JPH0978094A - Liquid oxygen-based bleaching agent composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an acidic type liquid oxygen-based bleaching agent composition capable of exhibiting good bleaching effect on vegetable spot and stain, excellent in storage stability, especially at high temperature and prevented from decomposition of hydrogen peroxide. SOLUTION: This bleaching agent composition contains 2.0-10wt.% hydrogen peroxide, 0.5-10wt.% anionic surfactant (e.g. an alkenyl sulfuric acid salt, an alkenyl ether sulfuric acid salt, an olefin sulfonic acid salt or an unsaturated fatty acid salt), 1.0-10wt.% uncross-linkable carboxylic acid-based polymer (e.g. an acrylic acid-based polymer or a maleic acid-based polymer) and 0-3.0wt.% organophosphorus compound and does not substantially contain a nonionic surfactant and has pH2-5.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a liquid oxygen bleaching composition, and more specifically, it has excellent storage stability and good bleaching power, particularly bleaching power against plant stains and stains. The present invention relates to a liquid oxygen bleaching composition.

[0002]

2. Description of the Prior Art Liquid type bleaching agents using hydrogen peroxide include alkaline and acidic bleaching agents. Decomposition of hydrogen peroxide is promoted in the alkaline region and delayed in the acidic region. Therefore, the acidic type has relatively storage stability at low temperatures, but still has insufficient storage stability at high temperatures.

There have been many studies to improve the storage stability of liquid bleach containing hydrogen peroxide. For example,
Japanese Examined Patent Publication No. 40-7774 discloses a storage-stable weakly acidic liquid bleaching agent using a combination of acidic sodium pyrophosphate, neutral sodium pyrophosphate and potassium pyrophosphate.
No. 84 discloses a stable liquid bleaching having a pH of 0.5 to 7 in which an organic acid selected from alkylidene diphosphonic acid, ethylenediamine tetraacetic acid, diethylenetriamine pentaacetic acid and nitrilotrimethylenephosphonic acid, a soluble tin salt and an ammonium salt are blended. The agent is a hydrogen peroxide stabilizer consisting of poly-α-hydroxyacrylic acid in JP-A-52-103386, and an organic acid, phosphoric acid or boric acid in JP-A-55-108500. A stable liquid bleaching agent having a pH of 1.8 to 5.5, which is a mixture of an acid and a nitrogen compound, is disclosed in JP-A-55-76161. Compounding a poly-α-hydroxyacrylic acid salt in a hydrogen bleaching system exerts a synergistic stabilizing effect. It is disclosed in JP-A-57-154457 that acrylic acid is added. A stabilizing aid for a hydrogen peroxide bleaching agent comprising a copolymer of acrylic acid ester and / or polyerylene glycol methacrylate is disclosed in JP-A-62-18.
Japanese Patent No. 5797 discloses a hydrogen peroxide-based bleaching stabilizer in which a poly-α-hydroxyacrylic acid salt and an organic phosphonate are used in combination. Furthermore, as an acidic hydrogen peroxide-based bleaching composition having improved storage stability at high temperature, JP-A-3-91
597 discloses an example in which polyacrylic acid having a specific molecular weight or a salt thereof is blended in a specific surfactant system, and JP-A-3-188198 discloses a polyacrylic acid having a specific molecular weight in a specific surfactant system. Examples of blending an acid polymer and / or a maleic acid-based polymer with a specific phosphorus compound are
JP-A-4-23897 discloses a nonionic surfactant,
An example in which a carboxylic acid polymer and a specific organic phosphonic acid compound are combined is disclosed in JP-A-4-28797, in which a polycarboxylic acid having a specific molecular weight in a specific surfactant system or a salt thereof and a specific water-soluble inorganic salt are used. The example which mix | blended was disclosed.

[0004]

However, the hydrogen peroxide-based bleaching agents containing these stabilizers have insufficient storage stability at high temperatures, and when used in an acidic system, they have a stabilizing effect on hydrogen peroxide. There is a problem that the effect is too strong and not sufficient, especially for plant stains such as grass juice and stains.

[0005]

Means for Solving the Problems As a result of earnest research by the present inventors, the stability during high temperature storage was remarkably improved by blending a specific surfactant and a carboxylic acid polymer or an organic phosphorus compound. Moreover, they have found that an acidic hydrogen peroxide liquid bleaching agent having a good bleaching power can be obtained, and have completed the present invention. That is, the liquid enzyme-based bleaching agent of the present invention contains the following components (a) to (c), or further (d), contains substantially no nonionic surfactant, and has a pH of 2-5. It is characterized by being in the range.

