TW387938B - Oxygenic bleaching composition - Google Patents

Description

V. Description of the invention Γ) Background of the invention The present invention relates to oxygen bleaching compositions used in clothing, kitchens, and hard surfaces, and more particularly, to liquid or powder oxygen-based bleaching compositions with high bleaching power. Among them, the organic peracid precursor contained therein is stable after long-term storage. ‘Oxygen-based bleach is a mainstream bleach for laundry because it can be used on leveling and patterned clothing. On the other hand, the bleaching power of this bleaching agent is worse than that of chlorine-based bleaching agents. Therefore, improving this situation is the first problem to be solved by this technique. Many studies have been performed to improve the bleaching power of bleaching agents, one of which is the use of organic peracid precursors. According to this method, stains are decomposed by organic peracids (formed by the reaction of organic peracid precursors and hydrogen peroxide in the washing liquid) with higher bleaching power. As for the peroxides used here (those that form hydrogen peroxide in the lotion), perboric acid and the like are widely used in powdery bleaching agents or heavy detergents with bleaching effect. Hydrogen peroxide is mainly used in liquid bleach. In addition, examples of the organic peracid precursor include tetraethylamidinoethylenediamine (TAED), glucopentaacetate (PAG), and sodium nonylbenzenebenzenesulfonate. Printed by the Shellfish Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs (please read the note on the back before filling out this page) because these organic peracid precursors have ester links, amidine links, and amidine links Therefore, they are usually unstable in water or hydrogen peroxide, and will decompose due to hydrolysis reaction or decomposition reaction of hydrogen peroxide to lose the activity of the organic peracid precursor. Therefore, it is necessary to suppress the hydrolysis reaction or the decomposition reaction of hydrogen peroxide in order to make the organic peracid precursor into a liquid bleaching composition. The idea of the reaction position of the cells can be used to suppress the hydrolysis reaction or decomposition reaction of hydrogen peroxide. This idea is based on: compounds with ester linkages in their molecules. The paper size applies to the Chinese National Standard (CNS) A4 specification (210X297 mm) • 4-A7 ._ 一 ... ::--B7 V. Invention The phenomenon that 2 () is incorporated into microcells changes the rate of hydrolysis reaction (W. Ogaki, Kagaku to Kogyo, 47 (1988)). By controlling the decomposition reaction rate with a surfactant, the decomposition of the bleach in the solution can be suppressed. In fact, Japanese Patent unexamined Publication (JP KOKAI) No. Hei 6-207 196 proposes a technique using ‘this institution. However, the use of this technique is limited, and the stability of organic peracid precursors, which are generally known to improve stability, is not satisfactory. On the other hand, a bleach activator used in a powdery oxygen-based bleaching agent containing a phenoxybenzene derivative is hydrolyzed by an alkali component. Therefore, bleach activators must be granulated in some way. For example, JP KOKAI No. Sho 61-1 1 1400 and JP K0KAI No. Hei 6-1 36390 propose granulation methods. In addition, granular materials have the problem that stability is improved by granulation but solubility is impaired at the same time. In such a case, it is necessary to make the bleach activator dissolve in a short period of time rather than generate an organic peracid to properly utilize the activity of the bleach activator. Description of the invention Printed by the Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs (please read the notes on the back before filling this page) The purpose of the present invention is to propose a liquid bleaching oxygen-based bleaching composition with high bleaching power The organic peracid precursors contained are stable after long-term storage. Another object of the present invention is to propose a powdery oxygen-based bleaching composition having excellent storage stability and capable of efficiently forming a peracid. It was found that when a water-insoluble organic peracid precursor with a special structure is used with hydrogen peroxide and an interfacial agent, or a special bleach is soaked in an oil-absorbing carrier and the mixture is mixed with a hydrogen peroxide-based hydrogen peroxide system The bleaching agent used in this paper applies the Chinese National Standard (CNS) A4 specification (210X297 mm) -5-... ............ ··· ... K / ·-.. ... ........ " .....-. '·.. Λ *, t ... .... V. Description of the Invention 彳), the aforementioned problems can be solved and based on This finding completes the present invention. In other words, the present invention proposes a liquid oxygen-based bleaching composition, which comprises hydrogen peroxide, a surfactant, and an ethoxybenzene derivative represented by formula (I): (i)

