JPH03503292A - Activator for inorganic percompounds - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed description of the invention] Dance keyaki is fun 3 Nakokawa life 3 ↓ sword Inorganic retrograde compounds, especially superdiluted starch and sodium perborate and sulfur carbonate Solid compounds that dissolve in water and dissociate hydrogen peroxide, such as Jium hydrogen peroxide. has long been used as an oxidizing agent for disinfection and bleaching. In diluted solution, The oxidation effect of compounds such as - is greatly influenced by temperature. Example λ, b, alkaline In the case of +(, O, or peroxide in the bleaching solution, soiled! textiles should be heated to about 80°C. Bleaching is fast enough at temperatures above. At lower temperatures, the acid of inorganic decomposition compounds The effect of oxidation can be improved by adding so-called activators. such activators Some of them have been proposed in the literature. Among them, carboxylic acid anhydride is [] proposed in the US (DE 893 (] 49) and has been used in bleaching agents (DE] 912579). By adding these activators, the peroxide solution at 95"C Overheating allows you to achieve virtually the same effect as using the body alone at just 60°C. The bleaching effect of an oxide aqueous solution can be increased.

Obviously lower than 60℃ for energy saving in washing and bleaching process The operating temperature, especially the operating temperature of 45°C or lower to cold water temperature, has become important in recent years. .

However, at temperatures of this order the effectiveness of known activators clearly decreases. . Therefore, efforts have been made to develop activators that are more effective over this temperature range. However, clear results have not yet been obtained. The question posed by the present invention is The problem is low temperatures below 80°C, especially non-free products at temperatures in the range of about 15-45°C. It was to improve the oxidation and bleaching effect of the decomposition compound.

isatoic anhydride or its derivatives as an activator in this temperature range. The use of It was found that the bleaching and bleaching effects were considerably enhanced. The activator in question is compatible with the following formula: This is a corresponding compound.

Isatoic anhydride (R=H5n=o) is IH-benz [dr].

]3] This is the systematic name of oxazine-2,4-geo, which itself is known as an industrial product. Ru. Isatoic anhydride derivatives suitable as activators are those in which RlX and n are any of the following: It is a compound corresponding to formula (1) which is: R-methyl, ethyl, n-propylene Pyl, isopropyl, n-butyl, isobutyl, propenyl, futhynyl, ncro Hequinyl, phenyl or benzyl group.

X-methyl, methoxy, chlorine, bromine or so, 0 group; n=o, 1 or 2 Some of these compounds are known per se, are commercially available, or are known (DE499822 and Peilsteins) Hunt Boots Dell Organinoschen Hemi (Beilsteins Ha ndbuch der organischen Chemie) Volume 27, series Serial number 4298, main part and 1st to 4th supplements).

Among these compounds, R or methyl, ethyl, n-propyl or isobutyl groups Of course, compounds in which the benzene ring is not substituted (n-O) are preferred. Preferably, unsubstituted isatoic anhydride (R=H.

n = O) is particularly preferred.

In the method of the invention, the oxidation effect of inorganic decomposition compounds at low temperatures is particularly increased. Desired applications such as jaW, products, hair or hard surface bleaching, organic or Isatoic anhydride and its derivatives as activators in the oxidation and disinfection of inorganic intermediates Can be used as The properties of most of these activators are similar to that of conventional carboxylic acid anhydrides. It is far superior to the best one.

