JPH04213400A - Liquid detergent composition - Google Patents

Abstract

PURPOSE:To obtain a liquid detergent composition which stably contains hydrogen peroxide and is excellent in the stability even after the lapse of time and detergency by compounding hydrogen peroxide, an anionic and/or nonionic surfactant, and glutaric acid or its salt. CONSTITUTION:A liquid detergent composition comprising hydrogen peroxide (a), an anionic surfactant and/or a nonionic surfactant (b) and glutaric acid or its salt (c). The addition of polyethylene glycol (d) to the above components (a) to (c) is preferred because of an improvement in the preservation stability and the inhibition of the generation of hydrogen peroxide. The proportions of the components (a) to (d) range from about 0.5 to 8wt.%, about 1 to 10wt.%, about 0.5 to 8wt.%, and about 0.1 to 10wt.%, respectively.

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

[Prior Art] Dirt in the house includes stains caused by mold and stains caused by calcium in tap water.
Liquid cleaning agents containing acids and oxidizing agents 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 (Japanese Unexamined Patent Publication No. 78905/1983) was common. Further, for the purpose of removing dirt derived from tap water in toilets and bathrooms, a composition containing organic acids such as malic acid and citric acid (Japanese Patent Application Laid-Open No. 71302/1983) has been disclosed. Furthermore, a composition comprising hydrogen peroxide, an organic acid, and a surfactant (Japanese Patent Application Laid-open No. 164400/1982) has been proposed as having both sterilizing properties and stain removal properties. The organic acids used in these liquid cleaning compositions are hydroxycarboxylic acids and unsaturated carboxylic acids due to their solubility.

However, in compositions in which hydrogen peroxide is used in combination with organic acids such as hydroxycarboxylic acids and unsaturated carboxylic acids, hydrogen peroxide decomposes during storage and oxygen gas is generated, causing the internal pressure of the container to increase. increases, the container swells,
There were problems such as rupture. In addition, liquid detergents containing organic acids as described above tend to cause precipitation over time, which poses a problem in terms of storage stability.

0004

OBJECTS OF THE INVENTION The present invention provides a liquid detergent composition in which hydrogen peroxide is stably blended and which has excellent stability over time and cleaning performance.

[0005]

[Means for Solving the Problems] The liquid cleaning composition of the present invention contains the following three components (a), (b), and (c), or further contains the four components (d). Features. (a) Hydrogen peroxide. (b) Anionic surfactant and/or nonionic surfactant. (c) Glutaric acid or its salt. (d) Polyethylene glycol.

[0006]

[Embodiment] Component (a), hydrogen peroxide, is blended in the composition in an amount of 0.5 to 8% by weight, preferably 1.5 to 5% by weight, from the viewpoint of effectiveness and stability as a disinfectant. This is desirable. 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 cleaning composition of the present invention in an amount of 1 to 10% by weight, more preferably 2 to 5% by weight.

The anionic surfactant is preferably one that is stable in the acidic to weakly acidic range,
12) Diphenyl ether disulfonate, alkyl (
C10-C14) Benzene Sulfonate, Alkane (C
10-C18) sulfonate, α-olefin (C12
~C16) Sulfonate, alkyl (C8-C12) phenol polyoxyethylene (p = 3-10) ether sulfate, alkyl (C8-C12) phenol polyoxyethylene (p = 3-16) ether sulfate sulfonate (NES-D ), polyoxyethylene (p=1-5) alkyl (C10-C16) ether sulfate, etc., and preferred are alkylbenzenesulfonates and alkanesulfonates. Note that p indicates the average number of added moles of ethylene oxide.

[0008] As a nonionic surfactant, a carbon number of about 8
-24 higher alcohols, polyhydric alcohols, fatty acids, fatty acid amides, fatty acid amines, alkylphenols, and alkylene oxide adducts of synthetic alcohols obtained by oxidizing n-paraffins and α-olefins. As the alkylene oxide, ethylene oxide, propylene oxide, and butylene oxide are used.