RiCOO where R] is an alkyl or alkenyl group, or aryl group having 1 to 20 carbon atoms; and Chi 2 is a substituent that does not make this compound water-soluble. The present invention also proposes a powdery oxygen-based bleaching composition comprising a peroxide bleach for generating hydrogen peroxide and a product prepared by immersing an oxyoxybenzene derivative of formula (I) in an oil-absorbing carrier. Lipophilic activator particles. A preferred embodiment of the present invention. First of all, a feature of the present invention is to propose the oxygen-based bleaching composition produced by the Central Bureau of Standards of the Ministry of Liquid Economy, as described below. The composition of the present invention contains 0.1 to 30% by weight (hereinafter referred to as%) (preferably 2 to 20%) hydrogen peroxide (component a), which is a bleaching substrate. Although the present invention may use any surfactant as component b, it is desirable that the surfactant used has at least one straight or branched alkyl or alkenyl group having 8 to 24 carbon atoms, or, Have at least one paper size applicable to Chinese National Standards (CNS) A4 specifications (210X297 mm) -6-A7 B7 Printed by the Bayer Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the invention 4) 8 to 24 carbons An aryl group substituted by an atomic alkyl group. Examples of such surfactants include anionic surfactants (such as: alkylbenzene sulfonates, soaps, sulphate polyoxyethylene ethyl sulfonates or fatty alpha-sulfomethyl esters) Ionic surfactants (such as: alkyl (poly) glycosides, polyoxyethylene ethyl ethers, sorbitol fatty acid esters, polyoxyethyl sorbitol fatty acid esters, polyoxyethylene fatty acid esters (Polyoxyethylene fatty acid ester, oxyethylene ethylpropyl group-linked polymer fatty acid-glyceride or amine oxide) or examples of surfactants include amphoteric surfactants, such as: carbonyl betaine% extended beet Base or hydroxy extended betaine. Also preferred non-ionic surfactants are straight-chain or branched-chain carboxylic acid alkylene oxides with 1 to 18 carbon atoms (ethylene oxide and / or propylene oxide). Compounds, their lower alkyl esters or glycerol fatty esters. The content of the surfactant (component b) in the composition of the present invention is preferably 1 to 40%, and more preferably 1 to 20%. The bleach activator used as the component C in the present invention is represented by the formula ( I) An alkoxybenzene derivative. In this formula, the alkyl or alkenyl group in Ri has 1 to 20 carbon atoms (preferably 1 to 10), which may have one or more oxygen atoms. As a substituent. Among these substituents, an alkoxy group having 1 to 10 carbon atoms (such as methoxy, ethoxy, or propoxy) or an aryl group having 6 to 15 carbon atoms (such as : Phenyl 'p-methylphenyl or p-ethylphenyl) Examples of aryl groups of 0 or R t include aryl groups having 6 to 12 carbon atoms, which may have 1 to 10 carbon atoms Alkyl, alkenyl, alkoxyhalo, or oxomu groups are used as substituents. For examples of these substituents, please read the back-Cautions before writing this page. The paper dimensions are applicable to Chinese national standards (CNS > A4 size (210X297 mm) A7 V. Description of invention $) Including 1 to 10 Alkyl or alkenyl groups of carbon atoms (eg methyl, ethyl, propyl, hexyl or nonyl) or alkoxy groups of 1 to 10 carbon atoms (eg methoxy, ethoxy or Propoxy), halogen (such as: chlorine or bromine), alkoxycarbonyl groups (such as: methoxycarbonyl, ethoxycarbonyl, or isopentoxycarbonyl) with 1 to 10 carbon atoms. The functional groups that do not make the compounds of the present invention water-soluble R2 are preferably those that do not release cation M (such as hydrogen cations or metal cations). SoM or COOM group. Specific examples of the R2 group include a hydrogen atom; an alkyl or alkenyl group having 1 to 10 carbon atoms (eg, methyl, ethyl, propyl, hexyl, or nonyl); Alkoxy (such as: methoxy, ethoxy, or propoxy); alkoxycarbonyl with 1 to 10 carbon atoms (such as: methoxycarbonyl, ethoxycarbonyl, or isopentoxycarbonyl) : Halogen (such as: chlorine or bromine) or aryl; An aryl group as a substituent. Of these substituents, the hydrogen atom, methyl, ethyl, methoxy, or ethoxy group is preferred \ Printed by the Consumers' Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs (Please read the note on the back Ϋ-item before filling out this Page) Although R2 may be located at the ortho, meta or para position of the RiCOO group, R2 is preferably located at the para position of the Rx C 0 0 group. In the present invention, the hydrophobic parameter (1 og P) of the derivative of formula (I) is not lower than 2.8. In addition, the derivative of the formula (I) is preferably one having no hydrophilic group in the molecule. Here, the hydrophobic parameter (10 g P) represents the distribution coefficient of the target compound between water and octanol. It is usually used as a parameter showing the properties of a compound. 1 "P" in ogP is represented by P = Co / Cw, and its paper size applies to the Chinese National Standard (CNS) A4 specification (210X297 mm) -8-A7 --- .- ·.. / ·-.. .. V. Description of the invention Order) is the activity ratio of a compound in water and octanol under equilibrium conditions, where C 0 represents the concentration of the compound in octanol and Cw represents the concentration of the compound in water. For example, Kagaku no Ryoili, Supplementary Notes, Vol. 1 22 (1 979), page 73 describes the hydrophobic parameters (10 g P) in detail. It is known that the distribution coefficient can be determined by the bottle vibration method or thin-layer chromatography HPLC method. In this patent specification, the distribution coefficient is calculated using the parameters described in Ghose, Pritchett and Crippen, J. Comp. Chem., 2_, 80 (1998). In particular, 10 g of the derivative (I) having a P of not less than 2.8 can be stably present in the liquid oxygen-based bleaching composition. In the present invention, log P 値 of the derivative of formula (I) is preferably 2.8 to 8.5, and more preferably 3.0 to 6.0. As used herein, a derivative of formula (I) without a hydrophilic group in its molecule means that neither R i nor R 2 contains an ionic dissociative functional group, such as: carboxyl, sulfo, phosphorus, amine, tetra Primary ammonium salt, hydroxyl or alcohol ethoxylate (-(OCH2CH2) nOH, n > 2). Here, these hydrophilic groups do not include hydroxyl groups protected by esters or ethers. Printed by the Consumers' Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs. In this case, 111 and 112 have substituents. It is hoped that the substituents do not include any hydrophilic groups. As mentioned above, molecules without a hydrophilic group become completely water-soluble, and such molecules exist in the cells stably because they are dissolved by the surfactant. These phenomena give molecules the advantage of not being easily attacked by hydrogen peroxide or water. The aforementioned phenoxybenzene derivative of the formula (I) can be obtained from a catalyst (in the presence of carbonate or sulfuric acid, the reaction between an acid anhydride (UII) and a substituted phenol (III), or In the presence of carbonates -9- (Please read the note on the back before filling this page) This paper size applies to China National Standard (CNS) A4 specifications (210X297 mm) A7.... B7 ... .. V. Description of the invention X), the reaction between fluorenyl chloride (IV) and substituted phenol (III) (II) These two reactions are based on the following reaction diagram: R2