The application of the present invention is to use hydrogen peroxide and and isatoic anhydride or its derivatives to react with each other. It consists of In an alkaline aqueous solution, both reactants come into contact with each other. Such a condition is established when the

Such conditions can vary within wide limits depending on the application. Sub game C1 pure In addition to pure aqueous solutions, for example when used for disinfection or oxidation of intermediate products, water and Mixtures with suitable organic solvents can be used as reaction medium. The pH value of the reaction medium is Depending on the application, it can be used in a wide range from a weakly acidic range (pH 4) to a strongly alkaline range (pH 13). You can select within a certain range. The alkaline range of pH 8-11 is suitable for activation reactions and This is preferred because it is particularly advantageous for the stability of the resulting decomposed compound. For this reason, the present invention The activator is sodium perborate or It is also preferred to use sodium carbonate with hydrogen peroxide. other appropriate degenerations Examples of compounds are phosphate hydrogen peroxide and urea peroxide. Depending on the case, After an activation reaction with suitable additives, the pH value of the medium is shifted, especially with acids. It may be preferable to shift to the sexual range. The amount of decomposition compound used is generally The solution contains 10 ppm to 10% active oxygen, preferably 50 to 5000 ppm active Select to contain oxygen. The amount of active agent used will also be influenced by the application.

Depending on the degree of activation desired, from 0.03 to 1 activator per mole of inorganic decomposition compound. It is used in amounts of 0.1 to 0.5 mol, preferably 0.1 to 0.5 mol, but in certain cases it may be lower. May be used in larger or smaller amounts.

Isatoic anhydride or derivatives thereof according to the invention in pure form or, where appropriate, For example, to increase storage stability, tablets, granules or finely divided coated forms (so-called used for active use in any of the special forms such as Prill, good. Granular forms produced by cohesive granulation are of particular importance in this regard. life Solutions or dispersions in organic solvents containing sex agents are suitable for mechanical metering use.

The isatoic anhydride or derivative thereof of the present invention can be activated with suitable compounds and cases. other ingredients necessary for the desired bleaching or oxidation process, such as pHJAI moderators and Preferably, it is used in the final formulation in the form of a mixture with stabilizers for degrading compounds. stomach Satoxylic anhydride and/or its derivatives can be added to I-[1]. 7 may exist. The optimum conditions are directly established during dissolution of the formulation, so that Mixing the compound with other additives makes it easier to apply and achieve the user's desired results. It becomes possible to get more safely. ), the invention also relates to formulations of this type. do.

In the case of laundry, essentially the components of common detergents and bleaches and the properties 1.8 of the present invention Agents may be combined. It is thus particularly suitable for processing textile products at -C low temperatures. formulations that can be used in several ranges up to the standard and conventional boil cleaning ranges. It is possible to prepare

In addition to suitable compounds and activators, the basic components of the type of cleaning agent and bleaching agent in question are The ingredients are bilters and surfactants. other typical auxiliaries and additives as appropriate; For example, anti-redeposition agents, peroxide stabilizers, electrolytes, optical brighteners, enzymes, perfume oils, foam stabilizers Agents and conti/joners may be present in the formulations of the present invention.

Examples of typical builders are condensed phosphates, alkali silicates, alkali carbonates salts, salts of aminocarphonic acids such as nitrilotriacetic acid, hydroquinethane/posho Salts of polyposonic acids such as citric acid or polysaccharides such as citric acid or polyacrylic acid. Salts of carbonic acids and insoluble aluminum silicates of theolite NaA and NaX types It is sodium sodium.

Suitable surfactants are especially surfactants of the nonionic and synthetic anionic type.

Examples of nonionic surfactants are long chain alcohols or alkyl phenols and alcohols. polyethylene glycol monoalkyl made from Borie/Nglycol monophenyl ether and long chain alkyl glycone It is.

Anionic surfactants are primarily long-chain sulfates and sulfonates, e.g. alkylbenzene sulfonate, fatty acid, z-stersulfonate, alkane sulfonate, 4-lefin sulfonate, fatty alcohol sulfate and polyethylene It is a sulfate salt of nglyfur monoether. Soaps and long chain acylcyanami You can also use salt.