Specifically, polyoxyethylene (p=5
~20) Lauryl ether, polyoxyethylene (p=
5-20) C10-C14 secondary alkyl ether, polyoxyethylene (p=5-20) hexadecyl ether, polyoxyethylene (p=5-20) nonylphenyl ether, polyoxyethylene (p=5-20) ) glyceryl monostearate, polyoxyethylene (p=5
-20) Octylphenyl ether, polyoxyethylene (p=5-20) monostearate, polyoxyethylene (p=5-20) stearylamide, etc.
Preferably polyoxyethylene (p=5-20) C1
2-C14 secondary alkyl ether, such as Softanol from Nippon Shokubai Kagaku Kogyo Co., Ltd.

[0010] Component (c) glutaric acid or its salt is:
Usually 0.5 to 8% by weight, preferably 1 to 6% by weight. If the blending amount is less than 0.5% by weight, the action as an acid will be weak and the detergency will be poor, which may be undesirable. On the other hand, if it exceeds 8% by weight, it may adversely affect the stability of hydrogen peroxide and generate oxygen gas, and storage stability may deteriorate and precipitation may occur over time.

[0011] Glutaric acid or its salt is difficult to obtain industrially with high purity, and even if it is obtained, it is expensive. Glutaric acid or salt has a weight ratio of succinic acid (salt)/glutaric acid (salt)/adipic acid (salt) of 18 to 30/60.
Since it is commercially available as a mixture of ~70/10 to 15 at low cost, there is no harm in preparing the liquid cleaning composition of the present invention using this mixture. In this case, glutaric acid (salt) exhibits a hydrotropic effect on succinic acid (salt) and adipic acid (salt), and succinic acid (salt),
Increases the liquid stability of adipic acid (salt).

Furthermore, from the viewpoint of improving storage stability and suppressing the generation of oxygen gas from hydrogen peroxide, polyethylene glycol is added as component (d) to the liquid cleaning composition in an amount of 0.1 to
It is preferable to blend 10% by weight, more preferably 0% by weight.
．． It is blended in an amount of 5 to 5% by weight. The polyethylene glycol preferably has a weight average molecular weight of 100 to 20,000, more preferably 100 to 2,000.

[0013] Furthermore, the liquid detergent composition of the present invention contains:
As a stabilizer for hydrogen peroxide, a chelating agent, an antioxidant, etc. can be added. Chelating agents 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 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 (BHA
), 2,6-di-tert-butyl-4-methylphenol (BHT), and the like. These stabilizers are
Depending on the concentration of hydrogen peroxide, there may be 0 in the liquid cleaning composition.
-5% by weight, preferably 0.01-3% by weight.

The liquid cleaning composition of the present invention may also contain known hydrotropes and colorants (for example,
Copper phthalocyanine pigment described in Publication No. 20519),
Optional components such as a pH adjuster and a viscosity adjuster can be appropriately blended. Further, the liquid cleaning composition of the present invention usually takes the form of an aqueous solution or an aqueous emulsion;
is suitably less than 6, preferably in the range of 1.5 to 4.5.

[0016]

Effects of the Invention In the present invention, hydrogen peroxide is stabilized by adding glutaric acid or its salt to a system containing hydrogen peroxide and a nonionic or anionic surfactant to prepare a disinfectant liquid detergent composition. It is possible to improve storage stability by preventing the formation of precipitates over time, and to significantly improve detergency. Further, by further blending polyethylene glycol, the stability of hydrogen peroxide and the storage stability of the composition can be further improved.

[0017] Therefore, the liquid cleaning composition of the present invention is effective for sterilizing cleaning, and is particularly suitable for use as a household cleaning agent for areas such as toilets, kitchens, microwave ovens, and bathrooms.