or H2SO4 K2C〇3

R1CO

R2

RiCOCl +

(III pyridine or K2CO3 The following examples illustrate the ethoxybenzene derivatives used in the present invention (the 値 in the brackets represents 10 g P 値), but of course it is not limited to these examples. (Please read the precautions on the back before filling (This page) Printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs • 10- This paper size is applicable to China National Standard (CNS) A4 (210X297 mm) 5. Description of the invention <) and 'c4H9 Cl (2.97) ο Human C9H19 C-3 (4.95) Ο

Α7 Β7 〇 person ο \ 7η15 C-2 (4.16) Ο 0 Λ

CllH23 C-4 (5.74) Ο

(Please read the precautions on the back before filling out this page). Packing. Order -Λ. Printed by the consumer cooperation of the Central Bureau of Standards of the Ministry of Economic Affairs

MeO— ^ ^ and C5Hu MeO C-7 (3.11) in parentheses are log p 値 and 0 C7H15 C-8 (3.90) This paper size applies Chinese National Standard (CNS) Α4 specification (210 X 297 mm) -11- Five, invention description $)

MeO

Ο MeO— ^

C-ll (2.89)

A7 B7

Ο MeO

Ο

Ο

(Please read the precautions on the back before filling out this page.) Packing. Γ Order Λ. Printed by the staff of the Central Bureau of Standards of the Ministry of Economic Affairs for consumer cooperation. Ο Ο Me

C-15 (3.93) C-16 (5.09) In the parentheses, log P 値 This paper size is applicable to China National Standard #CNS (A4) (210 × 297 mm) -12- 5. Description of the invention 1: 0)

Me

0 CgH19 and C-17 (5.88)

C7Hi5 and C-21 (5.41) A7 B7 0

Human C-20 (4.95) 0 II / == ^ oc-

COOMe C-22 (3.24) 15 (Please read the notes on the back before filling out this page) Pack. Γ Order Λ. Printed by the Staff Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs

COOMe

OC-CnH 11 ^ 23 C-23 (3.09) C-24 (3.89) C-25 (6.03) Log P in parentheses. This paper size is applicable to China National Standard (CNS) A4 specification (210X297 mm) -13 -A7 B7 V. Description of the invention < 1) 0II OC- c7h15 COOBu C-26 (5.09)

ΟII PC—CH3 COO _ C-27 (3.28)

