JPH01272699A - Bleaching agent composition - Google Patents

Abstract

PURPOSE:To obtain a composition, containing a substance capable of releasing hydrogen peroxide in an aqueous solution and aluminosilicate subjected to ion exchange with heavy metal ions and improved in bleaching effects while sustaining advantages of an oxygen based bleaching agent, such as a wide scope of application without offensive smell. CONSTITUTION:The objective composition containing (A) a substance capable of releasing hydrogen peroxide in an aqueous solution (preferred example; hydrogen peroxide, sodium percarbonate and sodium perborate monohydrate) and (B) an aluminosilicate (preferred example; A type, X type and Z type zeolites) subjected to ion exchange with heavy metal ions, such as preferably divalent Co or Mn. Furthermore, the blending ratio of both is preferably 0.1-20 pts.wt. component (B) based on 100 pts.wt. component (A).

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a bleach composition with enhanced bleaching effect, which is used for various purposes such as household use and industrial use.

[Conventional technology]

There are two types of bleaching agents: reducing bleaching agents and oxidizing bleaching agents. Oxidizing bleaching agents are widely used because they are more effective. Oxidizing bleaches are further divided into chlorine bleaches and oxygen bleaches, but chlorine bleaches discolor and fade the material being treated, so they cannot be used on colored and patterned clothing, and they have a unique odor. There are disadvantages such as having On the other hand, oxygen bleach can be used in a wider range of applications than chlorine bleach.
It is superior in that it does not have the characteristic odor of chlorine bleach and is easy to use.

However, among oxygen bleaches, hydrogen peroxide, percarbonate, perborate-hydrate, and hydrogen peroxide adducts such as pyrophosphate, citrate, sodium sulfate, urea, and sodium silicate, Peroxides that release hydrogen peroxide in an aqueous solution have inferior bleaching properties compared to chlorine bleach, and cannot achieve sufficient bleaching effects with short bleaching treatments, especially at low temperatures. It has the disadvantage that it requires quite a long treatment time to obtain the desired effect.

For this reason, TAED has traditionally been used for hydrogen peroxide and peroxides.
(tetraacetylethylenediamine), TAGtJ (tetraacenal glycoluril), PAG (pentaacetylglucose), and bleach activators such as heavy metals (JP-A-52-76281, JP-A-59-120698, etc.)
The bleaching effect has been enhanced by using it in combination with
The activation effects of these conventional bleach activators are not sufficient, and therefore, oxygen bleaches have not yet achieved satisfactory bleaching effects compared to chlorine bleaches.

[Problem to be solved by the invention]

Therefore, an object of the present invention is to provide an oxygen-based bleach composition with high bleaching effect.

[Means to solve the problem]

The present invention was made based on the knowledge that the use of aluminosilicate, which has been ion-exchanged with heavy metals such as divalent cobalt and manganese, as a bleach activator significantly increases the bleaching strength of oxygen-based bleaches. be.

Thus, the present invention provides a bleach composition containing a substance that releases hydrogen peroxide in an aqueous solution and an aluminosilicate ion-exchanged with a heavy metal.

The substance that releases hydrogen peroxide in the aqueous solution used in the present invention may be any substance that releases hydrogen peroxide when dissolved in water. For example, one or more of hydrogen peroxide, percarbonate, perborate, and hydrogen peroxide adducts such as birophosphate, citrate, sodium sulfate, urea, and sodium silicate are preferably used. However, it is particularly preferable to use hydrogen peroxide, percarbonates such as sodium percarbonate, and perborates such as sodium perborate hydrate.

The aluminosilicates ion-exchanged with heavy metals used in the present invention include those in which part or all of cations such as hydrogen, sodium, and potassium that can be exchanged with other cations in the aluminosilicates are replaced with heavy metals. It will be done.

The raw material aluminosilicate used for producing such aluminosilicate is prepared by adding a sodium silicate aqueous solution or a caustic soda aqueous solution to a sodium aluminate aqueous solution, stirring for a predetermined period of time, allowing the reaction to occur, and then converting the reaction product. An example is one produced by separating by suction filtration, washing with ion-exchanged water, and air drying.