(A) Hydrogen peroxide: 2.0 to 10% by weight. (B) Anionic surfactant containing at least one double bond in the molecule: 0.5 to 10% by weight. (C) Non-crosslinkable carboxylic acid polymer: 1.0 to 10
weight%. (D) Organic phosphorus compound: 0 to 3.0% by weight.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, hydrogen peroxide (a) which is a bleaching base is mixed in the composition in an amount of 2.0 to 10% by weight, preferably 3 to 7% by weight. Examples of the anionic surfactant having a double bond or more in the molecule which is used as the component (b) of the present invention include alkenyl sulfate, alkenyl ether sulfate, olefin sulfonate, unsaturated fatty acid salt and the like. . Particularly, an α-olefin sulfonate having 10 to 16 carbon atoms is preferable. The anion activator containing a double bond has an effect of suppressing generation of oxygen gas due to decomposition of hydrogen peroxide. The anionic surfactant containing a double bond used here may be used alone or as a mixture. Further, if the amount of the anion activator containing a double bond is 0.5% to 10%, an anion activator containing no double bond may be contained. (B) in the present invention
The blending amount of the components is 0.5 to 10% by weight, preferably 1.0
˜5.0% by weight. If the content of the component (b) is less than 0.5% by weight, sufficient storage stabilizing effect at high temperature is not exhibited, and if it exceeds 10% by weight, stability at low temperature deteriorates, which is not preferable.

In the present invention, the non-crosslinkable carboxylic acid polymer used as the component (c) is preferably an acrylic acid polymer or a maleic acid polymer. As the acrylic acid-based polymer which is the component (c) of the present invention, polyacrylic acid or a salt thereof is suitable and has an average molecular weight of 1,000 to 100,000, preferably 2,000 to 50.
Those in the range of 000 are suitable. This average molecular weight is 1
If it is less than 000 or more than 100,000, the storage stabilizing effect is rapidly reduced. Carbopol, which is often used as a thickening agent for hydrogen peroxide-based acidic liquid bleaching agents, is a polyacrylic acid having a large molecular weight and partially crosslinked, and is not crosslinked polyacrylic acid used in the present invention. Is different from.

Examples of the maleic acid-based polymer used as the component (c) include maleic acid homopolymers and copolymers of maleic acid and other vinyl monomers (including their partially and completely neutralized salts). To be Examples of the copolymer include a copolymer of maleic acid with a vinyl monomer such as acrylic acid, methacrylic acid, acrylic acid ester, methacrylic acid ester, or vinyl acetate. In particular, a copolymer with acrylic acid or methacrylic acid is preferable. The monomer ratio of maleic acid and other monomer is preferably in the range of maleic acid / monomer = 90/10 to 40/60. As the maleic acid-based polymer, one having an average molecular weight of 500 to 100,000, preferably 1,000 to 50,000, more preferably 5,000 to 30,000 is used. When the average molecular weight of the polymer is less than 500 or exceeds 100,000, the storage stabilizing effect is rapidly reduced.

In the present invention, it is preferable to add an organic phosphorus compound which is the component (d), if necessary, and by this addition, the stability of hydrogen peroxide can be enhanced synergistically for a long period of time. A specific example of the organophosphorus compound as the component (d) is alkylidene diphosphonic acid or a salt thereof, and 1-hydroxyethylidene-1,1-diphosphonic acid is particularly preferable. The amount of the component (d) used in the present invention is 0 to 3% by weight, preferably 0.5 to 2% by weight. (D)
If the blending amount of the components exceeds 3% by weight, a polymer separation problem may occur.

The composition of the present invention is balanced by adding water to the above components (a) to (d).
If necessary, alcohols such as isopropanol and ethylene glycol, hydrotropes such as polyethylene glycol and glycerin, thickeners, fragrances, dyes, fluorescent dyes, enzymes and the like may be added. Further, the composition of the present invention contains substantially no nonionic surfactant. When the nonionic surfactant is contained, deterioration of the storage container is promoted, which may lead to deterioration in storage stability.

The pH of the stock solution of the composition of the present invention is 2 to 5, preferably 3 using inorganic acids such as hydrochloric acid and sulfuric acid, organic acids such as p-toluenesulfonic acid and citric acid, or the above-mentioned component (d). It is adjusted to .0 to 4.5. When the pH of the composition exceeds 5, the storage stability is significantly reduced.

[0013]

INDUSTRIAL APPLICABILITY According to the present invention, a good bleaching effect is exhibited against plant stains and stains, and storage stability,
Particularly, an acidic type liquid oxygen bleaching composition having excellent storage stability at high temperatures and preventing decomposition of hydrogen peroxide can be obtained.

