JP2908892B2 - Liquid detergent composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a liquid detergent composition having a bactericidal effect and excellent detergency.

[0002]

2. Description of the Related Art Dirt in a house includes dirt caused by mold and dirt caused by calcium in tap water.
Liquid cleaners containing an acid or an oxidizing agent have been used to remove these stains. For example, as a sanitary cleaner that removes dirt such as mold and bacteria in the toilet,
A composition using sodium hypochlorite as an oxidizing agent (JP-A-52-78905) was generally used. Further, for the purpose of removing stains derived from tap water in toilets and bathrooms, compositions containing organic acids such as malic acid and citric acid (Japanese Patent Application Laid-Open No.
No. 51-71302). Further, a composition comprising hydrogen peroxide, an organic acid, and a surfactant (Japanese Patent Application Laid-Open No. 59-164400) has been proposed as having both sterilization and stain removal properties. And, the organic acids used in these liquid detergent compositions, from the viewpoint of their solubility,
They were hydroxycarboxylic acids and unsaturated carboxylic acids.

However, in a composition in which an organic acid such as a hydroxycarboxylic acid or an unsaturated carboxylic acid is used in combination with hydrogen peroxide, hydrogen peroxide is decomposed during storage to generate oxygen gas, and the pressure inside the container is reduced. And the container swells,
There were problems such as rupture. Further, the liquid detergent containing the above-mentioned organic acid precipitates over time, and has a problem in storage stability.

[0004]

SUMMARY OF THE INVENTION The present invention provides a liquid detergent composition which contains hydrogen peroxide in a stable manner and has excellent stability over time and cleaning performance.

[0005]

The liquid detergent composition of the present invention comprises the following three components (a), (b) and (c), or (d)
It is characterized by containing four components. (a) hydrogen peroxide. (b) Anionic and / or nonionic surfactants. (c) Glutaric acid or a salt thereof. (d) polyethylene glycol.

[0006]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS It is desirable that hydrogen peroxide as the component (a) be incorporated in the composition in an amount of 0.5 to 8% by weight, preferably 1.5 to 5% by weight, from the viewpoints of effectiveness and stability as a bactericide. In the present invention, anionic or nonionic surfactants are used as the component (b), and these may be used alone or in combination of two or more. These surfactants are preferably blended in the liquid detergent composition of the present invention in an amount of 1 to 10% by weight, more preferably 2 to 5% by weight.

As the anionic surfactant, those which are stable in an acidic to weakly acidic region are preferable, and alkyl (C ₄ to C _4)
12 ) Diphenyl ether disulfonate, alkyl (C
₁₀ -C ₁₄₎ benzene sulphonate, alkane (C ₁₀ ~
C ₁₈₎ sulfonate, alpha-olefin (C ₁₂ ~C ₁₆₎ sulfonates, alkyl (C ₈ ~C ₁₂₎ phenol polyoxyethylene (p = 3 to 10) ether sulfates, alkyl
(C ₈ ~C ₁₂₎ phenol polyoxyethylene (p = 3 to 1
6) Ether sulfate sulfonate (NES-
D), polyoxyethylene (p = 1 to 5) alkyl (C
_{10 to} C ₁₆ ) ether sulfate and the like, preferably alkylbenzene sulfonate and alkane sulfonate. Here, p represents the average number of moles of ethylene oxide added.

[0008] Nonionic surfactants include those having about 8 carbon atoms.
~ 24 higher alcohols, polyhydric alcohols, fatty acids, fatty acid amides, fatty acid amines, alkylphenols and n
-An alkylene oxide adduct of a synthetic alcohol obtained by oxidizing paraffin or an α-olefin is used. As the alkylene oxide, ethylene oxide, propylene oxide, and butylene oxide are used.

Specifically, polyoxyethylene (p = 5)
-20) lauryl ether, polyoxyethylene (p = 5
20) C ₁₀ ~C ₁₄ secondary alkyl ethers, polyoxyethylene (p = 5 to 20) hexadecyl ether, polyoxyethylene (p = 5 to 20) nonylphenyl ether, polyoxyethylene (p = 5 to 20 ) Glyceryl monostearate, polyoxyethylene (p = 5 to 20) octyl phenyl ether, polyoxyethylene (p = 5 to 20) monostearate, polyoxyethylene (p = 5 to 20) stearylamide and the like. , preferably a polyoxyethylene _{(p = 5~20) C 12 ~C} 14 secondary alkyl ethers, for example, there is Softanol of Nippon Shokubai Kagaku Kogyo Co., Ltd..