[0018]

[Examples] The effects of the present invention will be specifically explained below with reference to Examples. Prior to this, the evaluation method used in the Examples will be described. (1) Cleaning power test method

(a) Preparation of model urine scale A paste made by adding 150 parts by weight of water to 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 20 parts by weight of mucin and kneading the mixture. of,
0.16 g was uniformly applied to a 2.5 cm x 4.5 cm ground glass. This was dried in an oven at 105°C for 1 hour and used as a model urine scale.

(b) Evaluation method for cleaning power: Add 3 parts of model urine scale prepared by the above method to 100ml of cleaning agent.
After immersing for 0 seconds, rub twice with a sponge and visually judge whether dirt has been removed. ○: Most of the model urine stains are removed. △: The model urine stains are removed to some extent. ×: The model urine stains are almost impossible to remove.

(2) Test method for freeze-restoreability: Put a sample into a 100 ml glass bottle, and -2
After performing a freeze-restore cycle of 0°C (1 day)←→0°C (1 day), the appearance was visually evaluated after storage at 5°C for 1 day. ◎: Uniformly transparent after 4 cycles of freeze-restore ○: Uniformly transparent after 2 cycles of freeze-restore ×: Cloudy or precipitate formed after 2 cycles of freeze-restore

002
2] (3) Gas generation test method A sample was placed in a 300 ml plastic container, sealed tightly and stored at 50°C. The appearance of the bottle after storage was visually evaluated by comparing it with the appearance of the same container filled only with water. ◎: Equivalent to a water-filled product after 2 weeks storage ○: Equivalent to a water-filled product after 1 week storage ×: Clearly inferior to a water-filled product after 1 week storage (swelling)

Example 1 Sample No. 1 shown in Tables 1 to 4 below. Liquid cleaning agents Nos. 1 to 13 were prepared and evaluated for performance, and 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-C14 secondary alcohol ethoxylate (p=9) *1 - - 5
- C12-C14 secondary alcohol ethoxylate (p=12) - - - -
C12-C14 secondary alcohol ethoxylate (p=
15) 3 3 - - C12
~C13 oxo alcohol ethoxylate (p=12)
*2 - - - 3 Sodium dodecylbenzenesulfonate
- - - - C10 to C18 sodium paraffin sulfonate -
− − − Fumaric acid

− − − − Succinic acid

− − −
- citric acid

− − − − Glutaric acid

3 3 2
6 Adipic acid

− − − − Hydroxyethane diphosphonic acid
− − − − Polyethylene glycol: Molecular weight 200 −
− − − Polyethylene glycol: Molecular weight 400 −
- - - Polyethylene glycol: molecular weight 1000 -
− − − Copper phthalocyanine pigment *3 (
ppm)
− − − − Water

balance
Liquid pH (adjusted with NaOH)
2
4 3 3 Performance


Cleaning power

○ ○ ○ ○ Freeze-restorability

○ ○ ○ ○
Gas generation rate
○
○ ○ ○ *1) Softanol, manufactured by Nippon Shokubai Chemical Co., Ltd., *2) Ethylene oxide adduct of Dovanol 23, manufactured by Mitsubishi Yuka Co., Ltd., *3) C32H
14Cl2N8Cu

[0025]

[Table 2]

Comparison example

Sample No. 5 6 7 Composition w
t%

hydrogen peroxide

3 3 3 C12~
C14 secondary alcohol ethoxylate (p=9)*1
3 3 3 C12-C14 secondary alcohol ethoxylate (p=12) -
- - C12-C14 secondary alcohol ethoxylate (p=15) - - - C
12-C13 oxo alcohol ethoxylate (p=1
2) *2 - - - Sodium dodecylbenzenesulfonate
- - - C10 to C18 sodium paraffin sulfonate - - -
fumaric acid

3--Succinic acid

- 1.5 - Citric acid

− − 3
glutaric acid
−
− − Adipic acid

− − − Hydroxyethane diphosphonic acid
− − − Polyethylene glycol: Molecular weight 200 −
- - Polyethylene glycol: molecular weight 400
− − −
Polyethylene glycol: molecular weight 1000
− − − Copper phthalocyanine pigment *3 (ppm)
− − − Water