[0014]

【Example】

Examples 1 to 19 and Comparative Examples 1 to 4 Hereinafter, the present invention will be specifically described by showing Examples 1 to 19 and Comparative Examples 1 to 4 in Table 1, Table 2, Table 3 and Table 4 below. Are not limited to these examples. In addition,% in each example is% by weight.

The evaluation of each example was performed by the following methods. (1) Gas generation amount The bleaching agent composition shown in Table 1 was filled in a 500 ml Erlenmeyer flask with a stopper and a glass stopper (500 ml), and a glass tube with a stopper was used (a length of 100 cm or more for the stopper). The length below the pickpocket is 15 cm,
It has an inner diameter of 5 mm. ), Put it in a 50 ° C water bath for 5
After soaking for 0 hour, the amount of rise of the meniscus was defined as the amount of gas generated.

(2) Bleaching rate A bleaching agent having the composition shown in Table 1 was applied to 5 pieces of the bleaching agent-contaminated cloth prepared as follows, after applying 5 sheets per sample, and then the pH was adjusted to 1
After stirring for 10 minutes in a tap water of 20 ° C. adjusted to 0.5, the mixture was rinsed with tap water and dried, and the bleaching rate was calculated by the following formula.

[0017]

[Equation 1] The reflectivity was measured using a Z- # 80 colorimeter manufactured by Nippon Denshoku Co., Ltd.

Budo juice contaminated cloth A plain weave cotton cloth (# 100) is soaked in 100% grape juice (Dol) and soaked for 10 minutes. After that, it was naturally dried, and after pressing, a test piece of 5 × 5 cm was prepared and used for the experiment. Table 1 shows the results.

[0019]

[Table 1]Table 1: Example 1 2 3 4 5 6 7 Composition (% by weight) Hydrogen peroxide 5 5 5 5 5 5 5 Sodium polyacrylate *¹3 5 7 3 3 3 − Sodium polyacrylate *²− − − − − − 3 Maleic acid / acrylic acid − − − − − − − Copolymer *^Three Sodium polymaleate * ⁴ − − − − − − − AOS * ⁵ 3 3 3 2 5 10 5 CY-115 * ⁶ 0.5 0.5 − 0.5 0.5 0.5 − Polyethylene glycol *⁷− 2 − − 2 − − Polyethylene glycol *⁸− − 2 − − 5 −Alcohol ethoxylate * ⁹ − − − − − − − Ion-exchanged water Remaining Remaining Remaining Remaining Remaining Remaining Remaining pH 4.0 4.0 4.0 4.0 4.0 4.0 4.0 4.0 Gas generation rate (cm) 10 10 16 11 13 10 15 Bleach rate (%) 43 45 46 48 47 42 45 * 1) Average molecular weight: 15000 * 2) Average molecular weight: 8000 * 3) Average molecular weight: 70000 (Product name "Sokaran CP5" (manufactured by BASF) * 4) Average molecular weight: 5000 * 5) C₁₄Sodium α-olefin sulfonate / sodium hydroxymyristyl sulfonate = 6/4 mixture * 6) 1-Hydroxyethylidene-1,1-diphosphonic acid: trade name Feliox CY-115 (manufactured by Lion Corporation) * 7 ) Average molecular weight: 600 * 8) Average molecular weight: 2000 * 9) C₁₃Primary alcohol, ethylene oxide 9 mol adduct

[0020]

[Table 2]Table 2: Example 8 9 10 11 12 13 14 Composition (% by weight) Hydrogen peroxide 5 5 5 5 5 5 5 Sodium polyacrylate *¹− − − − − − − Sodium polyacrylate *²3 3 3 − − − − Maleic acid / acrylic acid − − − 3 3 3 3 Copolymer *^Three Sodium polymaleate * ⁴ − − − − − − − AOS * ⁵ 3 2 2 3 5 3 3 CY-115 * ⁶ 0.5 0.5 − 0.5 0.5 0.5 − Polyethylene glycol *⁷− 3 5 3 5 − − Polyethylene glycol *⁸− − − − − 5 −Alcohol ethoxylate * ⁹ − − − − − − − Ion-exchanged water Remaining Remaining Remaining Remaining Remaining Remaining Remaining pH 4.0 4.0 4.0 4.0 4.0 4.0 4.0 4.0 Gas generation rate (cm) 10 10 15 11 12 10 16 Bleaching rate (%) 44 45 48 43 45 46 46 * 1) Average molecular weight: 15000 * 2) Average molecular weight: 8000 * 3) Average molecular weight: 70000 (Product name "Sokaran CP5" (manufactured by BASF) * 4) Average molecular weight: 5000 * 5) C₁₄Sodium α-olefin sulfonate / sodium hydroxymyristyl sulfonate = 6/4 mixture * 6) 1-Hydroxyethylidene-1,1-diphosphonic acid: trade name Feliox CY-115 (manufactured by Lion Corporation) * 7 ) Average molecular weight: 600 * 8) Average molecular weight: 2000 * 9) C₁₃Primary alcohol, ethylene oxide 9 mol adduct