coo-c8h17

OC-CH 3 c2h5o

oc—c7h15 C-29 (4.25) -------- o equipment-- (Please read the back 4Γ-Notes before filling out this page) C-28 (4.07) The Ministry of Economic Affairs in the brackets is 1 ogp The paper size of the printed papers printed by employees of the Central Standards Bureau applies to the Chinese National Standard (CNS) A4 (210X 297 mm) -14- A7 B7 ...... V. Description of the Invention 彳 2) The composition of the present invention contains 0.001 to 5% (preferably 0.1 to 3%) bleach activator (component c). In addition, when the weight ratio between the component b and the component c is 1.5: 1 to 20: 1, the derivative (I) can be more stably present in the liquid oxygen-based bleaching composition. • Various components other than the foregoing may be added to the liquid oxygen-based bleaching composition as necessary. For example, a phosphonic acid compound (e.g., ethane-1,1-di-ortho-acid, ethane-1,1,2-triphosphonic acid, ethane-1-hydroxyl-1,1,2-tris Phosphonic acid, ethane-1-hydroxydiphosphonic acid or ethane-1,1,2,2-triphosphonic acid) and their phosphonium salts or their derivatives, chelators with carboxyl groups (such as trivalent nitrogen triacetic acid) , Iminodiacetic acid or ethylenediaminetetraacetic acid) and their base salts or their derivatives. The preferred amount of these clamps is about 0 to 5%. Printed by the Central Bureau of Standards, Ministry of Economic Affairs, Shellfish Consumer Cooperative, the remainder of the composition according to the invention may be water. In addition, alcohols (such as ethanol, isopropanol, or ethylene glycol) can be added to stabilize liquids at low temperatures or avoid reprocessing from freezing conditions, and hydrophilic agents (such as polyethylene glycol or glycerin) can be added. In addition, if necessary, it may be necessary to add, for example: thickeners, perfumes, dyes, fluorescent dyes or enzymes in detergents or bleaches commonly used in clothing. P Η of the original solution of the composition according to the present invention is preferably adjusted to 2 to 7, more preferably 3.0 to 5.0. The acidic substances in the pH adjuster used are: inorganic acids (such as hydrochloric acid, sulfuric acid or phosphoric acid) or organic acids (such as p-toluenesulfonic acid, citric acid, phosphonic acid derivatives or phosphoric acid derivatives), and alkaline substances Such as: sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate The paper size is applicable to Chinese National Standard (CNS) A4 (210X297 mm) -15- A7 B7 V. Description of the invention 彳 3), ammonia and the like . It is desirable to adjust p Η of the original solution to be within the aforementioned range, because the stability of the original solution at this time becomes good. Another feature of the present invention is to propose a powdery oxygen-based bleaching composition as described below. In the present invention, a hydrogen peroxide-based bleaching agent that generates bleach | matrix hydrogen peroxide includes percarbonate (such as sodium percarbonate or potassium percarbonate), perborate (such as sodium perborate), and perphosphate. , Bleaching powder, isocyanurate, hypochlorite, persulfate and adduct of hydrogen peroxide and perphosphonate, citrate, sulfate or sodium silicate. Particularly preferred are the mono- or tetrahydrates of sodium percarbonate and sodium perborate. These compounds may be used alone or in combination with each other. In the composition of the present invention, the content of the aforementioned hydrogen peroxide-based bleaching agent in the powdery oxygen-based bleaching composition is preferably 30 to 90%, and more preferably 30 to 70%. Printed by the staff of the Central Bureau of Standards of the Ministry of Economic Affairs for consumer cooperation (please read the note on the back of the W-item before filling out this page) The ethoxybenzene derivative represented by formula (I) and the one described in the first feature of the present invention the same. Here, it is desirable that R2 in formula (I) is an alkyl or alkenyl group having 9 to 10 carbon atoms (such as nonyl); an alkoxy group having 1 to 10 carbon atoms (such as methoxy group) , Ethoxy, or propoxy); alkoxycarbonyl groups with 1 to 10 carbon atoms (such as: methoxycarbonyl, ethoxycarbonyl, or isopentoxycarbonyl); halogens (such as: chlorine or bromine ); Or the aryl group. The composition of the present invention preferably contains 1 to 90% of the granular formula (I) derivative, and its content is more preferably 30 to 80%. It is hoped that the oil-absorbing carrier has an oil-absorbing power of 25 ml / 1 100 g or more. This paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) A7; ... B7 ....... ......... 5. Description of the invention μ) (100 ml to 600 g ml / 1 100 g is preferred) lipophilic carrier. Silicone carrier (such as: amorphous silica or aluminosilicate) is better. Examples of lipophilic amorphous silica include registered names Tokuseal AL-1 (Tokuyama Soda Co. Ltd.) '' Nipseal NA (Nihon Silica Co. Ltd.) '' Carpex # 100 (Sionog'i Phamaceutical Co.), SIPERNAT D10 (Degussa) 'Tokuseal NR (Tokuyama Soda Co. Ltd.), TIXOLE A25 (Coflan Chemical), Florite RN (Tokuyama Soda Co. Ltd.) and the like. In addition, clay minerals, zeolites, calcium silicates, silica glass, and hollow inorganic powders can also be used. It is desirable that the average diameter of these oil-absorbing carriers is 100 to 100 micrometers. A lipophilic bleach activator can be prepared by immersing a derivative of formula (I) in an oil-absorbing carrier using a conventional method. It is desirable that the melting point of the nonionic surfactant is 50 ° C or below. Examples of non-ionic surfactants include higher alcohols, polyhydric alcohols, fatty acids, fatty amines, fatty amines, alkanes having 10 to 20 carbon atoms (preferably 10 to 15 carbon atoms) Alkylene oxide and synthetic alcohols (obtained from the oxidation reaction of n-alkanes or α-olefins). The average addition mole number of alkylene oxides is 5 to 15 and 6 to 6 12 is preferred, or an alkylene oxide adduct of a carboxylic acid or carboxylic acid ester. Specific examples include POE alkyl ethers, POE alkylphenyl ethers, POE sorbitol fatty acid esters, POE sorbose fatty acid esters, polyethylene glycol fatty acid esters, POEPE PP alkyl ethers, POE castor oil, "POE alkylamine, glycerin fatty acid ester, high-carbon fatty acid alkanolamine, alkyl glycosides, alkylamine oxides, fatty acid POE methyl esters and the like" Here, POE stands for polyoxidized paper. This paper is suitable for Chinese families Standard rate (CNS) A4 specification (210X297 mm) Please read the back < ·