Glutaric acid or a salt thereof as component (c) is generally added in an amount of 0.5 to 8% by weight, preferably 1 to 6% by weight. When the amount is less than 0.5% by weight, the function as an acid is weak, and the detergency is poor. On the other hand, 8
If the content is more than 10% by weight, the stability of hydrogen peroxide may be adversely affected, and oxygen gas may be generated. In addition, the storage stability may deteriorate, and precipitation may occur over time.

Glutaric acid or a salt thereof is difficult to obtain industrially with high purity, and even if obtained, it is expensive. Glutaric acid or salt is succinic acid (salt) / glutaric acid
(Salt) / adipic acid (salt) weight ratio is 18-30 / 60-70 / 10-
Since the fifteen mixtures are commercially available at low cost, it is safe to use this mixture to prepare the liquid detergent composition of the present invention. In this case, glutaric acid (salt) exhibits a hydrotropic effect on succinic acid (salt) and adipic acid (salt), and increases the liquid stability of succinic acid (salt) and adipic acid (salt).

Further, from the viewpoint of improving storage stability and suppressing generation of oxygen gas from hydrogen peroxide, it is preferable that polyethylene glycol is added as a component (d) in the liquid detergent composition in an amount of 0.1 to 10% by weight, More preferably 0.5 to 5
% By weight. As polyethylene glycol,
Those having a weight average molecular weight of 100 to 20,000 are suitable, and more preferably 100 to 2,000.

Further, in the liquid detergent composition of the present invention,
As a stabilizer for hydrogen peroxide, a chelating agent, an antioxidant and the like can be blended. Examples of the chelating agent include aminopolycarboxylic acids such as ethylenediaminetetraacetic acid and diethylenetriaminepentaacetic acid; inorganic phosphorus compounds such as tripolyphosphoric acid and pyrophosphoric acid; 1-hydroxyethane-1,1-
Examples thereof include phosphonic acids such as diphosphonic acid and 2-phosphono-1,2,4-tricarboxylic acid, and salts thereof.

As antioxidants, tocopherol, gallic acid derivatives, butylated hydroxyanisole (BH
A), 2,6-di-tert-butyl-4-methylphenol (BHT) and the like. These stabilizers may be present in the liquid detergent composition in an amount of 0 to 5 depending on the concentration of hydrogen peroxide.
%, Preferably 0.01 to 3% by weight.

[0015] The liquid detergent composition of the present invention may further comprise a known hydrotrope or colorant (for example, Japanese Patent Publication No. 55-2051).
No. 9 copper phthalocyanine pigment), a pH adjuster,
Optional components such as a viscosity modifier can be appropriately compounded. The liquid detergent composition of the present invention usually takes the form of an aqueous solution or an aqueous emulsion, and its pH is suitably less than 6, preferably in the range of 1.5 to 4.5.

[0016]

According to the present invention, a sterilizing liquid detergent composition is prepared by adding glutaric acid or a salt thereof to a system containing hydrogen peroxide and a nonionic or anionic surfactant, thereby stabilizing hydrogen peroxide. In addition, the storage stability can be improved by preventing the formation of sediments over time, and the detergency can be significantly improved. Further, by further blending polyethylene glycol, the stability of hydrogen peroxide and the storage stability of the composition can be further improved.

Therefore, the liquid detergent composition of the present invention is effective for sterilization and washing, and is particularly suitably used as a detergent for toilets, around kitchens, around microwave ovens, around bathrooms and the like.

[0018]

EXAMPLES Hereinafter, the effects of the present invention will be specifically described with reference to examples. Prior to this, the evaluation method used in the examples will be described. (1) Detergency test method

(A) Preparation of model scales 50 parts by weight of calcium phosphate, 10 parts by weight of urea, 10 parts by weight of calcium urate, 10 parts by weight of calcium hippurate and mucin
A paste obtained by adding 150 parts by weight of water to 20 parts by weight and kneading the mixture was uniformly applied to 0.16 g of a 2.5 cm × 4.5 cm ground glass. This was dried in an oven at 105 ° C. for 1 hour to obtain model scale.