Typical cleaning and bleaching agents of the present invention include, for example, the following groups: Anionic and i' or nonionic surfactants 05-20% by weight, preferably 5 ~15% by weight polycondensed phosphate, alkali silicate, alkali carbonate, silicate acetate Builders from the group consisting of sodium aluminum and mixtures thereof 05-60% by weight, preferably 5-40% by weight Salts of aminocarboxylic acids, polynas Virta from the group consisting of salts of fonic acids, salts of polycarphonic acids and mixtures thereof -0 to 20% by weight, preferably 0.5 to 8% by weight of inorganic percompound 2 to 35% by weight, preferably 1. < is 5-30% by weight of isatoic anhydride and/or its 03 to 20% by weight, preferably 1 to 10% by weight of derivatives of common auxiliaries and additives. Additives and water remainder In addition to combined cleaning and bleaching agents, peroxide-containing or peroxide-free The activator of the invention for laundry purposes as a formulation used as an additive for detergents. You can also manage. They are active agents or mixtures of active agents and compounds and optionally other auxiliaries and additives, in particular stabilizers, pH regulators, enhancers. Essentially contains a viscous agent and a surfactant.

A typical bleaching additive of the present invention has, for example, the following composition.

Inorganic suitable compounds 5-50% by weight, preferably 15-35% by weight of isatoic anhydride and/or its 2-30% by weight, preferably 5-25% by weight of derivatives of peroxide stabilizers 0-5% by weight, preferably 01-3% by weight pH regulator 0-40% by weight, preferably 5-30% by weight of other common auxiliaries and additives remainder In addition to clouding compounds and active agents, hard surface cleaning formulations also contain certain surfactants. , Birku, and in the case of polishing and polishing, it contains an abrasive component. These formulations Since they are often applied at room temperature, the use of the activators of the present invention has a significant impact on bleaching and disinfection effects. It has a particularly useful gongdong.

In the case of disinfectants, the formulations are particularly important. That's in this case This is because safety during use must satisfy stricter requirements. activator and In addition to suitable mineral compounds, disinfectants based on the active agents of the present invention are generally used as pond aids. agents and additives such as pH regulators, stabilizers and surfactants. special place In some cases, disinfectants contain already very widespread turbid compounds activated against certain microorganisms. It may further contain special germicidal agents to promote a germicidal effect.

Typical disinfectants of the invention include, for example, mono-inorganic percompounds having the following composition: 5 to 40%, preferably 10 to 20% isa-1-acid anhydride and/or 2-40% by weight of its derivatives, preferably 5-20% by weight of peroxide stabilizers 0-5% by weight, preferably 01-3% by weight surfactant 0.1-20% by weight, preferably 0.2-5% by weight of other auxiliaries and additives remainder However, the use of the active agents of the present invention is not limited to the above-mentioned or other types of use. It is not limited. Therefore, depending on the cost, this may be a more preferable method. For example, in the industrial field, the amount of each drug used is generally important. It is.

Figure 1 The abbreviations shall have the following meanings and shall be used: ・AS-acrylic acid CMC-carboxymethylcellulose E D T A-Tetrasodium salt of ethyleneaminetetraacetic acid EI)'FMP= Ethylenediaminetetramethylenephosphonic acid hexasodium salt (peroxide stabilizer ) EO-Ethylene Oquinde r(T', C-hydroxyethylcellulose MA-maleic anhydride 1. Composition of phosphate-containing bleach laundry detergent in powder form (wt%) Soap (C+t-+R) 1, 5 dodecyl Sodium benzene sulfonate 9.0 fat Alfur Etchinle cc+t-18+1OEo) 3.5 Sodium triphosphate 20.0 Sodium silicate (3,2) 5.0 Theorai 1-NaA 15. OEDTMP O, 3MA-AS Fuvolimer (60:40) 1.5 Sodium perborate - hydrated Product 18.0 Isatoic anhydride 　　　　　30 Brightener, fragrance, enzyme, carboxymethyl cellulose, N a, S04 and water Remaining cleaning temperature 20-9 Excellent bleaching results are obtained using this detergent at concentrations of 5 to lo9/C at 5°C. Obtained.