I write this page Printed by the Shellfish Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs-17- Printed by the Shellfish Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs A7 ··· V. Description of the Invention 彳 5) Ethylene, and P ο P stands for Polypropylene Oxide . It is desirable that the particles contain 0 to 50% (preferably 1 to 20%) of a nonionic surfactant. In the present invention, it is preferable to use another adhesive. Examples of preferred binders include non-ionic surfactants doped with ethylene oxide or polyethylene glycols having a melting point of 20 to 100 ° C (at 40 ° C or better). When a nonionic surfactant is also used as a binding material, a nonionic surfactant may be used as a binder. The particles may contain 5 to 7.0% (preferably 10 to 50%) of the bonding material. In the present invention, it is desirable that the bleach activator granules in the form of a bar are made by passing an adhesive through a granulator. From the viewpoint of bleaching effect, it is desirable that the bleaching composition contains 0.5 to 30% of bleach activator particles based on the total amount of the bleaching composition, and the content thereof is preferably 1% or more. According to the present invention, a liquid or powdery oxygen-based bleaching composition is proposed, which has excellent bleaching power and can bleach all stains, and is stable even after long-term storage at high or low temperature. The following examples serve to illustrate the invention. Examples 1-10 and Comparative Examples 1-2 The liquid oxygen-based bleaching composition described in the following Schedule 1 was prepared, which contained 0.1 in addition to the components listed in Schedule 1 % Of the formulated fragrance, the rest is deionized water, and the pH of the solution is adjusted to 3-5 with sodium hydroxide or sulfuric acid. The characteristics of the solution were evaluated as follows. The results obtained are also listed in Schedule 1. (1) Stability of organic peracid precursors The bleaching composition listed in the attached table is stored at 50 ° C for 4 weeks, and the percentage of the remaining precursors is determined by Η P L C. (2) The size of clothing paper soiled with red wine is applicable to China's national standard (CNS > Α4 size (210X297 mm) -18--------- ο equipment-* (Please read the Pay attention to the items and fill in this page) Order A7 B7 printed by the Shell Standard Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 5. Preparation of the invention) Imitation) Material Woven cotton cloth (phosphine 100) Soaked in red wine (Suntry Reserve Red, Suntry Co., Ltd.) for about 5 minutes, and then air-dried. After pressing, a test piece of 8 x 8 cm was obtained from the soiled cloth for measurement. (3) Bleaching rate · Five pieces of tartar cloth stained with red wine soaked in the manner described above were soaked in a solution with the composition shown in Table 1. This solution was diluted 300 times with water in advance and left at 30 ° C. 1 hour. These were arranged in a commercially available detergent solution (Koso TOP, supplied by LION Co.) using a standard concentration of 6 67 p pm. The solution was stirred at 20 ° C for 10 minutes, the cloth was rinsed with tap water, dried, and the reflection on the surface of these cloths was measured. The bleaching rate is calculated from the following formula: bleaching rate (%) = 100 × (reflection of bleached cloth (reflection of a dirty cloth) / (reflection of untreated cloth-reflex of a dirty cloth)) Here, the reflection 値 is measured with a ζ-Σ 80 chromaticity colorimeter (Nihon Densyoku, Co. Ltd.). This paper size is applicable to Chinese National Standard (CNS) A4 specification (210X297 mm) -19 · (Please read the back, please note before filling in this page)

Printed by the Central Bureau of Standards of the Ministry of Economic Affairs

V. Description of the invention 彳 7) A7 B7 Schedule 1 Example No. 1 2 3 4 5 6 Peroxide MCK) 5 5 5 5 5 5 Interfacial ring LAS 10 10 10 5 8 2 5 bleach activator α) C-1 C- 2 C-3 C-4 C-5 C-6 2 1 1 1 1 1 Ethane-1-hydroxy-1-diphosphonic acid (!!!) 0.1 0.1 0.2 0.3 0.5 1 Acid dye (ppm) 100 100 100 100 100 100 pH 3 3 3 4 3 3 Storage stability (residual rate) 85 91 92 95 91 92 Bleaching rate after storage 57 52 55 56 54 58 This paper size applies Chinese National Standard (CNS) A4 specification (210X297) ) -20-

AB 5. Description of the invention Cut) Schedule 1 (mine) printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economics Example number 7 8 9 10 r 2 'Hydrogen peroxide 00 5 5 5 5 5 5 Boundary, compound LAS 5 5 3 10 10 10-10 White activator (Magic C-8 C-13 C-17 2 0.5 0.3 0.7 1 0.5 Ethane-1-hydroxy-1-diphosphonic acid 01!) 1 0.5 0.2 1 0.2 0.1 ΗΤΑ (ίϋ ) 0.3 EDTA (X) 0.3 pH 3% 3 4 4 3 4 Storage stability (residual rate) 97 98 99 96 0 0 Bleaching rate after storage 59 54 51 57 25 26 Methyl ethyl salicylate: The log P value is 1.28, and the log P value for acetaminophen is 1.55. Γ and 2 · represent comparative examples. (Please read the precautions on the back before filling this page) This paper size applies to Chinese national standards (CNS > A4 size (210X297 mm) -21-Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs A7 B7 V. Description of the invention彳 9)