Balance liquid pH (adjusted with NaOH)

3 3 3 Performance


Cleaning power

× ○ ○ Freeze-restorability

× × ○ Gas generation rate
× ○
× *1) Softanol manufactured by Nippon Shokubai Chemical Co., Ltd. *2) Ethylene oxide adduct of Dovanol 23 manufactured by Mitsubishi Yuka Co., Ltd. *3) C32H14Cl2N
8Cu

[0026]

[Table 3]

Example

Sample No. 8 9 10 Composition wt%

hydrogen peroxide

3 3 5 C12
~C14 secondary alcohol ethoxylate (p=9)*
1 - - - C12 to C14 secondary alcohol ethoxylate (p=12) - -
3 C12-C14 secondary alcohol ethoxylate (p=15) - - - C1
2-C13 oxo alcohol ethoxylate (p=12
) *2 − − − Sodium dodecylbenzenesulfonate
3-1 C10-C18 sodium paraffin sulfonate-3
- Fumaric acid

− − − Succinic acid

- - 1.5 Citric acid

− − −
glutaric acid

3 3 3 Adipic acid

- - 0.5 Hydroxyethane diphosphonic acid
- - 0.1 Polyethylene glycol: Molecular weight 200
− − − Polyethylene glycol: Molecular weight 400
- - - Polyethylene glycol: molecular weight 1000 -
- - Copper phthalocyanine pigment *3 (ppm
) −
− − Water

Balance liquid pH (adjusted with NaOH)
3 3 3 Performance

Cleaning power

○ ○ ○ Freeze-restorability
○ ○
○ Gas generation rate

○ ○ ○ *1) Softanol, manufactured by Nippon Shokubai Chemical Co., Ltd., *2) Ethylene oxide adduct of Dovanol 23, manufactured by Mitsubishi Yuka Co., Ltd., *3) C3
2H14Cl2N8Cu

[0027]

[Table 4]

Example

Sample No. 11 12 13
Composition wt%

hydrogen peroxide

5 5 5 C
12-C14 secondary alcohol ethoxylate (p=9
)*1 − − − C12 to C14 secondary alcohol ethoxylate (p=12) −
3 3 C12-C14 secondary alcohol ethoxylate (p=15) 3 − −
C12-C13 oxo alcohol ethoxylate (
p=12)*2 − − − Sodium dodecylbenzenesulfonate
- 1 1 C10-C18 sodium paraffin sulfonate -
− − Fumaric acid

− − − Succinic acid

- 1.5 1.5 Citric acid
−
− − Glutaric acid

3 3 3 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 *3 (ppm)
-20 20 water

balance
Liquid pH (adjusted with NaOH)
3
3 3 Performance


Cleaning power
○
○ ○ Freeze-restorability

◎ ◎ ◎ Gas generation rate

◎ ◎ ◎ *
1) Softanol manufactured by Nippon Shokubai Chemical Co., Ltd. *2)
Manufactured by Mitsubishi Yuka Co., Ltd., ethylene oxide adduct of Dovanol 23, *3) C32H14Cl2N8Cu

00
28] Example 2 Sample N from Example 1 was applied to the steam stains (used for one month) on a plastic bathtub that could not be easily removed by rubbing.
o. After sprinkling the undiluted composition of No. 1 on the tub and leaving it for 1 minute, the surface of the tub was rubbed back and forth 10 times with a urethane sponge to evaluate dirt removal, and it was found that dirt removal was good.

Claims (2)

[Claims] 1. A liquid cleaning composition comprising (a) hydrogen peroxide, (b) an anionic surfactant and/or a nonionic surfactant, and (c) glutaric acid or a salt thereof. [Claim 2] Further, (d) Polyethylene glycol The liquid cleaning composition according to claim 1, comprising: