) in the liquid bleach detergent composition before and after storage was dropped by the iodometry method, and the residual ratio of the component (a) was determined by the following formula.
(A) Component residual rate (%) = [(a) component content after storage] / [(a) component content before storage] × 100

[Bleaching performance]
After mixing 1 mL of liquid bleach detergent composition and 1000 mL of 4 ° DH water, put the meat sauce contaminated cloth (4 sheets) prepared by the following method into it, and bleach it at 20 ° C and 80 rpm for 10 minutes using a tartometer. Went. The reflectance of the cloth surface before and after the treatment was measured, and the bleaching rate was determined by the following formula. The reflectance was measured by Spectro Color meter SE2000 (manufactured by Nippon Denshoku Industries Co., Ltd.).

・ Preparation of Meat Sauce Contaminated Cloth Solid content of Meat Sauce (Ripe Tomato Meat Sauce (May 27, 2007 Expiration Date, Lot No .: D5527JF) / Canned 259 g of Canned Content) manufactured by Kagome Co., Ltd. mesh (open eyes; 500 μm) ), And the resulting liquid was heated until boiling. Cotton gold cloth # 2003 was immersed in this solution and boiled for 15 minutes. After removing from the fire for 2 hours and allowing to reach 30 ° C., the cloth was taken out and the excess liquid was removed with a spatula and allowed to dry naturally. Then, it was pressed and subjected to an experiment as a 10 cm × 10 cm test cloth.

[Liquid feeling]
The state immediately after the preparation of the liquid bleach detergent composition was visually observed, and the liquid feeling was evaluated according to the following criteria.
○: Transparent and uniform state.
X: It is not transparent and uniform, such as precipitation or cloudiness.

The symbols in the table are as follows.
A-1; a compound having the following structure

B-1; polyoxyethylene lauryl ether (oxyethylene average addition mole number 6, HLB11.7)
_{· B-2; C 12 H} 25 O- (C 2 H 4 O) 7 - (C 3 H 6 O) 2 - (C 2 H 4 O) 4 -H (HLB15.8)
-B'-1; polyoxyethylene lauryl ether (oxyethylene average addition mole number 4, HLB9.7)
B′-2; polyoxyethylene lauryl ether (oxyethylene average addition mole number 35, HLB 18.0)
C-1: alkyl (carbon number 12) sodium benzenesulfonate d-1; ethane-1-hydroxy-1,1-diphosphonic acid (Daiquest 2010, manufactured by Solusia)
E-1: propylene glycol

Claims (3)

(A) Phthalimide percarboxylic acid represented by the following general formula (1) [hereinafter referred to as component (a)], (b) polyoxyethylene having an HLB (Griffin method) of 10.5 to 17.5 Alkyl ether type nonionic surfactant (hereinafter referred to as component (b)) 3 to 30% by mass, (c) anionic surfactant (hereinafter referred to as component (c)) 0 to 10% by mass, and water The mass ratio of the component (b) to the component (c) is 1/1 to 2/3 as (b) component / [(b) component + (c) component], and the pH at 20 ° C. is 2 to 2. A liquid bleach detergent composition which is 5.5.

[Wherein, n represents an integer of 1 to 15, and M represents a hydrogen atom, an alkali metal atom or an alkaline earth metal atom. ]   The liquid bleach detergent composition according to claim 1, wherein the mass ratio of the component (a) to the component (b) is (a) component / (b) component = 1/10 to 1/150.   The liquid bleach detergent composition according to claim 1 or 2, further comprising (d) a metal sequestering agent.