KR20020052547A - Bleach detergent composition - Google Patents

Abstract

PURPOSE: Provided is a bleaching detergent composition which comprises 3-30 parts by weight of oxygen based peroxide containing epsilon-phthalimidoperoxyhexanoic acid, and which shows high washing, bleaching and disinfecting effects at low temperature with relatively small amount of bleaching components. CONSTITUTION: The bleaching detergent composition comprises 3-30 parts by weight of oxygen based peroxide containing epsilon-phthalimidoperoxyhexanoic acid. The composition comprises 60 parts by weight or less of percarbonate and 60 parts by weight or less of perborate as the oxygen based peroxide. The composition shows high washing, bleaching and disinfecting effects at low temperature with relatively small amount of bleaching components by applying epsilon-phthalimidoperoxyhexanoic acid having peracid group in molecule, without using percarbonate or perborate as bleaching detergent, and TAED(tetra acetyl ethylene diamine) or NOBS(nonanoyloxybenzene sulfonate) as bleaching activator.

Description

Bleach detergent composition

The present invention relates to a bleach detergent composition. More specifically, the present invention does not require a separate bleach activator, including an oxygen-based bleach component having a peracid in a molecule, and relates to a bleach detergent composition having excellent low temperature bleaching activity.

Bleach detergents generally contain builders represented by surfactants, alkaline agents and ion sealants, and additives such as enzymes, fluorescent brighteners, and fragrances, as well as general laundry detergents. So it consists of a process of first preparing a detergent base and adding bleach to it. In addition, percarbonate or perborate is used as the oxygen-based bleach, and TAED (tetra acetyl ethylene diamine) is most commonly used as a bleach activator, and some companies use nonanoyloxybenzene sulfonate (NOBS). As described above, US Pat. Nos. 4,064,062 and 4,338,210, etc., are described in detail.

In addition to these organic bleach activators, many bleach activators using transition metals such as Mn have been reported. US Patent Nos. 5,830,839, 4,731,196, 5,409,627, 5,246,621, 5,227,084 and 5,114,611 and the like. In the technology using the transition metal Mn, the bleach activator reacts with percarbonate or perborate in an aqueous solution to create a peracetyl or perhydroxy group to increase the bleaching activity.

In a more conventional manner, the molecular formula of percarbonate is 2Na ₂ CO ₃ ㆍ 3H ₂ O ₂ and the perborate is NaBO ₃ H ₂ O. First, the reaction between percarbonate and TAED produces peracetyl ions as follows.

_{2Na 2 CO 3 3H 2 O 2} + (CH 3 CO) 2 NCH 2 CH 2 N (CH 3 CO) 2 → CH 3 COO - + by-products

And the reaction of percarbonate with NOBS likewise produces peracetyl ions.

_{2Na 2 CO 3 3H 2 O 2} + C 8 COO-Ar-SO 3 NA → C 8 COO - + by-products

In the case of the transition metal, it reacts with the peroxide to generate perhydroxy ions as the transition metal is reduced from +2 to +3.

By this mechanism, the bleaching activity is increased. This is because the peroxide itself decomposes at low temperatures to produce perhydroxy ions and has a disadvantage of being made well at high temperatures. This causes a drop in activity at low temperatures. TAED and NOBS were developed to compensate for this. These materials react with peroxides in aqueous solutions to form peracetyl ions more easily, as described in the above mechanism. Therefore, the bleaching activity was higher than that of the peroxide itself, and the activity temperature was also greatly reduced. Although slightly different depending on the peroxide (percarbonate), it played a role of lowering the temperature of 40 ° C to 60 ° C or more. In addition, a bleach activator using a transition metal such as manganese, which is developed later, may form perhydroxy ions at a lower temperature, thereby lowering the active temperature until 20 ° C. However, when the low temperature bleaching activator using the transition metal is applied, the reaction is so extreme that it may damage the fiber and the color, which has become a focus of development and application.

As such, previous attempts to increase bleaching activity have been made by applying a bleach activator used as a catalyst rather than a peroxide alone.

Therefore, in the present invention, as described above, ε-phthalimidoperoxyhexanoic acid having a peracid group in the molecule without using percarbonate or perborate inevitably included in the bleach detergent and without using TAED or NOBS as a bleach activator The application of (phthalimidoperoxyhexanoic acid) revealed that even a relatively small amount of bleaching agent exhibits high cleaning, bleaching and bactericidal properties at low temperatures.

The present invention relates to a bleach detergent composition comprising 3 to 30 parts by weight of an oxygen-based peroxide including an ε-phthalimidoperoxyhexanoic acid.

Existing bleach contains bleach activator such as TAED (Tetra acetyl ethylene diamine) which acts as a catalyst for activating the bleach component, oxygen peroxide or perborate. The bleach activator reacts with the oxygen-based bleach component to form peracetyl ions with higher bleaching activity. However, the present invention does not require a special bleach activator by containing a peracid component stabilized with an oxygen-based bleaching component, that is, ε-phthalimidoperoxy hexanoic acid. Because it contains peracid in the molecule, the bleaching power is excellent at low temperature around 20 ℃ than the previous bleach detergent. In addition, the low-temperature bleaching activity is not only double the washing power, but also excellent sterilization effect against harmful bacteria.