2. Test of bleaching ability on various test stains on textile products Under the following conditions, Phos-7 5-(・Using a non-containing cleaning agent) (Atlas 5 standard Launderometer) C test was conducted. Ta; Liquid volume: 250m1 Textile products/Filled fiber products (white cotton) 639 test textile products 2.19 Water hardness 10’Gh (German hardness lf) Temperature 30 °C is 40'C cleaning time 30 minutes (heating time 31.;) ( 3°C/min) Rinse 3x30 seconds Cleaning agent composition (wt%) Alkylhensensulfonic acid sodium salt 7 tallow alcohol + 5 E 0 5, 5Na, Co3 12 Sodium silicate, 3.2) 3.3 Light NaA 28EDTA 　　　　　　　　　　　　O,3 Sodium perborate tetrahydrate 28CM C+HE Cl・5 N a, S O4 and water Remaining amount used; Cleaning agent 7.169/C activator 1413m9/'Q or l, 26 mmol/Q The test was rated 1- by standard reflectance measurement of dry textile products. Below The results shown in the table below are B a SO measured at a wavelength of 460 nm, - The conventional reflectance values for 100 and 2 are shown in %. A relatively high value is In contrast, it shows bright textile products.

30℃(J test) Activator Usage Amount Red wine, red currant, black tea adhesion How many red wines per IQ Adhesive cotton Adhesive cotton Anti-wrinkle cotton Polyester/No cotton 46 ．． 1 51.8 33.9 54.2 Isatoic acid 143m g 52.6 55.4 41.0 58.6 Anhydride 1.2 6 mmol 55.1 59.2 44.5 59.1 Lid Ruic acid 143mg 47.5 51.3 35.7 53 ．． 7 Anhydride 1. ．． 26 mmol 47.7 53.8 36.0 54.1:] Huccinic acid 143mg 47.3 54.8 36.6 53.8 Anhydride 1.26 mmol 47.7 53 ,7 36,1 53.8 First? - Clothing test at 40°C Activator Amount used: Red wine, red currant, black tea adhesion, red rfisi adhesion, 1. , (f3. O-Ichikant'4*t@('H?f*ffl-p51A*3) 41x-x-r+1. -/: without cotton 44.5 38,0 54.4 51.3 tonic acid 143mg 49.6 45.5 58.2 53.6 Anhydrous l, 26 open o1 5 2.7 47,7 60,7 53.3 Phthalic acid], 43m g 45.0 39.2 55.2 50.8 Anhydrous 1,26 open o1 45.8 41,1 54.8 51.4 Huccinic acid! 43B 45.0 40.0 54.8 5 0.4 Anhydride 1.26++u++ol 44.6 39.2 54 ．． 8 503 At any temperature, perborate exhibits conventional anhydride activity. Better than drugs!・The standard reflectance value is that it is extremely activated by acid anhydrides. It is clear that

Similarly good results were obtained when N--methylisatoic anhydride was used.

3. Test of bleaching ability on textile products under US washing condition F Vv’hirlpoo using a detergent containing Fe River (T1de) The test was carried out using a propeller washing machine.

Liquid volume 2 65Q Textile products: Filled fiber products (white cotton) 2.3 kg-) - 8 test stains ( 2.19 cloth for each) Water hardness: 56°Gh (CaCO399mg, C a: Mg=3: 1) Cleaning time: 14 minutes Temperature:　　　　　　　24°C (Night cleaning) Amount used (per IQ) / Cleaning agent 1 ．． 35y + perborate-aqueous phase 67.5mg Ten active agent 54mg As in Example 2, the results were evaluated by conventional reflectance measurement. Table 3 shows various tests The test results obtained in the case of soiling are compared with conventional activators (average of 4 tests). average value)・ The second wave Activator　　　　Red currant　Red wine several necks　Black tea attached　　100 cotton with red wine attached Anti-wrinkle cotton Anti-wrinkle cotton polyester/cotton perboric acid Salt and live 40.5 36.9 27.1 47. 7 No sex drugs isatoic acid Anhydride 45.7 39.6 33.0 50. 3 Teto Uase Chill J Chire 42,7 38.0 3i, 1 48.7 Sulkhov Ryo-Kol 4], 8 38.5 30.3 4 8.9 ester Na salt This result indicates that isatoic anhydride can be used for tableware under US cleaning conditions. show.