Attached Table 2 Buying Case No. 11 12 13 14 15 16 Hydrogen Peroxide (X) 5 5 5 5 5 5 Boundary, hafnium compound Methyl ester nonion 1 Methyl ester non ion 2 10 10 5 1 8 4 6 4 6 bleach Activator u) Cl C-2 C-3 C-4 C-5 C-6 0.5 1 0.5 1 1 1 Ethane-1-hydroxy-1-diphosphonic acid (¾) 0.1 0.3 0.3 0.3 0.3 0.3 NTACK) 0.2 EDTAOC) 0.2 Fragrance (ϋί) 0.1 0.1 0.1 0.1 Acid dye (PPm) 100 100 Deionized water remaining pH 3 2 4 4 3 4 Storage stability (residual rate) 88 Ji 90 91 92 93 95 Bleaching rate after storage 51 / · 53 54 60 57 58 + Zhinongren Anti-Tongzhou Jiahuo Standard (CNS) A4 Specification (210X297 mm) -22 A7 B7 V. Invention Description and) Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs Table 2 (mine) Example No. 17 18 19 20 3 · Hydrogen peroxide (X) 5 5 5 5 5 oxide Methyl ester nonion 1 Methyl ester nonion 2 4 6 10 10 10 5 bleach activator u) C-8 C -13 017 0-19 Methylacetamidosalicylic acid_ 1 1 1 1 1 Ethane-1-hydroxy-1-diphosphonic acid (X) 0.3 0.5 0.5 0.5 0.3 Fragrance α) 0.1 0.1 0.1 Acid dye (ppm ) 100 go to water By pH 3 4 5 3 3 Storage stability (residual rate) after the appearance of white Li River rate after 919,089,900 5,754,525,223 storage reservoir square square square square square 3- representative of Comparative Example. -------- “Packing 丨 One (please read the note on the back Ϋ-item before filling out this page) ΐτ This paper size applies to China National Standards (CNS) Α4 size (210X 297 mm) -23- A7 B7 V. Invention Descriptions) Examples 1 1-2 0 and Comparative Example 3 The properties of the liquid bleaching composition listed in Schedule 2 were evaluated using the same method as described in Example 1. Here, the following methods were used. Determine the appearance stability of each composition: After the composition listed in the attached table 2 is stored in a 'culture machine at -5 ° C for 2 weeks, the appearance of liquid-liquid phase separation or crystal precipitation is observed with the naked eye, and It is expressed in the following way: 〇: The appearance is colorless and transparent, and there is no change from storage. X = Crystal precipitation or liquid phase separation occurs. Here, the surfactants listed in Table 1 are as follows: Alcohol ethoxylate: Softanol SC90 (supplied by LION Co.), alcohol having 12 to 14 carbon atoms, alcohol having 12 to 14 carbon atoms, EOp = 9. Linear alcohol ethoxylate: Emalex 710 (Nihon Emulsion), the linear alcohol has 12 carbon atoms, EOp = 10. LAS: sodium alkylbenzenesulfonate (R = C16) Printed by the Shellfish Consumer Cooperative of the Central Bureau of Standards and Quarantine of the Ministry of Economic Affairs (please read the back of the document first, and note the family items before filling out this page) AOS: C14.16, α-bond niacinate sodium Methyl ester nonion 1: C12-14 fatty acid polyoxyethyl methyl vinegar (P = 1 1)

Methyl ester nonion 2: C12-14 fatty acid polyoxyethyl ethyl methyl vinegar (P = 8) Here, EO stands for ethylene oxide, and p stands for the average addition mole number of ethylene oxide. Attached Table 3 This paper size is applicable to Chinese National Standard (CNS) A4 specification (21〇 × 297 mm) -24- " ~ A7 B7 V. Invention Description)