[0021]

[Table 3] Table 3: Example 15 16 17 18 19 Composition (wt%) Hydrogen peroxide 5 5 5 5 5 Sodium polyacrylate * ¹ − − − − 3 Sodium polyacrylate * ² − − − − − Maleic acid / acrylic acid copolymer * ³ − − − − − Sodium polymaleate * ⁴ 3 3 3 3 − C ₁₄ alkenyl sulfate − − − − 3 AOS * ⁵ 3 2 2 3 − C ₁₄ alcohol EO adduct * ¹⁰ − − − − − CY-115 * ⁶ 0.5 0.5 − 0.5 0.5 Polyethylene glycol * ⁷ − 3 5 3 − Polyethylene glycol * ⁸ − − − − − Alcohol ethoxylate * ⁹ − − − − − Ion-exchanged water Remainder Remainder Remainder pH 4.0 4.0 4.0 4.0 4.0 Gas generation rate (cm) 11 10 15 11 12 Bleach rate (%) 47 48 46 48 45 * 1) Average molecular weight: 15000 * 2) Average molecular weight: 8000 * 3) Average molecular weight: 70,000 (Product name "Sokaran CP5" (BASF Company Ltd.) * 4) Average molecular weight: 5000 * 5) C ₁₄ alpha-sodium olefin sulfonate / hydroxy myristyl sulfonic acid sodium = 6/4 mixture * 6) 1-hydroxyethylidene-over 1,1-diphosphonic acid: trade name Ferriox CY-115 (manufactured by Lion Corporation) * 7) Average molecular weight: 600 * 8) Average molecular weight: 2000 * 9) C ₁₃ primary alcohol, ethylene oxide 9 mol adduct * 10) Ethylene oxide of myristyl alcohol 12 mol adduct

[0022]

[Table 4] Table 4: Comparative Example 1 2 3 4 Composition (wt%) Hydrogen peroxide 5 5 5 5 Sodium polyacrylate * ¹ 2 − − − Sodium polyacrylate * ² − − 3 3 Maleic acid / Acrylic acid copolymer * ³ - 2 - - sodium polymaleic acid * ⁴ - - - - C ₁₄ alkenyl sulfates - - - - AOS * ⁵ - - 0.1 - C ₁₄ alcohol EO adduct * ¹⁰ - - - 2 CY-115 * ⁶ 0.5 − − − Polyethylene glycol * ⁷ − − − − − Polyethylene glycol * ⁸ − − − − Alcohol ethoxylate * ⁹ − 3 − − Ion-exchanged water Remainder Remainder Remainder pH 4.0 4.0 4.0 4.0 Gas generation rate (cm) 32 25 27 31 Bleach rate (%) 20 30 25 27 * 1) Average molecular weight: 15000 * 2) Average molecular weight: 8000 * 3) Average molecular weight: 70,000 (trade name "Sokaran CP5" (manufactured by BASF) * 4) Average molecular weight : 5000 * 5 ) C ₁₄ sodium α-olefin sulfonate / sodium hydroxymyristyl sulfonate = 6/4 mixture * 6) 1-hydroxyethylidene-1,1-diphosphonic acid: trade name Feliox CY-115 (manufactured by Lion Corporation) ) * 7) Average molecular weight: 600 * 8) Average molecular weight: 2000 * 9) C ₁₃ primary alcohol, ethylene oxide 9 mol adduct * 10) Myristyl alcohol 12 mol ethylene oxide adduct

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical indication C11D 3/37 C11D 3/37 17/08 17/08

Claims (1)

[Claims] 1. (a) Hydrogen peroxide: 2.0 to 10% by weight, (b) Anionic surfactant containing one or more double bonds in the molecule: 0.5 to 10% by weight, (c) Non-crosslinkable carboxylic acid polymer: 1.0 to 10
%, (D) Organophosphorus compound: 0 to 3.0% by weight, substantially no nonionic surfactant, and p
A liquid oxygen-based bleaching composition, wherein H is in the range of 2 to 5.