KR100456756B1 - Oxygen bleach composition - Google Patents

Abstract

The present invention relates to an oxygen-based bleach composition, in particular, in the oxygen-based bleach composition, including a di-limonene (D-limonene) of the bleach activator tetraacetylethylene diamine (TAED, tetra acetyl ethylene diamine) difficult to remove the oil stain The present invention relates to an oxygen-based bleach composition which is not only easy to remove stains of hydrophilicity and hydrophobicity by supplementing the removal ability, but also has excellent self-sterilization ability against bacteria.

Description

Oxygen bleach composition {OXYGEN BLEACH COMPOSITION}

The present invention relates to an oxygen-based bleach composition, and more particularly, to an oxygen-based bleach composition having excellent removal power of hydrophobic stains and excellent self-sterilization power.

Bleach generally contains oxygen-based peroxides and bleach activators in addition to builders represented by surfactants, alkali agents, ion-blocking agents, and additives such as enzymes, fluorescent brighteners, and fragrances, like general bleach detergents. Conventional bleach is prepared by the process of preparing a detergent granular detergent powder using an additive and a cleaning component except a peroxide and a bleach activator, and adding a bleach component and an additive thereto.

Generally, percarbonates and perborates are used for oxygen-based peroxides, and tetraacetylethylenediamine (TAED) is most commonly used as a bleach activator. US Pat. Nos. 4,064,062, 4,338,210, and 6,197,737 disclose a bleach using nonanoyloxybenzene sulonate (NOBS) as a bleach activator.

In the case of tetraacetylethylenediamine, the bleaching power for hydrophilic juice stains is excellent, but there is a limit to the removal of oily stains such as sebum and blood from the human body. In this case, it is advantageous to use a bleach activator such as nonanoyloxybenzenesulfonate which is a hydrophobic bleach activator. However, nonanoyloxybenzenesulfonate is expensive, and there is a problem in economics that a large amount must be used as compared to tetraacetylethylenediamine.

For the same reason, Korean Patent No. 113025 discloses a dry cleansing detergent containing a limonene derivative, and Korean Patent Application No. 1992-013010 discloses a liquid bleach composition containing D-limonene. It is starting. However, the above-mentioned prior arts disclose only the local stain removal effect of the liquid bleach and the dry cleansing detergent, and have a problem in that the hydrophobic stain removal effect is insignificant and the bactericidal power against bacteria is low.

Therefore, there is a further need for an oxygen-based bleach composition not only having excellent hydrophobic stain removal but also having excellent bactericidal activity against bacteria.

In order to solve the above problems, the present invention can not only easily remove hydrophobic stains that are difficult to remove with tetraacetylethylenediamine (TAED), but also has excellent self-sterilization ability against bacteria, and is economical because the price is low. It is an object to provide an oxygen-based bleach composition.

In order to achieve the above object, the present invention provides an oxygen-based bleach composition comprising a di-limonene in an oxygen-based bleach composition comprising a peroxide, a bleach activator, a surfactant, a builder.

Hereinafter, the present invention will be described in detail.

While the present inventors have studied a method for enhancing the function of the oxygen-based bleach against the hydrophobic stain, the oxygen-based bleach added with di-limonene to the oxygen-based bleach composition not only significantly improved the hydrophobic stain removal ability, but also has a self-sterilizing ability against bacteria. It was confirmed that this excellent and excellent effect also in economics, the present invention was completed based on this.

The present invention includes D-limonene in a conventional oxygen-based bleach composition composed of a peroxide, a bleach activator, a surfactant, and the like, to compensate for the hydrophobic stain removal ability of the tetraacetylethylenediamine (TAED, tetraacetylethylenediamine) as a bleaching agent. The present invention relates to an oxygen-based bleach which is not only hydrophilic but also has a markedly improved bleaching power and a force against hydrophobic stains, and excellent self-sterilization ability against bacteria.

The di-limonene used in the present invention is represented by the following general formula (1), and can be used natural di-limonene, which is a monocyclic terpene, which is usually obtained as a by-product in the production of citrus sugar, and synthetic di-limonene obtained from petroleum. The natural di-limonene is obtained by steam distillation of citrus peel and pulp generated from citrus juice production such as lemon, orange, tangerine, and has an oil phase containing about 94 to 98%. Di-limonene is an oily liquid substance that is excellent in removing oil stains such as carbon black stains, milk, chocolate, ice cream, lipstick, etc., and has self-sterilizing power.