(B) Detergency Evaluation Method After the model urine prepared by the above method is immersed in 100 ml of the detergent for 30 seconds, the stain removal when rubbing twice with a sponge is visually determined. ：: Model scale dirt is almost completely removed △: Model scale dirt is removed to some extent ×: Model scale dirt is hardly removed

(2) Test method for freeze-recovering property Put a sample in a 100 ml glass bottle,
After performing the (1 day) freeze-recovery cycle, the appearance when stored at 5 ° C. for 1 day is visually determined. ：: Uniform and transparent in 4 cycles of freeze-recovery ○: Uniform and transparent in 2 cycles of freeze-recovery ×: Cloudy or precipitated in 2 cycles of freeze-recovery

(3) Gas generation test method A sample was placed in a 300 ml plastic container, sealed, and stored at 50 ° C. The appearance of the bottle after storage was compared with the appearance of the same container containing only water, and visually judged. ◎: Equivalent to water-sealed product after storage for 2 weeks ○: Equivalent to water-sealed product after storage for one week ×: Storage is clearly inferior to water-sealed device after storage for one week (expansion)

Example 1 Liquid detergents of Sample Nos. 1 to 13 shown in Tables 1 to 4 described below were prepared, and their performance was evaluated. The results are shown in the same table.

[0024]

[Table 1]Example Sample No. 1 2 3 4  Composition wt% Hydrogen peroxide 5 3 4 1.5 C₁₂~ C₁₄Secondary alcohol ethoxylate (p = 9) *¹− − 5 − C₁₂~ C₁₄Secondary alcohol ethoxylate (p = 12)----C₁₂~ C₁₄Secondary alcohol ethoxylate (p = 15) 3 3 − − C₁₂~ C₁₃Oxo alcohol ethoxylate (p = 12) *^Two− − − 3 Sodium dodecylbenzenesulfonate − − − − C_Ten~ C₁₈Sodium paraffin sulfonate----Fumaric acid----Succinic acid----Citric acid----Glutaric acid 332 6 Adipic acid----Hydroxyethanediphosphonic acid----Polyethylene glycol: Molecular weight 200----Polyethylene glycol: molecular weight 400----Polyethylene glycol: molecular weight 1000----Copper phthalocyanine pigment *^Three(ppm) − − − −Water balance Liquid pH (adjusted with NaOH) 2 4 3 3  Performance Detergency ○ ○ ○ ○ Freezing recovery ○ ○ ○ ○Gas generation ○ ○ ○ ○  * 1) Softanol, manufactured by Nippon Shokubai Chemical Industry Co., Ltd. * 2) Ethylene oxide adduct of dovanol 23, manufactured by Mitsubishi Yuka Co., Ltd. * 3) C₃₂H₁₄Cl_TwoN₈Cu

[0025]

[Table 2]Comparative example Sample No. 5 6 7  Composition wt% Hydrogen peroxide 3 3 3 C₁₂~ C₁₄Secondary alcohol ethoxylate (p = 9) *¹3 3 3 C₁₂~ C₁₄Secondary alcohol ethoxylate (p = 12)---C₁₂~ C₁₄Secondary alcohol ethoxylate (p = 15)---C₁₂~ C₁₃Oxo alcohol ethoxylate (p = 12) *^Two− − − Sodium dodecylbenzenesulfonate − − − C_Ten~ C₁₈Sodium paraffin sulfonate---Fumaric acid 3--Succinic acid-1.5-Citric acid--3 Glutaric acid---Adipic acid---Hydroxyethanediphosphonic acid---Polyethylene glycol: molecular weight 200---Polyethylene glycol : Molecular weight 400---Polyethylene glycol: Molecular weight 1000---Copper phthalocyanine pigment *^Three(ppm) − − −Water balance Liquid pH (adjusted with NaOH) 3 3 3  Performance Detergency × ○ ○ Freezeability × × ○Gas generation × ○ ×  * 1) Softanol, manufactured by Nippon Shokubai Chemical Industry Co., Ltd. * 2) Ethylene oxide adduct of dovanol 23, manufactured by Mitsubishi Yuka Co., Ltd. * 3) C₃₂H₁₄Cl_TwoN₈Cu