In the above synthesis reaction, various aluminosilicates can be synthesized by changing the concentration of sodium aluminate, sodium silicate, reaction time, and reaction temperature, but A-type zeolite, X-type zeolite, and Y-type zeolite are preferably used. Ru. As the raw material aluminosilicate, those with various particle sizes can be used, but it is preferable to use those with an average particle size of 0.1 to 5 μ, preferably 1 to 2 μ. may be used alone or in combination of two or more.

Examples of heavy metals exchanged with cations such as sodium in the aluminosilicate include chromium, manganese, iron, cobalt, nickel, copper, and zinc, and divalent cobalt and manganese are preferably used. Note that these heavy metals may be used alone or in combination of two or more.

The aluminosilicate ion-exchanged with heavy metals used in the present invention is obtained by dispersing the raw material aluminosilicate in water, then adding a water-soluble salt (hydrochloride, etc.) of the heavy metal thereto,
It can be produced by a method such as exchanging sodium cations and the like in the raw material aluminosilicate with heavy metal ions. In this case, 0.1% or more, preferably 30% or more of the cation exchange sites of the aluminosilicate are ion-exchanged with heavy metals.

The amount of the above-mentioned heavy metal ion-exchanged zeolite with respect to peroxide is 0.1 per 100 parts by weight of peroxide.
~20 heavy backgrounds are appropriate, particularly preferably 1~10
Parts by weight. If it is less than 0.1 part by weight, the bleaching blade will be weak;
This is because even if the amount exceeds 0 parts by weight, the bleaching blade will reach saturation, which is not economical.

The bleaching agent of the present invention has essential ingredients, but in addition to these, the following ingredients include surfactants, binder materials, enzymes, fragrances,
The bleach can be used in any form, and the substance that releases hydrogen peroxide is a powder mixture of a hydrogen peroxide adduct with a particle size of 150 to 2000 μm and the above aluminosilicate; These can be widely used in the form of granules and the like.

Furthermore, the bleachable composition of the present invention can be suitably blended into bleaching detergents. In this case, the bleaching detergent can be prepared by a conventional method by adding appropriate other known components shown below to the composition of the present invention. For example, it can be prepared by adding inorganic/organic builders, anionic/nonionic surfactants, enzymes, fragrances, pigments, fluorescent agents, etc. here,
Inorganic and organic builders include sodium sulfate, sodium silicate, sodium tripolyphosphate, ethylenediaminetetraacetic acid, nitrotriacetic acid,
1-hydroxyethane-1,1=diphosphonic acid and its salts, etc. As anionic surfactants, sulfonates and sulfates having an alkyl group having about 8 to 22 carbon atoms, and There are alkylbenzene sulfonates having 9 to 15 carbon atoms, α-olefin sulfonates having about 8 to 22 carbon atoms, and fatty acid soaps having about 10 to 22 carbon atoms. Preferred salts are alkali metal salts, particularly preferred are sodium salts. The nonionic activator has a linear or branched argyl group having about 6 to 12 carbon atoms, and has 5 to 25 ethylene oxides per 1:f alkylphenol.
Ethylene oxide condensation of an aliphatic alcohol in which 5 to 30 moles of ethylene oxide are condensed to 1 mole of a linear or branched aliphatic alcohol having about 8 to 22 carbon atoms. A nonionic surfactant with the trade name of "Pururo;Tsuta" obtained by condensing propylene oxide with propylene glycol and further condensing it with ethylene oxide.
There are 18 aliphatic mono- or jetanolamides, amine oxides having alkyl groups of about 8 to 24 carbon atoms, and methyl and/or ethyl groups.

In addition, enzymes that can be incorporated into bleaching detergents include hydrolytic enzymes that promote the addition and removal of water, oxidoreductases that promote redox, and enzymes that transfer groups from one molecule to another.
Transferase, which alters dirt and promotes its removal; gauze, which breaks down intermolecular bonds and decomposes dirt, and promotes removal; lyase, which isomerizes molecules and chemically alters dirt, promoting removal. Enzymes can be used, and among these, hydrolytic enzymes are preferred, and among the hydrolytic enzymes, proteases are especially preferred. Specific examples of proteases include serine protease, pepsin, trypsin, chymotrypsin, collagenase, keratinase, esterase, subtilisin, papain, carboxybebutitase A and B.
, aminobebutitase. Preferred proteases are serine proteases. These include, for example, "Alcalase": Novo Industries "Esperase"; Ninovo Industries "Virobrase"; Nagase Sangyo; "Maxatase": Gist Procades rALP-
2J: Meiji Seika ■ "Sverase": Easily available as a commercial product from Pfizer and others. When blending an enzyme, the blending amount in the bleaching detergent is preferably in the range of 0.01 to 5% by weight.

In addition, when blending the composition of the present invention into a bleaching detergent, an aluminosilicate ion-exchanged with a heavy metal can be prepared in granular form. In this case, 100 parts by weight of an aluminosilicate ion-exchanged with a heavy metal is mixed with 5 to 200 parts by weight of one or a mixture of two or more binders having fluidity at 5 to 60°C, preferably 10 to 40°C. 10-
It is preferable to granulate using 100 parts by weight.

Here, the binder is one or two selected from nonionic surfactants, polyethylene glycol, polypropylene glycol, liquid paraffin, and higher alcohols, which have fluidity at 5 to 60°C, preferably 10 to 40°C.
Mixtures of N or more may be used. For example, preferred nonionic surfactants include the following (A) to (F):

(A) Polyoxyethylene alkylene or alkenyl ether having an alkyl group or alkenyl group having an average carbon number of 10 to 20 and to which 1 to 20 tons of ethyl L,... oxide is added (B) Average It has an alkyl group having 6 to 12 carbon atoms, and has 1 to 12 carbon atoms.
Polyoxyethylene alkylphenyl ether (C) with 20 moles of ethylene oxide added, average carbon number 10
~20 alkyl or alkenyl groups L, 1~20
Polyoxypropylene alkyl or alkenyl ether to which mol of propylene oxide has been added (D) Polyoxybutylene alkyl or alkenyl ether having an alkyl or alkenyl group with an average carbon number of jO to 20 and to which 1 to 20 mol of butylene oxide has been added (E) A nonionic activator having an alkyl group or alkenyl group having an average carbon number of 10 to 20 and adding a total of 1 to 20 moles of ethylene oxide and propylene oxide or ethylene oxide and butylene oxide, where ethylene oxide 7/propylene oxide or butylene oxide ratio is 0.1/9.9-9.9
/ 0.1.

(F) Copolymer 2 of ethylene oxide and propylene oxide, or copolymer of ethylene oxide and butylene oxide.

Using these binders 4, the average particle size is 300μ by a conventional method.
It is extremely convenient to handle the granular material.

〔Effect of the invention〕

Although the mechanism of action of the present invention is unknown, using an aluminosilicate that has been ion-exchanged with heavy metals as an activator can efficiently activate substances that release hydrogen peroxide in an aqueous solution, and can effectively activate oxygen-based bleaches. A high bleaching effect can be obtained while retaining the advantages.

Next, the present invention will be specifically explained with reference to examples, but the present invention is not limited to the following examples.

Reference Example 1 118g of aluminosilicon gold layer sodium aluminate (Showa Light Metal H-10),
An aqueous solution prepared by mixing and dissolving 74 g of a 30% sodium silicate aqueous solution and 6 g of caustic soda in 50 l of ion-exchanged water was added.

After stirring and reacting at the predetermined temperature and time shown in Table 1, the product was filtered, washed with ion-exchanged water, and air-dried to obtain three types of aluminosilicates.

Table 1 Reference Example 2 1 Children's factory aluminum alloy at 25℃,
Dissolve 40 g of anhydrous cobalt chloride in 21 ml of ion-exchanged water,
While stirring, the aluminosilicate synthesized in Table 1 and 200 g of commercially available synthetic zeolite were gradually added, and the mixture was stirred at room temperature for 6 hours. Thereafter, filtration was performed using 5C filter paper, and the product was thoroughly washed with ion-exchanged water at 40°C. Thereafter, it was dried at 110° C. for 1 hour to obtain the desired product.

The same procedure was carried out when anhydrous manganese chloride was used instead of anhydrous cobalt chloride.

Table 2 shows the obtained aluminosilicate (hereinafter referred to as activator), the raw material aluminosilicate, the heavy metal used, and the ratio of cations in the aluminosilicate exchanged with heavy metal.

The zeolites A, X and Y have the following properties.

Table 2 Example 1 Bleaching containing sodium percarbonate or sodium perborate and the activator shown in Table 2 in the weight ratio shown in Tables 3 and 4. After each bleaching agent composition was prepared, the following bleaching effect test was conducted using these bleaching agent compositions.

The results are shown in Tables 3 and 4.

A plain-woven cotton cloth (#100) made by Hoshi Wataruguo was washed in a washing machine at 30 times the bath ratio at 50° C. for 15 minutes using a commercially available detergent (Tofub ■), and then dehydrated for 5 minutes. Washing and dehydration were performed again in the same manner. Next, overflow rinsing was performed for 15 minutes, followed by dehydration for 5 minutes. The overflow and dehydration operations were repeated a total of 5 times, and then air-dried to obtain a pretreated cloth.

Next, a 0.5% black tea solution was boiled for 5 minutes, and the above pretreated cloth was immersed in the solution at a bath ratio of 30 times, boiled for 30 minutes, left at 40°C for 30 minutes, and then air-dried. (black tea cloth).

The bleach compositions of Examples and Comparative Examples were added to tap water at 20°C to a concentration of 0.5%, and a black tea cloth was immersed in the solution at a bath ratio of 100 times for a predetermined period of time (30 minutes). I left it alone. The thus treated test cloth was sequentially dehydrated for 1 minute, overflow rinsed for 1 minute, and dehydrated for 1 minute in a washing machine, and then dried by ironing to obtain a bleached cloth.

The reflectance of the pretreated cloth, black tea cloth, and bleached cloth was measured using a colorimeter (Σ80, manufactured by Nihon Heavy Industries Co., Ltd.), and the bleaching effect was calculated using the following formula.

Bleaching effect (%) = Reflectance of pre-treated cloth - Anti-black tea cloth! R Degree Example 2 The bleaching detergent shown in Table 5 was added to water with a hardness of 3° DH at 25°C to a concentration of 0.8%, In this, bath ratio 5
Soak a tea cloth in 0x and leave it for 30 minutes.

Then, with a clean cotton knitted cloth, the temperature was 5.25℃ and the hardness was 3℃.
H water was added to adjust the detergent concentration to 0.15%, which was 30 times the bath ratio.
ing) for 10 minutes at a rotational speed of 12 rpm. The test cloth thus treated was sequentially dehydrated for 1 minute, overflow rinsed for 1 minute, and dehydrated for 1 minute in a washing machine, and then dried with an eye dryer to obtain a bleached cloth.

-Abduction-wash side one group-(weight%) L A S -Na” 7
AOS-Na” 17
Zeolite (Type 4A) 15 Sodium silicate 10 Sodium carbonate 10 Chinovar CB
S-X Re O12 enzyme (alcalase 2
．． OT) ” 0.4 water
5. Sulfur 1 and Muni L
-11 remaining 5 parts *1) Sodium linear alkylbenzene sulfonate whose alkyl group has 12 carbon atoms *2) Sodium C14-11 α-olefin sulfonate

Claims (1)

[Claims] A bleach composition comprising a substance that releases hydrogen peroxide in an aqueous solution and an aluminosilicate ion-exchanged with a heavy metal.