Similar increases in the oxidation effectiveness of inorganic compounds are achieved in other applications.

4. Shelf life test The active agent was stored in a mixture with a powdered phosphate-free detergent. The mixture is It contained 3% active agent in pure form or in consolidated granular form.

The cleaning agent had the following composition (% by weight):

Soap 1,5 Sodium Rubensene Sulfonate Thorium 8.0 Fatty Alcohol Ethquinate 4, ONa, Co3 　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　 3. 5 Zeolite N a A, 25 Hydroxy/Ethanedipho Sulfonate (Na salt) 0.3MA-AS copolymer (60:40) 5% Sodium borate Chillcellulose, Na, SO2 and water Remainder 1) E 30 11 9 98 based on activator granules in powder form pure activator and binder as binder. Manufactured from Luhoquin/Mesenlucerol. The granules contain 94% by weight of active substrate. I was reading.

Weathering test of a mixture containing the active agent in granular form at 30°C/80% relative humidity I put it in a lined bag and stored it on the plane. Experiment by putting the pond mixture in a bag without lining. Stored in room 1. In both cases, initially and after storage for 4 and 8 weeks, The peracid formed when the mixture is dissolved in water under standard conditions was initially and iodine measured. - Measured by

Table 3 assumes that the production of filtrate acid in the early stage of storage is 100%, and shows the number of Show the result of the value. The excellent stability of isatoic anhydride is evident under both storage conditions. It is.

Table 4 Active agent Peracid production (%) O weeks After 4 weeks After 8 weeks after the interval Succinic anhydride 100 30 0 Phthalic anhydride 100 19 0 Isatoic anhydride 100 8 5 67 Fuccinic anhydride (granular) 100 16 0 F Tallic anhydride (granular) 100 0 - Isatoic anhydride (granular) 100 88 585 Disinfectant Composition (wt%) Sodium perborate-aqueous phase 120 Isatoic anhydride 12 ON ay COs 15 -0N84PtO+ 25.0EDTMP 1.2 Nonylphenol ethoxylate (9EO) 1.3 NatsOa and water The remainder is dissolved in water at room temperature After that, the powdered disinfectant was used in the form of a disinfectant bath. Approximately 4g/(l usage For this concentration, the required disinfection time was less than 60 minutes.

6. Test for groove-extinguishing effect German Society of Hygiene and Microbiology (Deutsche Ge5ellschaft) furHygiene und Mikrobiology (DGH M) Guidelines for the testing and evaluation of chemical disinfection methods (“R1ch tlinien fur die Prufung und Bewertu ng chemistry design This test was carried out by a so-called quantitative suspension test based on carried out. In this test, a bacterial suspension (107 to 10' Thoroughly mix 10ml of diluted disinfectant at 20'C. 5.15.30 and 60 After a contact time of seconds, remove 0.1 ml of the resulting mixture and add 10 ml of culture medium. was inoculated. Incubate these cultured bacteria at 37°C (72h). It can be determined whether there are bacteria that can multiply.

Test solution: the cleaning agent of Example 2 in water with a hardness of 17°GH adjusted to pH 10 Usage amount, cleaning agent 10g/Q Activator 150.300 or 600m9/Q Temperature: 37°C Culture medium dicasein pebtone/soybean flour peptone/agar Four types of test bacteria were used. The results for each case are shown in the table below as the maximum failure time (minutes).