[0026]

[Table 3]Example Sample No. 8 9 10  Composition wt% Hydrogen peroxide 335C₁₂~ C₁₄Secondary alcohol ethoxylate (p = 9) *¹− − − C₁₂~ C₁₄Secondary alcohol ethoxylate (p = 12) − − 3 C₁₂~ C₁₄Secondary alcohol ethoxylate (p = 15)---C₁₂~ C₁₃Oxo alcohol ethoxylate (p = 12) *^Two− − − Sodium dodecylbenzenesulfonate 3-1 C_Ten~ C₁₈Sodium paraffin sulfonate-3-Fumaric acid---Succinic acid--1.5 Citric acid---Glutaric acid 33 33 Adipic acid--0.5 Hydroxyethanediphosphonic acid--0.1 Polyethylene glycol: molecular weight 200---Polyethylene glycol : Molecular weight 400---Polyethylene glycol: Molecular weight 1000---Copper phthalocyanine pigment *^Three(ppm) − − −Water balance Liquid pH (adjusted with NaOH) 3 3 3  Performance Detergency ○ ○ ○ Freezeability ○ ○ ○Gas generation rate ○ ○ ○  * 1) Softanol, manufactured by Nippon Shokubai Chemical Industry Co., Ltd. * 2) Ethylene oxide adduct of dovanol 23, manufactured by Mitsubishi Yuka Co., Ltd. * 3) C₃₂H₁₄Cl_TwoN₈Cu

[0027]

[Table 4]Example Sample No. 11 12 13  Composition wt% Hydrogen peroxide 55 5 C₁₂~ C₁₄Secondary alcohol ethoxylate (p = 9) *¹− − − C₁₂~ C₁₄Secondary alcohol ethoxylate (p = 12) −33 C₁₂~ C₁₄Secondary alcohol ethoxylate (p = 15) 3--C₁₂~ C₁₃Oxo alcohol ethoxylate (p = 12) *^Two− − − Sodium dodecylbenzenesulfonate − 11 C_Ten~ C₁₈Sodium paraffin sulfonate---Fumaric acid---Succinic acid-1.5 1.5 Citric acid---Glutaric acid 3 33 Adipic acid-0.5 0.5 Hydroxyethane diphosphonic acid-0.1 0.1 Polyethylene glycol: molecular weight 200 2--Polyethylene glycol : Molecular weight 400-2-Polyethylene glycol: Molecular weight 1000--2 Copper phthalocyanine pigment *^Three(ppm) − 20 20Water balance Liquid pH (adjusted with NaOH) 3 3 3  Performance Detergency ○ ○ ○ Freezeability ◎ ◎ ◎Gas generation ◎ ◎ ◎  * 1) Softanol, manufactured by Nippon Shokubai Chemical Industry Co., Ltd. * 2) Ethylene oxide adduct of dovanol 23, manufactured by Mitsubishi Yuka Co., Ltd. * 3) C₃₂H₁₄Cl_TwoN₈Cu

Example 2 Sample No. 1 of Example 1 was used to remove scale stains (used for one month) attached to a poly bath which could not be easily removed by rubbing.
After sprinkling the stock solution of No. 1 and leaving it to stand for 1 minute, the surface of the tub was rubbed back and forth 10 times with a urethane sponge, and the stain removal was evaluated.

Continued on the front page (58) Fields surveyed (Int. Cl. ⁶ , DB name) C11D 3/20 C11D 3/39 C11D 7/18 C11D 7/26 C11D 17/00 WPI / L (QUESTEL)

Claims (2)

(57) [Claims] 1. A liquid detergent composition comprising (a) hydrogen peroxide, (b) an anionic surfactant and / or a nonionic surfactant, and (c) glutaric acid or a salt thereof. 2. The liquid detergent composition according to claim 1, further comprising (d) polyethylene glycol.