Di-limonene in the present invention is 0.01 to 10 parts by weight based on the total composition, almost completely harmless to humans and the environment. If the content of di-limonene is less than 0.01 parts by weight, it is difficult to expect the desired bleaching effect, and if it exceeds 10 parts by weight, there is a problem that the bleaching power according to the amount of use is lowered.

[Formula 1]

The peroxide used in the present invention may be used percarbonate (sodium percarbonate, M ₂ C ₂ O ₆ ), or perborate (sodium perborate, MBO ₃ ), it is preferably included in 40 to 80 parts by weight based on the total composition. .

The bleach activator used in the present invention may use tetraacetylethylenediamine (TAED) or nonanoyloxybenzenesulfonate (NOBS). The bleach activator is included in an amount of 0.01 to 15 parts by weight based on the total composition, when the content is less than 0.01 parts by weight, the effect of activating the peroxide is not sufficient, when more than 10 parts by weight excessively decomposes the peroxide There is this.

In addition, the surfactant used in the present invention may be an anionic surfactant or a nonionic surfactant, it is preferably included in 5 to 15 parts by weight based on the total composition.

Anionic surfactants include linear alkylbenzenesulfonates (R ₁ -CH ₂ -SO ₃ Na, wherein R ₁ is alkyl having 9 to 15 carbon atoms), fatty acid salts (R ₂ -CH ₂ -COONa, where R ₂ Is an alkyl having 11 to 16 carbon atoms, an alkalsulfonate (R ₃ = CH-SO ₃ Na, wherein R ₃ is an alkyl having 11 to 18 carbon atoms), or an alpha olefin sulfonate (R ₄ -CH = CH-CH ₂ SO ₃ Na, wherein R ₄ is alkyl having 12 to 18 carbon atoms, and the like can be used. Nonionic surfactants include fatty alkoxypolyoxyethylene glycol (R ₅ -CH- (O-CH ₂ -CH ₂ ) _l -OH, wherein R ₅ is alkyl of 11 to 18 carbon atoms, and l is 5 to 25 Integer), fatty acid polyoxyethylene glycol (R ₆ -CO- (O-CH ₂ -CH ₂ ) _m -OH, wherein R ₆ is alkyl of 11 to 18 carbon atoms, m is an integer of 5 to 25), alkyl Phenylpolyoxyethylene glycol (R ₇ -Ar-O- (CH ₂ 0CH ₂ -O) _n -H, wherein R ₇ is alkyl of 11 to 18 carbon atoms, Ar is a benzene ring, n is 5 to 25 Integer), or polyoxyethylene glycol (H- (O-CH ₂ -CH ₂ ) _i -OH, wherein i is an integer having a total molecular weight of 1,000 to 30,000) and the like can be used.

The builder used in the present invention is an alkali builder, which enhances the cleaning power of the surfactant, is included as an alkali agent for the preparation of the detergent, and a medium of the absorber. Examples include carbonates such as sodium carbonate (Na ₂ CO ₃ ), sodium bicarbonate (NaHCO ₃ ), silicates such as layered crystalline α-Na ₂ SiO ₃ , or β-Na ₂ SiO ₃ , or sulfates. Can be used

The builder is included in an amount of 10 to 50 parts by weight based on the total composition, when less than 10 parts by weight is not sufficient to enhance the cleaning power of the surfactant, when more than 50 parts by weight is less economical compared to the effect enhancement There is this.

The oxygen-based bleach composition of the present invention may include other additives such as inorganic salts such as sodium carbonate and sodium sulfate, fluorescent dyes, enzymes, flavoring agents, and the like, which are commonly used in detergents, in addition to the above materials. The fluorescent dye is included at most 0.3 parts by weight, and the enzyme is preferably included in 0.01 to 3 parts by weight.

Method for producing the oxygen-based bleach of the present invention containing the above components are as follows. First, in the mixer, the neutralized reaction is carried out by adding an anionic surfactant, or nonionic surfactant, which is not neutralized, and an alkali builder, and di-limonene is added thereto, followed by coating to prepare a granular detergent powder. Peroxides, bleach activators, and other additives can then be added to make oxygen-based bleaches.

More specifically, a stirring blade is attached to a vertical or horizontal rotating shaft rotating at a high speed, and an alkali neutralizer and a non-neutralized anionic or nonionic surfactant are added to the powder builder to cause a neutralization reaction to the mixer rotating at a high speed. To form fully neutralized particles, to which di-limonene is added, or simultaneously coated with a particulate coating such as zeolite to prepare a detergent base. Thereafter, granular peroxides, bleach activators, and other additives are added to prepare oxygen-based bleaches. In this case, the coating material may be zeolite, tar, silica, clay, and the like.

Hereinafter, preferred examples are provided to help understanding of the present invention, but the following examples are merely to illustrate the present invention, and the scope of the present invention is not limited to the following examples.

EXAMPLE

Examples 1 to 3, and Comparative Examples 1 or 2

To the bleach composition using a conventional method in the composition ratio as shown in Table 1. First, the neutralized reaction was performed by adding an anionic surfactant or a nonionic neutralizer or a non-neutral surfactant and an alkali builder in a mixer, and adding di-limonene to it, followed by coating to prepare a granular detergent powder. The oxygen-based bleach composition was then prepared by adding peroxides, bleach activators, and other additives. The unit is parts by weight .

division Example 1 Example 2 Comparative Example 1 Comparative Example 2 Comparative Example 3 LAS 5 10 5 3 - Polyoxyethylene alkyl ether 3 - 3 5 One Alpha olefin sulfonate One - One - - Soda ash (sodium carbonate) Remaining amount Remaining amount Remaining amount Remaining amount Remaining amount Forget-me-not (sodium sulfate) 3 3 3 3 - Zeolite 4A 3 2 3 4 - Percarbonate 70 60 70 75 95 Tetraacetyletherdiamine ¹⁾ 2 3 - 3 0.5 Nonanoyloxybenzenesulfonate ²⁾ - - 4 - - Di-limonene ³⁾ 0.5 One - - - Other additives Fluorescent dyes ⁴⁾ 0.15 0.15 0.15 0.15 0.15 Enzyme ⁵⁾ 0.5 0.5 0.5 0.5 0.5 1) Tetraacetyletherdiamine: MiKon ATC-Green (Waiksa) 2) Nonyloxybenzenesulfonate: nonyloxybenzensulfonate (Asa synthesis) 3) Di-limonene: Florida chemical 4) Fluorescent dye: Tinopal DMA-X ( Shiva specialty chemical) 5) Enzyme: Savinase 12.OT (Novozyme)

Bleaching power, washing power, and bactericidal power of the bleach composition prepared in Examples 1 or 2 and Comparative Examples 1 to 3 were evaluated in the same manner as in Experimental Examples 1 to 3 below.

Experimental Example 1. Bleaching force

Red wine (EMPA 114), coffee (wfk BC-2), red pepper (wfk 10P), and tea (wfk BC-3) were uniformly applied to 8 × 8 cm 2 white cotton cloth and dried. To a Terg-o-tometer, water (water temperature 20 ° C., hardness 50 CaCO ₃ pm) and 1 g / L of the bleach prepared in Examples 1 or 2 and Comparative Examples 1 to 3 were added. The cotton cloth was put here, it washed for 10 minutes, it rinsed for 3 minutes, and it dried naturally.

After washing the cotton cloth before and after using a colorimeter to measure the whiteness, bleaching power was calculated by substituting Equation 1 (Kubellka-Munk's eq) as follows.

[Equation 1]

In Equation 1, R _s is the surface reflectivity of the contaminated cotton cloth, R _b is the surface reflectivity of the cotton cloth after decontamination, and R _o is the surface reflectivity of the white cotton cloth.

division Example 1 Example 2 Comparative Example 1 Comparative Example 2 Comparative Example 3 Red wine pollution 88% 88% 78% 74% 65% Coffee pollution 88% 87% 85% 79% 62% Pepper pollution 89% 91% 88% 78% 70% Secondary pollution 84% 83% 82% 78% 45%

Through Table 2, it was confirmed that the bleaching power of the bleach composition prepared in Examples 1 and 2 including di-limonene according to the present invention is excellent in all contamination of red wine, coffee, pepper, tea.

Experimental Example 2. Washing power

In a Terg-o-tometer, water (water temperature 20 ° C., hardness 133 CaCO ₃ pm) and 1 g / L of the bleach prepared in Examples 1 or 2 and Comparative Examples 1 to 3 were added thereto. Into each of the 8 x 8 cm 2 cotton cloth (2 sheets each) and 5 x 5 cm 2 contaminated cloth (8 sheets) were contaminated with wfk 10D and wfk 20D. It was washed for 10 minutes, rinsed for 3 minutes, and then dried naturally.

After measuring the whiteness before and after washing the contaminated cotton cloth using a colorimeter, the bleaching force was calculated by substituting Equation 1 (Kubbelka Munch formula) of Experimental Example 1, and the results are shown in Table 3 below. It was.

division Example 1 Example 2 Comparative Example 1 Comparative Example 2 Comparative Example 3 wfk 10D 66% 67% 63% 45% 15% wfk 20D 73% 75% 71% 55% 10% Japan Laundry Science Association 85% 87% 70% 52% 13%

Through Table 3, it can be confirmed that the washing power of the bleach composition prepared in Examples 1 and 2 containing di-limonene according to the present invention is superior to the washing power of Comparative Examples 1 to 3 not containing di-limonene. there was.

Experimental Example 3. Sterilization

In this experimental example P.aeruginosa (Pseudomonas aeruginosa), E.coli (Escherichia coli), Klepsiella pneumoniae (Klebsiella pneumoniae), Stphylococcus epidermis (skin flora), Staphylococcus aureus (hwanonggyun), Vibrio parahaemolyticus (parahaemolyticus), Shigella flexneri (Shigella ), 11 species of Acineobacter baumannii , Aeromonas hydrophyla , Enterobacter aerogenes and Salmoella typhimurium were used. SDC medium consisting of 15 g / L of composition was used.

1 L of 0.85% NaCl aqueous solution (20 ° C.) was prepared in 6 beakers, and the bacteria were added at a concentration of 2.0˜5.0 × 10 ⁵ / mL, followed by stirring. The bleach composition prepared in Examples 1 or 2 and Comparative Examples 1 to 3 was added thereto at a rate of 1.0 g / L, and the time course was measured. At this time, the beaker without the detergent was used as a control.

After 15 minutes and 20 minutes of detergent addition, 1 mL of each was taken and serial dilution (0.85% NaCl aqueous solution was used as the dilution buffer), followed by incubation in a solid medium and incubated in an incubator at 37 ° C. for 24 hours. Example 1 or 2, Comparative Examples 1 to 3, and the control was colony counted (colony counting), and compared to the control to determine the mycelial mortality, the results are shown in Table 4 below.

division 15 mins 20 minutes Example Comparative example Example Comparative example One 2 One 2 3 One 2 One 2 3 P.aeruginosa 99.9 99.9 75.4 80.5 85.8 99.9 99.9 99.9 99.9 99.9 E.coli 99.9 99.9 99.9 99.9 99.9 99.9 99.9 99.9 99.9 99.9 K.pneumoniae 99.9 99.9 92.0 90.2 93.1 99.9 99.9 99.9 99.9 99.9 S.epidermis 99.9 99.9 81.2 91.2 83.5 99.9 99.9 99.9 99.9 99.9 S.aureus 99.9 99.9 93.1 87.6 88.4 99.9 99.9 99.9 99.9 99.9 Vibrio 99.9 99.9 91.8 82.6 94.5 99.9 99.9 99.9 99.9 99.9 parahaemolyticus 99.9 99.9 88.3 91.2 97.8 99.9 99.9 99.9 99.9 99.9 S.flexneri 99.9 99.9 84.6 93.4 99.2 99.9 99.9 99.9 99.9 99.9 A.baumannii 99.9 99.9 97.2 95.2 90.6 99.9 99.9 99.9 99.9 99.9 A.hydrophyla 99.9 99.9 93.1 86.4 88.4 99.9 99.9 99.9 99.9 99.9 E.aerogenes 99.9 99.9 99.9 99.9 99.9 99.9 99.9 99.9 99.9 99.9 S.typhimurium 99.9 99.9 99.9 99.9 99.9 99.9 99.9 99.9 99.9 99.9

Through Table 4, the bleach composition prepared in Examples 1 and 2 containing di-limonene according to the present invention compared to Comparative Examples 1 to 3 containing no di-limonene 15 minutes added detergent to the bacteria It was found that the later death rate was excellent.

As described above, the oxygen-based bleach composition of the present invention is easy to remove hydrophilic and hydrophobic stains by supplementing the removal ability of oil stains that are difficult to remove with tetraacetylethylenediamine (TAED) as a bleach activator, and self sterilizing ability against bacteria. This is excellent, and the price is economical advantage.

Claims (5)

a) 40 to 80 parts by weight of percarbonate (M ₂ C ₂ O ₆ ), or perborate (sodium perborate, MBO ₃ ); b) 0.01 to 15 parts by weight of tetraacetylethylenediamine (TAED), or nonanoyloxybenzenesulfonate (NOBS); c) 5 to 15 parts by weight of surfactant; d) 10 to 50 parts by weight of alkali builders; And e) 0.01 to 10 parts by weight of di-limonene Oxygen-based bleach composition comprising. delete The method of claim 1, An oxygen-based bleach composition obtained by extracting the di-limonene from a citrus peel or by synthesizing from petroleum hydrocarbons. delete delete