Table 3 Composition of bleach activator granules Granule number 1 2 3 4 5 Lipophilic 鞴 * NR 60 NR 35 NR 25 NR 30 NR 35 111 »-Methyl ester nonion 15 10 10 漯 White activator C-2 C-13 C-8 C-29 40 50 65 60 50 Adhesive: PEG 10 5 NR: Tokuseal NR: Branched alcohol ethoxylate: Ρ 0 Ε (ρ = 9) C 1 2 ~ C (Please read the back first (Note f, please fill out this page) Please print 7010 '5 5 1 1 by the Consumer Cooperatives of the Central Procurement Bureau of the Ministry of Economic Affairs. °°° · 10 · 0 · Yuanyuan Charm; Linear Alcohol Ethyl Oxide: POE (p = 10) lauryl ether: Methyl ester nonion 1: fatty acid polyoxyethylene methyl vinegar (C 12, p. = 10) PEG: polyethylene glycol (molecular weight 6000). The bleach activator granules prepared as described above were used in the bleaching composition shown in Table 4 to evaluate the generation rate of organic peracid and its storage stability. The results are listed in Schedule 5. Schedule 4 Formulation of bleaching composition OK) Percarbonate, white activator, granules LAS-Na, non-aquatic surfactant, 钙 -calcium hemihydrate, fragrance, Guanglang sodium carbonate This paper is applicable to Chinese National Standards (CNS) A4 specifications (210X297 mm) -25- 387938 at-: B7 V. Description of the invention 2 (3) LAS — Na: linear alkyl (Ci.-C14) sodium benzenesulfonate non-ionic surfactant: POE ( p = 9) Secondary alkyl ether enzyme: Ruo Zhong (Novo Industries. Co., alkali 6.0T) Fluorescent agent: Chinopal CBS-'X (Ciba Geigy Co. Ltd.) (3) It was evaluated that the bleaching composition was dissolved in deionized water so that the concentration of the bleaching composition was 2000 O p pm, and the mixture was stirred for 10 minutes, and the amount of peracid formed was measured by iodine titration. Here, the amount of organic peracid produced is calculated by taking all the bleach activator prepared as organic peracid as 100%. (4) Evaluation of storage stability Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs (please read the precautions on the back before filling this page) Put the bleach composition in a glass bottle, cover it, and let it stand in continuous circulation The incubator was placed at 45 ° C, 85% relative humidity and 25 ° C, 65% relative humidity for two weeks. An appropriate amount of the sample was dispersed and dissolved in deionized water so that the concentration of the bleaching composition was 3 000 p pm. After stirring for 10 minutes, the generation rate of organic peracid was evaluated by iodometric titration. Here, the organic peracid generation rate before storage is taken as 100%, and the residual rate of the bleach activator is calculated. Organic peracid generation rate and storage stability are listed in Appendix 5 below. Attached Table 5 Evaluation results of white composition White granules of white activator No. 1 2 3 4 5 Storage rate of acid before storage 95X 97 97 96 98 Storage stability (residual rate of white activator) 97X 98 97 97 96 This paper size applies to Chinese national standards (CNS > A4 size (2 丨 0X297mm) -26-

Claims (1)

Attachment la: Amendment No. 87104894 to 7th Case 9f __ ^ Application for Patent Amendment Amendment Lee Fan Tuan. — A kind of liquid oxygen system drift 8δ. Said. "Year Month Day _ Bu Yun Bu Zheng 1-30% by weight hydrogen peroxide '1-4 0% by weight surface active agent and 0.001-5% by weight An ethoxybenzene derivative represented by formula (I): R > 2 RjCOO (I) where Ri is an alkyl or alkenyl group, or an aryl group having 1 to 20 carbon atoms; and R2 does not make this The compound has a water-soluble substituent. 2. The bleaching composition according to item 1 of the scope of patent application, wherein the hydrophobic parameter (log P) of the 醯 oxybenzene derivative is not lower than 2.8. 3. The bleaching composition of the first item, wherein the surfactant is a surfactant having at least one linear or branched alkyl or alkenyl group having 8 to 24 carbon atoms, or a surfactant having at least one A surfactant with an aryl group replaced by an alkane with 8 to 24 carbon atoms (please read the note above and write this page first) Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 4. For example, the bleaching composition of the third patent application range, wherein the surfactant is a nonionic surfactant or an anionic surfactant 5. The bleaching composition according to item 2 of the patent application, wherein the hydrophobic parameter (log P) is 2.8 to 8. 5. 6. The bleaching composition according to item 1 of the patent application, wherein R 2 Is a hydrogen atom, an alkyl or alkenyl group with 1 to 10 carbon atoms, an alkoxy group with 1 to 10 carbon atoms, an alkoxy group with 1 to 10 carbon atoms National Standard (CNS) A4 Specification (210 X 297 male *) Annex la: No. 87104894 No. 7 Case 9f __ ^ Application for Patent Model Group Amendment October 1980 Lee Fan Tuan. — A kind of liquid oxygen system drift 8δ. Said. "Year Month Day _ Bu Yun Bu Zheng 1-30% by weight hydrogen peroxide '1-4 0% by weight surface active agent and 0.001-5% by weight An ethoxybenzene derivative represented by formula (I): R > 2 RjCOO (I) where Ri is an alkyl or alkenyl group, or an aryl group having 1 to 20 carbon atoms; and R2 does not make this The compound has a water-soluble substituent. 2. The bleaching composition according to item 1 of the scope of patent application, wherein the hydrophobic parameter (log P) of the 醯 oxybenzene derivative is not lower than 2.8. 3. The bleaching composition of the first item, wherein the surfactant is a surfactant having at least one linear or branched alkyl or alkenyl group having 8 to 24 carbon atoms, or a surfactant having at least one A surfactant with an aryl group replaced by an alkane with 8 to 24 carbon atoms (please read the note above and write this page first) Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 4. For example, the bleaching composition of the third patent application range, wherein the surfactant is a nonionic surfactant or an anionic surfactant 5. The bleaching composition according to item 2 of the patent application, wherein the hydrophobic parameter (log P) is 2.8 to 8. 5. 6. The bleaching composition according to item 1 of the patent application, wherein R 2 Is a hydrogen atom, an alkyl or alkenyl group with 1 to 10 carbon atoms, an alkoxy group with 1 to 10 carbon atoms, an alkoxy group with 1 to 10 carbon atoms National Standard (CNS) A4 Specification (210 X 297 male *) Is 38T938 VI. Patent application scope, processing element or aryl group 07 • For the bleaching composition of item 1 of the patent scope, where R is hydrogen, a Group, ethyl, methoxy, or ethoxy group 0-A liquid oxygen-based bleaching composition containing • 0.1 to 30% by weight of hydrogen peroxide; 1 to 40% by weight of nonionic #Surfactant and / or anionic surfactant, this surfactant is a surfactant having at least one straight or branched alkyl or alkenyl group having 8 to 24 carbon atoms, or An alkane having at least one aryl group with 8 to 24 carbon atoms Surfactant substituted with a radical; 0.001 to 5% by weight of an ethoxybenzene derivative represented by the formula (I): {锖 Read the note on the back of the S section first and write the script I > Members of the Seibu Intellectual Property Bureau ’s consumer cooperation agreement include Ri, an alkyl or alkenyl group, or an aryl group having 1 to 20 carbon atoms; and R2 is a substituent that does not make this compound water-soluble. Selected from a hydrogen atom, an alkyl or alkenyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkoxycarbonyl group having 1 to 10 carbon atoms, halogen and aromatic Base; and water. 9. A powdery oxygen-based bleaching composition comprising 30-90% by weight of a peroxide bleach for generating hydrogen peroxide and applying the formula (I) to the paper standard of China National Standard (CNS) A4 (210 X 297 mm) -2 · A8 387938 S D8 6. The lipophilic bleach activator granules prepared by soaking the phenoxybenzene derivative in the oil-absorbing carrier within the scope of the patent application; (Please read the note on the back first $ 项 再 * Write this page) R ^ OO ~ \ _ / (I) where 'is an alkyl or alkenyl, or aryl group having 1 to 20 carbon atoms: instead it does not make this compound water-soluble Substituents. 10. The bleaching composition according to item 9 of the scope of the patent application, wherein the hydrophobic parameter (oog P) of the ethoxybenzene derivative is not lower than 2.8. 1 1. The bleaching composition according to item 9 of the scope of patent application *, wherein the oil absorption force of the oil-absorbing carrier is 25 ml / 100 g or more. 12. The bleaching composition according to item 9 of the scope of patent application, wherein the oil-absorbing carrier is amorphous silica or aluminosilicate. 13. The bleaching composition according to item 9 of the scope of patent application, wherein the peroxide bleach for generating hydrogen peroxide is a percarbonate or a perborate. Printed by the Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. 1-4. Such as the white composition of Shentouzhuan. The scope of profit. Item 9., where the hydrophobic parameter (10 £ P) is 2.8 to 8 . 5. 15. The bleaching composition according to item 9 of the scope of the application for patent, wherein the ruler 2 is a hydrogen atom, an alkyl or alkenyl group having 1 to 10 carbon atoms, and an alkoxy group having 1 to 10 carbon atoms. , An alkoxycarbonyl group having 1 to 10 carbon atoms, a halogen or an aryl group. 16. If the bleaching composition in item 9 of the scope of patent application, where -3- this paper size applies Chinese National Standard (CNS) A4 specification (210 X 297 mm) 387938 A8B8C8D8 VI. Patent application surface lipophilic bleaching Activator particles contain nonionic surfactants> 17 powdery oxygen-based bleaching compositions containing: 30 to 90% of a peroxide bleach selected from percarbonate and perborate; and lipophilicity Bleaching activator particles, which are prepared by soaking a methoxybenzene derivative of formula (I) in an oil-absorbing carrier selected from amorphous silica or aluminosilicate; R2 R ^ OO (I) Economic The Ministry of Intellectual Property Bureau ’s consumer cooperation has printed Du, where Ri is an alkyl or alkenyl group or aryl group with 1 to 20 carbon atoms; and R2 is a substituent that does not make this compound water-soluble. Hydrogen, alkyl or alkenyl having 1 to 10 carbon atoms, alkoxy having 1 to 10 carbon atoms, alkoxycarbonyl having 1 to 10 carbon atoms, halogen and aryl. 1 8 .. The bleaching composition as described in item 17 of the Li-Wu Wai, comprises 1 to 90% by weight of a derivative represented by formula (I), 5 to 70% by weight of a lipophilic carrier and a nonionic interface. Active agent. n ^ H Γ t ^ I ϋ ϋ I * ^ II n ϋ ^ ^ · 1 ϋ ^ ^ I ^ I ^ ^ 1 National Standard (CNS) A4 Specification (210 * 297 mm) -4-