In the bleaching system applied in the present invention, by applying ε-phthalimidoperoxyhexanoic acid having a peracid in a molecule, a reaction between peroxide and a catalyst is not required, and it decomposes in an aqueous solution to form peracetyl ions, thereby improving the bleaching activity. Cause Thus, the bleaching activity is excellent and the active temperature range is about 20 ° C. However, the reactions do not occur as rapidly as the transition metals, which does not cause clothing and color damage. Compared with the existing bleaching system, it has excellent washing power and bleaching power at a low temperature of 20 ° C or less, and shows excellent efficacy in sterilizing power.

In the present invention, the powder detergent base is first prepared by using a direct neutralization reaction between an acidic unneutralized anionic surfactant and an alkali builder used in a conventional detergent in a mixer having a vertical or horizontal rotary shaft.

Add unneutralized surfactants and nonionic surfactants to the powder raw material consisting of alkali builders and other powder raw materials that cause the neutralization reaction to the granulator rotating at high speed, where the stirring blades are mounted on the vertical and horizontal rotating shafts rotating at high speed. A non-neutralizing surfactant and other liquid components are added at the same time to make slightly sticky particles, which are then coated with fine particles such as zeolite to prepare a detergent base. Bleach detergent is completed by adding a granular epsilon phthalimidoperoxy hexanoic acid and its additive here.

The surfactant applied in the present invention is an anionic surfactant, a linear alkylbenzelsulfonate (R ₁ -CH ₂ -SO ₃ Na: R ₁ = C ₉ ~ C ₁₅ alkyl), fatty acid salt (R ₁ -CH ₂ -COONa : R ₂ = C ₁₁ -C ₁₆ alkyl), alkanesulfonate (R ₃ = CH-SO ₃ Na: R ₃ = C ₁₁ -C ₁₈ alkyl), and alphaolefinsulfonate (R ₄ -CH = CH-CH ₂ -SO ₃ Na, R ₄ = C ₁₂ -C ₁₈ alkyl).

In addition, as a nonionic surfactant, fatty alcohol polyoxyethylene glycol (R ₅ -CH- (O-CH _2- ).

CH ₂ ) _n -OH; n is an integer of 5-25, R ₅ = C ₁₁ -C ₁₈ alkyl), fatty acid polyoxyethylene glycol (R ₆ -CO- (O-CH ₂ -CH ₂ ) _m -OH; m = 5-25 of Integer, R ₆ = C ₁₁ -C ₁₈ alkyl), alkylphenylpolyoxyethylene glycol (R ₇ -Ar-O- (CH ₂ -CH ₂ -O) iH; Ar = benzene ring, i = 5-25 Integer, R ₇ = C ₁₁ -C ₁₈ alkyl), and polyoxyethylene glycol (HO-CH ₂ CH ₂ ) _i -H; i = an integer and the total molecular weight is 1000-30000) 1 or more types can be mentioned.

On the other hand, the following carbonates (e.g., sodium carbonate (Na ₂ CO ₃ ) or sodium hydrogen carbonate (NaHCO ₃ )) as a medium of alkaline agents and absorbents as builders to prepare detergents that enhance the cleaning power of the above-mentioned surfactants , Silicates (eg layered crystalline α-Na ₂ SiO ₃ or β-Na ₂ SiO ₃ ), phosphates (eg orthophosphoric acid, pyrophosphoric acid, tripolyphosphoric acid, tetrapolyphosphoric acid Or salts thereof), phosphonates (e.g., diethylenetriaminepentamethylenephosphonate, aminotrimethylenephosphonate, 1-hydroxyethylene-1, 1-diphosphonide), nitrilotriacetic acid Or salts thereof, ethylenediaminetetraacetic acid or salts thereof, and carboxymethylcellulose, polyethylene glycol, polyvinyl alcohol, polyvinylpolydon, polyacrylic acid as physical assistants for recontamination prevention and absorber. It is used to select one or more from the copolymer or the salt thereof, or a sulfate of a salt thereof, maleic acid and vinyl ether.

According to the present invention, the component ratio is an anionic surfactant: nonionic surfactant: builder in a detergent concentrate powder consisting of a ratio of 3: 1: 5 ~ 1: 1: 20 0.5 parts by weight or less as an optical brightener as an additive, enzyme 1.0 Below parts by weight, antifoaming agent is applied below 0.5 parts by weight to complete the detergent base. Oxygen peroxide is applied here in an amount of 3 to 30 parts by weight, more preferably 5 to 25 parts by weight.

Oxygen-based peroxides comprise 20 to 100 parts by weight of ε-phthalimidoperoxyhexanoic acid, up to 60 parts by weight of percarbonate, up to 60 parts by weight of perborate, and up to 10 parts by weight of bleach activator (TAED).

Although described in the following experimental examples, the application of ε-phthalimidoperoxyhexanoic acid as a peracid is the best in bleaching activity at low temperatures and the effect is increased when used in combination with other oxygen-based bleach activators. This can be seen through this study.

Hereinafter, the present invention will be described in detail with reference to Examples and Comparative Examples, but the technical scope of the present invention is not limited thereto.

Examples and Comparative Examples

Bleach detergent compositions of Examples and Comparative Examples were prepared using the composition shown in Table 1 below.

Table 1. Comparative Examples and Examples

Detergent composition Comparative Example 1 Comparative Example 2 Example 1 Example 2 Example 3 fatty acid 2.0 2.0 2.0 2.0 2.0 Polyoxyethylene alkyl ether 8.0 8.0 8.0 8.0 8.0 Alpha olefin sulfonate 8.0 8.0 8.0 8.0 8.0 Alkyl sulfonate 5.0 5.0 5.0 5.0 5.0 Soda ash (sodium carbonate) 30.0 30.0 30.0 30.0 30.0 Forget-me-not (sodium sulfate) Remaining amount Remaining amount Remaining amount Remaining amount Remaining amount Zeolite 4A 20.0 20.0 20.0 20.0 20.0 Percarbonate 15.0 6.0 Perborate 0.02 15.0 6.0 ε-phthalimidoperoxy hexa noric acid 7.0 7.0 13.0 TAED ¹⁾ 2.0 2.0 1.0 1.0 Sequest agent ²⁾ 0.02 0.02 0.02 0.02 0.02 Mold Dyes ³⁾ 0.3 0.3 0.3 0.3 0.3 Enzyme ⁴⁾ 0.3 0.3 0.3 0.3 0.3 Antifoam ⁵⁾ 0.4 0.4 0.4 0.4 0.4

1) TAED: Mikon ATC-Green Wykes

2) Dequest 2066D Solusia

3) Tinopal CBS-X Chiba Specialty Chemical

4) Savinase 12.0T Novo Nordisk

5) LDC1215 Korea Silicon Silicon

Experimental Example 1. Bleaching force experiment

The washing power was compared with the bleaching power of Comparative Example and Example for red wine stains (EMPA 114), coffee stains (wfk 10K), red pepper stains (wfk 10P) at 20 ℃ using a Terg-o-tometer.

Table 2. Bleaching force test results

In general, the application of percarbonate was superior to the application of perborate to bleaching. However, it was found that the bleaching power of applying the epsilon-phthalimidoperoxyhexanoic acid, which is the peracid component applied in the present invention, was excellent in both red wine and red pepper stain.

Experimental Example 2. Washing force experiment

The cleaning power was compared with the bleaching power of the comparative example and the Example for cotton staining cloth (wfk 10D and Japan Laundry Association) and mixed staining cloth (wfk 20P) at 20 ° C using Terg-o-tometer.

Table 3. Test Results

Likewise, the percarbonate application was superior to the perborate application. However, it can be seen that the cleaning power of applying the ε-phthalimidoperoxyhexanoic acid, which is the peracid component applied in the present invention, is excellent in all artificial contaminated cloths.

Experimental Example 3. Sterilization test

A 0.85% aqueous NaCl solution (20 ° C.) was prepared for each sample according to Comparative Examples and Examples using an SDC medium having a medium composition (Casitone 30g, Tween-80 5g, Soyton 5g, NaCl 5g, Lecithin0.7g, Agar 15g / L). Prepare 1 L each beaker and add the bacteria shown in Table 4 at a concentration of 2.0 ~ 5.0 × 10 ⁵ / ml, and then start stirring. The time course is measured while adding Comparative Examples and Examples to the aqueous solution of 0.85% NaCl added strain at the rate of 1.0g / L. At this time, the bacterial solution without detergent is used as a blank test. After 20 minutes and 30 minutes after the addition of the sample, take 1ml of serial dilution (use 0.85% NaCl aqueous solution as dilution buffer), spread it on solid medium, and incubate at 37 ℃.

Incubate in r) for 24 hours to determine the reduction rate compared to the blank test through colony counting (colony counting) for each Comparative Example and Example.

Application strains tested were E. coli (ATCC 8739), typhoid fever (ATCC 19430), P. aeruginosa (AT

CC 6538), pneumococcal bacterium (ATCC 9621) was used.

Table 4. Test Results

As shown in Table 4, the sterilization power of the single use of the peracid component, ε-phthalimidoperoxyhexanoic acid, was the best, and the low temperature of 20 ° C resulted in better sterilization than those mixed with percarbonate. I could see that.

The bleach detergent composition according to the present invention is applied by using ε-phthalimidoperoxyhexanoic acid having a peracid group in the molecule without using percarbonate or perborate as bleach and without using TAED or NOBS as a bleach activator. As a small amount of bleaching ingredient, it shows high washing power, bleaching power and bactericidal power at low temperature.

Claims (2)

Bleach detergent composition characterized in that it contains 3 to 30 parts by weight of an oxygen-based peroxide including ε-phthalimidoperoxyhexanoic acid. The bleach detergent composition according to claim 1, which contains 60 parts by weight or less of percarbonate and 60 parts by weight or less of percarbonate as an oxygen-based peroxide.