1st Activator Concentration Staphylococcus aureus Escherichia coli Pseudomonas aeruginosa Candida ←q/ Q’） 60 >60 >60 Isatoic acid 300 5 5 5 5 anhydride 150 5 5 >60 6ON-methyl 600 5 15 30 5 Isatoic acid 300 15 30 60 15 Anhydride 150 60 >60 >60 >60 These results clearly (and do not reflect) the excellent activation effect of the activator of the present invention. ing.

international search report international search report EP 8900210 S^　　　27010

Claims (13)

[Claims] 1. General formula: ▲Contains mathematical formulas, chemical formulas, tables, etc.▼ [wherein R is H, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, propenyl, butenyl, cyclohexyl, phenyl or benzyl Represents any substituent, X is H, methyl, methoxy, chlorine, bromine or SO3 (2) selected from the group consisting of groups, where n is either 0, 1 or 2; ] Activity of isatoic anhydride for inorganic percompounds in oxidizing, disinfecting and bleaching solutions Use as an agent. 2. n in the general formula is 0, and R is H, methyl, ethyl, n-propyl or i Use of isatoic anhydride according to claim 1, which is a sopropyl group. 3. Use according to claim 1 of unsubstituted isatoic anhydride. Claims 1 to 4. The active effect mainly appears in an aqueous solution at a pH value of 4.8 to 11. Uses described in any of Section 3. 5. 1 to 0.03 mol to activate 1 mol of active oxygen from the inorganic percompound, Any of claims 1 to 3, preferably using 0.5 to 0.1 mol of activator. Uses listed above. 6. General formula: ▲Contains mathematical formulas, chemical formulas, tables, etc.▼ [wherein R is H, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, propenyl, butenyl, cyclohexyl, phenyl or benzyl Represents any substituent, X is H, methyl, methoxy, chlorine, bromine and SO3 (2) selected from the group consisting of groups, where n is either 0, 1 or 2; ] It is characterized by containing isatoic anhydride as an activator, and contains inorganic percompounds and active oxidizing, bleaching or or disinfectant formulations. 7. n in the general formula is 0, R is H, methyl, ethyl, n-propyl and i Claim 6 contains isatoic anhydride which is any of the sopropyl substituents. formulation. 8. 7. A formulation according to claim 6 comprising unsubstituted isatoic anhydride. 9. Inorganic percompounds include sodium perborate, sodium percarbonate, and mixtures thereof 9. A formulation according to any of claims 6 to 8, selected from the group consisting of: 10. 1 to 0.03 mol, preferably 0.5 to 0.1 mol per mol of inorganic percompound 9. A formulation according to any of claims 6 to 8 comprising molar of active agent. 11.0.5-20% by weight, preferably 5-15% by weight of anions and/or is a nonionic surfactant, 0.5 to 60% by weight, preferably 5 to 40% by weight of condensation Phosphate, alkali silicate, alkali carbonate, sodium aluminum silicate 0 to 20% by weight, preferably is 0.5 to 8% by weight of aminocarboxylic acid salts, polyphosphonic acid salts, polycarboxylic acid salts, builder from the group consisting of salts of phosphoric acids and mixtures thereof; 2-35% by weight, preferably 5-30% by weight of inorganic percompound, 0.3-20% by weight %, preferably from 1 to 10% by weight of activator, the remainder common auxiliaries and additives. 7. A combination cleaning bleach as claimed in claim 6, comprising water and water. 12.5 to 50% by weight, preferably 15 to 35% by weight of inorganic percompound, 2-30% by weight, preferably 5-25% by weight of active agent, 0-5% by weight, preferably is 0.1-3% by weight peroxide stabilizer, 0-40% by weight, preferably 5-30% by weight. % pH adjuster, balance other common auxiliaries and additives 7. A bleaching additive according to claim 6, comprising: 13.5 to 40% by weight, preferably 10 to 20% by weight of inorganic percompound, 2-40% by weight, preferably 5-20% by weight of active agent, 0-5% by weight, preferably is 0.1-3% by weight peroxide stabilizer, 0.1-20% by weight, preferably 0.2 ~5% by weight surfactant, balance other auxiliaries and additives A disinfectant according to claim 6, comprising: