KR100502955B1 - Granulate composition for detergent to prevent from spotting on clothes - Google Patents

Abstract

In the present invention, since the complex salt formed by the reaction of the photobleaching component and the cationic surfactant is not dissolved in water in the stationary state such as when immersing for hand washing or washing pretreatment, the photobleaching component is dyed into the fiber of the fiber to prevent staining. At the same time, a granulation agent comprising a complex salt in which the complexing salt of the photobleaching component and the cationic surfactant in the granule composition dissolves uniformly and rapidly under the stirring condition of a washing machine or the like so that the photobleaching component adheres to the fiber to perform bleaching and washing. The present invention relates to a granulated composition for preventing dyeing stains for addition.

Description

 Granule composition for detergent to prevent from spotting on clothes}

The present invention relates to a granulated composition for preventing staining stains for addition of granular detergent including a complexing salt for photo-bleaching, and more specifically, bleaching and washing by dissolving uniformly and rapidly under the stirring conditions of a washing machine or the like to adhere to fibers. The present invention relates to a granule composition for preventing staining stains for addition of granular detergent, which can suppress generation of dyeing stains that generally occur in a stationary state such as when immersion for hand washing or washing pretreatment.

In general, as a photobleaching component suitable for use in laundry detergents, materials using metallo porphrins, metallo phthalocyanine, metallo naphthalocyanine, and the like are currently being actively studied.

Originally, metallo porphrin, metallo phthalocyanine and metallo naphthalocyanine, which only have hydrogen attached to their parent ring, are used as color pigments and have no effect on laundry.

As a method for using such a compound for bleaching and washing, there are methods described in European Patent Nos. 0553607, 0553608, 0596184, 0596186, 0596187, 0692947 and the like. These methods are those in which a hydrophilic substituent is attached to the parent ring of the compounds so that they can be dissolved in water. Typically, these hydrophilic substituents substitute three or more in the parent nucleus.

 US Patent No. 3,927,967 describes the use of photoactive agents, such as zinc phthalocyanine sulfonate, for use as granular detergents.

These photobleaching components can absorb electromagnetic radiation in the visible range and can emit both energy absorbed in a form that imparts bleaching action to the fabric. Both protons are considered to produce oxidatively active single phase oxygen. Certain photoactivators such as zinc phthalocyanine sulfonate and aluminum phthalocyanine sulfonate have been found to be commercially applicable in the field of granular detergent compositions.

However, as described above, materials such as metallo porphrin, metallo phthalocyanine, and metallo naphthalocyanine having water-soluble substituents, when used in detergent compositions, may be used as the color of the photobleaching component dye under specific washing conditions. Green to blue dye stains are generated on the laundry. Such stains are frequently generated, especially when hand washing or when the laundry is soaked for a long time without sufficiently dissolving the detergent in the washing machine.

That is, compounds such as metallo porphrin, metallo phthalocyanine, and metallo naphthalocyanine, which have water-soluble substituents as photobleaching components, function as dyes having a color from green to blue. At the same time, natural fiber strains such as cotton, rayon, or silk can easily dye fibers by hydrogen bonding and van der Waals forces. That is, many consumers put the cloth in the detergent solution for hand washing or as a pretreatment of the laundry, and leave the cloth for a long time without sufficiently dissolving the detergent containing the photobleaching component. As it melts into the fiber and dyes into the fiber, it is easy to get dissatisfaction with the general consumer because it appears in the human eye as a stain with a color from green to blue, which is unique to the light bleaching ingredient.

On the other hand, European Patent No. 0119746 has a method of spraying a solution containing a diluted photobleaching component onto the detergent composition as a method for adding a water-soluble photobleaching component to the detergent composition, but this method is very ineffective due to the affinity with the fiber of the photobleaching component. It is regarded as a method, and a more improved method is to uniformly mix the photobleaching component in the entire detergent composition to dilute the partial overconcentration, but this method also is in view of consumer marketing which involves changing the color of the detergent powder itself. Risks must be taken, and this method is also not a complete solution, although staining due to dyeing may be reduced by dilution of concentration, rather than the method described above.

Due to this problem of dyeing, the photobleaching components have been added only in very small amounts which show little photobleaching effect when actually added to laundry detergents, especially granular detergents.

Korean Patent Publication No. 96-14750 discloses an encapsulating material which does not dissolve in a nonionic surfactant as a carrier of a photobleaching component so as to be rapidly encapsulated in cold water. However, the rapid dissolving of the photobleaching component like this method does not provide the perfect solution to solve the problem of dyeing, considering the affinity with the fiber which is a characteristic of the photobleaching component as a direct dye. In some cases, there is a possibility to increase stains. The experimental results of the present inventors have shown that the microcapsules products marketed in this way actually cause dye stains.

The technical problem to be achieved by the present invention is to prevent the photobleaching component from being dissolved in water in a stationary state, thereby preventing chemical reactions with the fiber, and the photobleaching component is dissolved quickly and uniformly under the vortex or stirring conditions of a general washing machine, and thus strongly It is an object of the present invention to provide a granular composition for preventing dyeing stains for addition of granular detergent, which can be made to have an excellent photobleaching effect under sunlight drying conditions after washing.

In order to achieve the above technical problem, the present invention is obtained by reacting a photobleaching component having a water-soluble anionic substituent and a cationic surfactant, and includes a complex salt for washing that does not cause dye stains, the photobleaching component is 0.001 to 0.5% by weight To provide a granular detergent composition comprising the laundry complex salt to the content of%, further comprising an oil absorbent, a binder.

(1) complex dyeing for preventing stains

The dyeing stain preventing laundry complexing has already been mentioned by the applicant for the dyeing stain preventing complex through the application of the Republic of Korea Patent Application No. 2002-54938 (September 11, 2002).

The cationic surfactant in the complex salt is characterized by reacting with the photobleaching component to form a water-insoluble complex salt. The cationic surfactant is preferably a quaternary ammonium represented by the following general formula (1), (2) or (3).

(Wherein R ₁ is a substituted or unsubstituted alkyl group or alkenyl group having 8 to 22 carbon atoms, R ₂ is a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms, X is a halogen atom, acetate, phosphate, nitrate, Or methylsulfate)

Wherein R ₁ and X are as defined above.

Wherein R ₃ is hydrogen or a substituted or unsubstituted alkyl group or alkenyl group having 1 to 22 carbon atoms, R ₄ is a substituted or unsubstituted alkyl group or alkenyl group having 8 to 22 carbon atoms, R ₅ and R ₆ are carbon atoms 1-4 alkyl groups, X represents a halogen atom, acetate, phosphate, nitrate, or methylsulfate)

The compound of formula 1, which can be preferably used as the cationic surfactant of the present invention, is an ester of a quaternary ammonium compound, so-called esterquat, which is at least one long-chain hydrophobic alkyl or alkenyl substituted by a carboxyl group. Have a group Such compounds are known compounds and are described, for example, in EP 0239910 or WO95 / 24460.

In addition, the compound of formula (2), which can be preferably used as the cationic surfactant of the present invention, is 1-methyl-1-[(steroylamido) ethyl] -2-octadecyl-4,5-dihydroimime Dazolinium chloride, 1-methyl-1-[(oleylamido) ethyl] -2-oleyl-4,5-dihydroimidazolinium methyl sulfate, 1-methyl-1-[(tallowamido ) Ethyl] -2-tallow-4,5-imidazolinium chloride, 1-methyl-1-[(palmitoyl amido) ethyl] -2-octadecyl-4,5-dihydroimidazolinium Chloride, 1-methyl-1-[(steroylamide) ethyl] -2-octadecyl-4,5-dihydroimidazolinium chloride or 1-methyl-1-[(tallowamido) ethyl ] -2-hydrotallow-4,5-imidazolinium chloride.

Specific examples of the compound of formula 3 suitable for use in the present invention include tallow trimethyl ammonium chloride; Ditallow dimethyl ammonium chloride; Ditallow dimethyl ammonium methyl sulfate; Dihexadecyl dimethyl ammonium chloride; Di (hydrogenated tallow) dimethyl ammonium chloride; Dioctadecyl dimethyl ammonium chloride; Distearyldimethylammonium chloride; Diicosyl dimethyl ammonium chloride; Didocosyl dimethyl ammonium chloride; Di (hydrogenated tallow) dimethyl ammonium methyl sulfate; Dihexadecyl diethyl ammonium chloride; Dihexadecyl dimethyl ammonium acetate; Ditallow dipropyl ammonium phosphite; Ditallow dimethyl ammonium nitrate; And di (coconut-alkyl) dimethyl ammonium chloride.

In the present invention, another essential component for reacting with the cationic surfactant to form the anti-staining laundry complex salt is a water-soluble photobleaching component having an anionic substituent. Examples of the water-soluble photobleaching component having an anionic substituent in the mother nucleus usable as the detergent composition contemplated by the present invention include those described in European Patent Nos. 0553607, 0553608, 0596184, 0596186, 0596187, or 0692947. Those having an anionic substituent capable of forming a complex salt with the surfactant.

These are not particularly limited as long as they are commonly used in detergents, but examples thereof include metal porphyrins, metal phthalocyanines and metal naphthalocyanines having water-soluble anionic substituents. Preferred are water-soluble metal phthalocyanines having an anionic substituent, more preferably zinc phthalocyanine sulfonate and aluminum phthalocyanine sulfonate alone or in combination.

The granular composition for granular detergent addition according to the present invention using the above-mentioned anti-staining laundry complexing salt may further include at least one selected from the group consisting of the above-described anti-staining anti-dyeing oil absorbent and a binder.

The granule composition according to the present invention may further include at least one detergent component or compatible auxiliary components selected from the group consisting of organic surfactants and washing enhancers.

The average mole number of the cationic surfactant forming a complex salt with the photobleaching component with respect to 1 mol of the photobleaching component having an anionic substituent is 1 to 100 mol, preferably the photobleaching component 1 to enable the total complexing of the anionic substituents of the parent nucleus. The average number of moles of cationic surfactant per mole is 4 to 40 moles.

The complex salt may be obtained by reacting a cationic surfactant with a photobleaching component in a solvent capable of dissolving either a cationic surfactant or a photobleaching component or a complex salt.

The amount of the solvent in the present invention can be determined in consideration of the reaction time and production rate of the complex salt and the method applied to the granular detergent, the amount of the suitable solvent is preferably 5 to 95% by weight of the total weight including the photobleaching component and cationic surfactant More preferably, it is 10 to 90 weight%, More preferably, it is 20 to 90 weight%.

The complex salt thus formed completely or almost loses the water solubility of the photobleaching component before the reaction, so that the complex salt is much more soluble in nonpolar organic solvents such as chloroform or dichloromethane than water.

As a preferable solvent for the present invention, any solvent can be used without particular limitation as long as it is usually used in the preparation of the detergent. As the preferred solvent, one or more of the photobleaching component, the cationic surfactant, or the resulting complex salt may be dissolved or solubilized. Examples of such solvents include water; Lower alcohols such as ethanol, propanol and isopropanol; Polyhydric alcohols such as glycerol and propylene glycol; Alkyl polyglycosides such as decyl polyglucose and dodecyl polyglycose; Higher aliphatic alcohols having 12 or more carbon atoms; fatty acid; Polyoxyethylene; And one or more selected from the group consisting of nonionic surfactants.

Particularly preferred as a solvent in the present invention is a nonionic surfactant, and any of the nonionic surfactants contemplated may be any known to be useful as a detergent for cleaning contaminated fabric. Suitable nonionic surfactants are commercially available and are derived from the condensation of ethylene oxide or the corresponding reactants and reactive-hydrophobic compounds. Hydrophobic organic compounds may be aliphatic, aromatic or heterocyclic compounds, but mixtures of aliphatic and aromatic compounds are preferred.

Preferred types of hydrophobic compounds are higher aliphatic alcohols and alkylphenols, but other compounds such as carboxylic acids, carboxamides, mercaptans, sulfonamides and the like can also be used.

Ethylene oxide condensates with higher alkylphenols or higher fatty alcohols are preferred types of nonionic compounds.

Usually the hydrophobic component should contain at least about 6, preferably at least about 8 carbon atoms, the preferred range of carbon number being about 8 to 22, especially for aliphatic alcohols of 10 to 18 carbon atoms, higher alkylphenols. In this case, it may contain 12 to 20 carbon atoms. The amount of alkylene oxide can vary considerably depending on the hydrophobic component, but as a general guideline and rule, at least about 3 to 200 moles, preferably about 5 to 50 moles of alkylene oxide, per mole of hydrophobic component have the desired solubility and washability. Or compatibility with other ingredients.

Preferred types of nonionic surfactants can be represented by the compounds of formula (4) or (5).

(Wherein R ₇ is primary or secondary alkyl having about 8 to 22 carbon atoms and m is an integer of 5 to 50)

(Wherein R ₈ is primary or secondary alkyl having 4 to 12 carbon atoms and n is an integer of 5 to 50)

In the compound of Formula 4, R ₇ represents primary or secondary alkyl having about 8 to 22 carbon atoms, preferably primary or secondary alkyl having 10 to 18 carbon atoms, and primary or secondary carbon having 12 to 15 carbon atoms. More preferred are primary alkyls and mixtures thereof.

In the compound of Formula 5, R ₈ represents primary or secondary alkyl having 4 to 12 carbon atoms, preferably primary or secondary alkyl having 8 to 12 carbon atoms, octyl, isooctyl, and 8 and 9 carbon atoms. Nonyl is more preferred.

Examples of preferred alcohols capable of preparing the compound of Formula 4 include lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol and oleyl alcohol, and mixtures thereof. A typical example of the nonionic surfactant of Formula 5 is lauryl alcohol condensed with 5 to 11 moles of ethylene oxide. Typical examples of the nonionic surfactant of the above formula (6) are isooctylphenol or nonylphenol condensed with 3 to 8 moles of ethylene oxide.

Other examples of nonionic surfactants that may be used are polyoxyalkylene esters such as organic acids such as higher fatty acids, rosin acids, tall oil acids, acids derived from petroleum oxidation products. These esters typically contain about 3 to 40 moles of ethylene oxide or their equivalent and about 10 to 22 carbon atoms in the acid component.

Other surfactants are alkylene oxide condensates with higher fatty acid amides. Fatty acid groups generally contain about 8 to 22 carbon atoms and, as a preferred example, may be condensed with about 3 to 40 moles of ethylene oxide. Corresponding carbox amides and sulfone amides can also be used as substantial counterparts.

The complex salt preparation prepared in this way is added to the granular detergent to prevent the photobleaching component from dyeing into the fiber of the fiber in the static state, such as when immersed for hand washing, while uniformly and rapidly dissolving in the fiber under the stirring conditions of a general washing machine. Dyeing is performed to bleach and wash.

The content of the complex salt preparation added to the granular detergent is contained so that the pure photobleaching component is 0.001% to 0.5% by weight based on the total weight. More preferably, it is 0.001 weight%-0.1 weight%.

(2) oil absorbents

The oil absorbent included in the anti-staining stain-proof laundry granule composition for adding the granular detergent of the present invention may be used alone or in combination of sulfate, carbonate, silicate, and clay as a substance capable of absorbing the solvent.

When sulfate is used as the oil absorbent, forget-me-not (Na ₂ SO ₄ ) is preferable, and when carbonate is used, sodium carbonate is preferable.

In the case of using a silicate as the oil absorbent, a crystalline laminated silicate represented by the following formula is particularly preferable.

LMSi _x O _{2y +} 1H ₂ O

L is an alkali metal and is preferably sodium, M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20.

Crystalline laminated sodium silicates of this type are described in EP-A 2 164 514, the preparation of which is described in DE-A 34 17 649, DE-A 37 18 350. Preferred x for the purposes of the present invention is 2, 3 or 4. More preferably x is 2, M is sodium and y is 0.

These materials are commercially available, and in particular, the structural formula represented by δ-Na ₂ Si ₂ O ₅ is available as NaechS-5, NaSKS-6, NaSKS-7 from Hoechst.

In the present invention, water-insoluble aluminum silicate can be used as the oil absorbent. The aluminosilicate may be crystalline or amorphous. Preferred aluminosilicate materials for the present invention have the following formula.

Mz [(AlO ₂ ) ₂ (SiO ₂ ) _y ] _x H ₂ O

Wherein M is a calcium exchange cation, Z and Y are at least 6 and the molar ratio of z to y is from about 1.0 to 0.5, and x is at least 5, preferably from about 7.5 to 275 and particularly from about 10 to 264. Preferably, the aluminosilicate material is in hydrated form, containing about 10 to 28%, in particular about 18 to 22%, of water.

Such aluminosilicate cation exchanger has a particle diameter of about 0.1 to 10 microns, preferably about 0.2 to 4 microns (a particle diameter is determined by analytical methods such as microscopy using a scanning electron microscope). Mean particle diameter of the ion exchange material).

Aluminosilicate ion exchange materials usable in the present invention are commercially available, or can be obtained naturally or synthetically. Synthetic crystalline aluminosilicate ion exchange materials useful in the present invention may include zeolite A, zeolite B, zeolite X, zeolite HS, zeolite P, and mixtures thereof.

Particularly preferred crystalline aluminosilicate ion exchange material in this alias is zeolite P, the general formula of which is

Na ₂ O x SiO ₂ Al ₂ O ₃ yH ₂ O

(Where x is 2 and y is 0 to 5)

As such, the crystalline aluminosilicate used in the complex salt granules has an average oil diameter of 0.7 to 2 micrometers and an average pore size of 0.3 micrometers, which has high oil absorption and is preferable for improving the fluidity of the granules. As such crystalline aluminosilicates, such zeolites are generally known and are commercially available as Dowsil A24 from Crossfield, for example. This is preferable from the viewpoint of oil absorption and hard water softening properties than zeolite 4A having the same chemical structure.

When the clay component is used as the oil absorbent, preferred clays are smectite clays, and examples thereof include sodium and potassium montmorillonite, sodium saponites, sodium hectorites, and the like. have. The clay used in the present invention is preferably a fine particle having a particle diameter of 50 microns or less.

It is also preferred that smectite clays suitable for the present complex salt granules have a cation exchange capacity of at least about 50 meq / 100 g.

Suitable smectite clays for the present invention include those commercially available, such as Gelwhite GP of Georgia Kaolin, Nolclay BC and Volclay NO.325 from American Colloid.

The oil absorbent used in the present invention may be used alone or mixed components, the content may be 10 to 90% by weight relative to the total weight of the photo-bleaching component-containing granules. In particular, 15 to 80 weight% is preferable, and 20 to 60 weight% is more preferable.

(3) binder

A binder may be used in the granular composition for preventing staining stain for adding the granular detergent of the present invention to achieve a powdery form in a granular form. In the present invention, the solvent may be used as a binder for this purpose and may be further added separately.

Preferred examples of such binders are nonionic surfactants or polyethylene glycols.

The nonionic surfactant for the binder may be any known to be useful as a detergent for cleaning contaminated fabric. Suitable nonionic surfactants are commercially available and are derived from the condensation of ethylene oxide or the corresponding reactants and reactive-hydrophobic compounds. Hydrophobic organic compounds may be aliphatic, aromatic or heterocyclic compounds, but mixtures of aliphatic and aromatic compounds are preferred.

Preferred types of hydrophobic compounds are higher aliphatic alcohols and alkylphenols, but other compounds such as carboxylic acids, carboxamides, mercaptans, sulfonamides and the like can also be used.

Ethylene oxide condensates with higher alkylphenols or higher fatty alcohols are preferred types of nonionic compounds.

Usually the hydrophobic component should contain at least about 6, preferably at least about 8 carbon atoms, the preferred range of carbon number being about 8 to 22, especially for aliphatic alcohols of 10 to 18 carbon atoms, higher alkylphenols. In this case, it may contain 12 to 20 carbon atoms. The amount of alkylene oxide can vary considerably depending on the hydrophobic component, but as a general guideline and rule, at least about 3 to 200 moles, preferably about 5 to 50 moles of alkylene oxide, per mole of hydrophobic component have the desired solubility and washability. Or compatibility with other ingredients.

Preferred types of nonionic surfactants can be represented by the compounds of formula (4) or (5).

<Formula 4>

(Wherein R ₇ is primary or secondary alkyl having about 8 to 22 carbon atoms and m is an integer of 5 to 50)

<Formula 5>

(Wherein R ₈ is primary or secondary alkyl having 4 to 12 carbon atoms and n is an integer of 5 to 50)

In the compound of Formula 4, R ₇ represents primary or secondary alkyl having about 8 to 22 carbon atoms, preferably primary or secondary alkyl having 10 to 18 carbon atoms, and primary or secondary carbon having 12 to 15 carbon atoms. More preferred are primary alkyls and mixtures thereof.

In the compound of Formula 5, R ₈ represents primary or secondary alkyl having 4 to 12 carbon atoms, preferably primary or secondary alkyl having 8 to 12 carbon atoms, octyl, isooctyl, and 8 and 9 carbon atoms. Nonyl is more preferred.

Examples of preferred alcohols capable of preparing the compound of Formula 4 include lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol and oleyl alcohol, and mixtures thereof. A typical example of the nonionic surfactant of Formula 5 is lauryl alcohol condensed with 5 to 11 moles of ethylene oxide. Typical examples of the nonionic surfactant of the above formula (6) are isooctylphenol or nonylphenol condensed with 3 to 8 moles of ethylene oxide.

Other examples of nonionic surfactants that may be used are polyoxyalkylene esters such as organic acids such as higher fatty acids, rosin acids, tall oil acids, acids derived from petroleum oxidation products. These esters typically contain about 3 to 40 moles of ethylene oxide or their equivalent and about 10 to 22 carbon atoms in the acid component.

Another binder that can be preferably used in the present invention may include polyethylene glycol. In particular, it may comprise a compound of molecular weight 100 to 10000, more preferably 200 to 8000.

The binder used in the present invention may be used alone or in combination thereof, and the content thereof may be 10 to 90% by weight based on the total weight of the photobleaching component-containing granules. 15-80 weight% is especially preferable, and 20-60 weight% is more preferable.

(4) other auxiliary ingredients

In the present invention, as an auxiliary ingredient for preparing granules, it is possible to use without limitation as long as it is generally used in detergent. Specific examples thereof include one or one selected from aminostilbene-based, biphenyl-based, coumarin-based, pyrazoline-based or quinoline-based one or more fluorescent brighteners and / or proteases, amylases, lipases or cellulase. Antifoaming agents may be added. The auxiliary component used in the present invention is preferably 10% by weight or less, more preferably 5% by weight.

Preparation of Complex Salt Granules

The complex salt prepared in the above method may be applied to a granular detergent as it is, but may be applied to make granules.

More specific methods of granulating the complex preparation into granules include , for example, a ribbon mixer (bauddal agent) and a nauda mixer (Honkawa Micron) using the above-described complex salt preparation and the above-mentioned oil absorbent and binder. ), V-type mixer (made by Baudal), Henschel mixer, pan fertilizer, batch mixer such as high speed mixer or lodge mixer, ketomix reactor (KETTEMIX REACTOR, manufactured by BALLESTRA), flexo mixer (FLEXO MIXER) It can be granulated using a continuous mixer such as Hosogawa Micron) and Flojet Mixer (Baudicks).

In the case of a batch type, the mixer used for the production of the complex salt of the present invention is, for example, a ribbon mixer (made by Baudal), a mixer made by Honkawa Micron, a V-type mixer (made by Baudal), a Henschel mixer, and a panpere. And a mixer, and a mixer equipped with a stirrer and a pulverizer such as a high speed mixer or a loew crab mixer can be used. In the case of the continuous type, a ketomix reactor (KETTEMIX REACTOR, manufactured by BALLESTRA), a flexo mixer (manufactured by Hosogawa Micron), a float jet mixer (manufactured by Baudics), and the like can be used. have.

The complex salt granule obtained by the production method of the present invention is preferably 20% by weight or less, more preferably 10% by weight or less of large particles having a particle diameter of 1410 µm or more. If the large particles exceed 20% by weight, solubility decreases, which is not preferable.

The complex salt granules obtained by the production method of the present invention do not need to be specifically crushed, but may be sieved when the average particle size is desired to be smaller. The complex salt granules thus prepared are applicable by metered addition to the granular detergent composition.

Hereinafter, although this invention is demonstrated in more detail according to the following Example, this invention is not limited to this Example.

Preparation Example 1 Preparation of Complex Salt (I)

1400 grams of methyltriethanolammoniummethylsulfate dioleyl ester, a compound having the structure of Formula 1, as a cationic surfactant was added to 2300 grams of polyoxyethylene (EO = 7 mol) lauryl ether, heated and maintained at a temperature of 60 ° C, and completely dissolved. 300 g of an aqueous 16% zinc phthalocyanine tetrasulfonate (sodium salt) solution was added dropwise while stirring as a photobleaching component. At this time, a uniform solution phase having a dark greenish blue color was obtained.

Preparation Example 2 Preparation of Complex Salt (II)

1000 g of 1-methyl-1-[(oleylamido) ethyl] -2-oleyl-4,5-dihydroimidazolinium methyl sulfate, a compound having the structure of formula 2 as a cationic surfactant, 2300 grams of ethylene (EO = 7 mol) lauryl ether was heated and maintained at a temperature of 60 ° C., completely dissolved, and then stirred with 300 g of a 16% zinc phthalocyanine tetrasulfonate (sodium salt) aqueous solution as a photobleaching component. 5 minutes was dripped. At this time, a uniform solution phase having a dark greenish blue color was obtained.

Preparation Example 3 Preparation of Complex Salt (III)

1400 grams of dimethyl distearyl ammonium chloride, a compound having the structure of Formula 3, as a cationic surfactant was added to 2300 grams of polyoxyethylene (EO = 7 mol) lauryl ether, heated and maintained at a temperature of 60 ° C, and completely dissolved. As a solution, 300 g of a 16% zinc phthalocyanine tetrasulfonate (sodium salt) aqueous solution 300g was added dropwise while stirring. At this time, a uniform solution phase having a dark greenish blue color was obtained.

<Confirmation of complexitis>

The absorbance of the complex salt preparations obtained in Preparation Examples 1 to 3 was measured by the following test method.

1. Laboratory Instruments and Reagents

1) Separation funnel 300ml

2) Chloroform (Merck, HPLC)

3) Water (deionized to 18Mohm, Millipore)

4) magnetic stirrer

5) Beakers (200ml)

2. Experimental conditions

1) UV / Vis spectrophotometer: Hewlett-Packard HP8452

2) UV scanning range: 190-800nm

3) UV cell: 1 * 2cm quartz cell

3. Experimental Results

0.05 grams of each complex salt preparation prepared in Preparation Examples 1 to 3 was dispersed in a mixture of 100 ml deionized water and 100 ml chloroform, mixed in a separatory funnel, separated by phase extraction, and the complexed material was extracted with a chloroform layer and measured on a UV spectrophotometer. Analyze by adjusting the concentration to make it possible.

UV scanning assay results for each formed complex salt are shown in FIGS. In addition, the absorbance of the aqueous solution of zinc phthalocyanine tetrasulfonate sodium salt is shown in FIG. 4 for comparison.

As can be seen from FIGS. 1 to 4, the spectrum of the complex salt preparation of the present invention shows a slight difference from the UV spectrum of the original aqueous solution of zinc phthalocyanine tetrasulfonate sodium salt, which has a change in the maximum absorption wavelength of UV. It was confirmed that the solubility of the complex salt was not water soluble and that the solubility was large in a non-aqueous solvent such as chloroform.

Preparation Example 4 Preparation of Complex Salt Granules

After In the complex preparations obtained in Preparation Examples 1, 2, and 3 in a high speed mixer (simgang industrial ㈜ claim, 1200 liter), it was added a Glauber's salt and zeolite P. The stirrer was run at 120 rpm and Chopper 2500 rpm, until granules were obtained. The obtained granules may be used as they are but were pulverized and selected using a sieve if necessary.

 Hereinafter, specific examples of the components used in the examples of the present invention are as follows.

Cationic surfactant 1): Bis (acyloxyethyl) -hydroxyethylmethylammonium methosulfate (trade name DEHYQUART-AU-46 from Cognis)

Cationic Surfactant 2): Alkyl amidoamponium acetate (trade name DEHYQUART 2415 PLV of Gnisa).

Cationic Surfactant 3): Cetyltrimethylammonium chloride (trade name DEHYQUART A-CA of Gnisa)

Cationic surfactant 4): Dimethyl distearyl ammonium chloride (trade name Aerosurf TA101 from Witco)

Cationic Surfactant 5): Methyl Tallowamidoethyl Tallowimidazoliniummethyl Sulfate (trade name Varisoft 475 from Whitco Inc.)

Photo-bleaching component 1): water-soluble phthalocyanine sulfate (trade name Tinolux BMC of Shiva Chemical)

Photo-bleaching ingredient 2): Water-soluble phthalocyanine sulfate (trade name Tinolux BBS of Shiva-Geigy Co., Ltd.)

Nonionic surfactant 1): polyoxyethylene lauryl ether (the average added mole number of ethylene oxide is 7 mol)

Nonionic surfactant 2): polyoxyethylene lauryl ether (3 mol of ethylene oxide average added moles)

Nonionic surfactant 3): polyoxyethylene lauryl ether (the average added mole number of ethylene oxide is 15 mol)

Nonionic surfactant 4): polyoxyethylene lauryl ether (with average molar number of added moles of ethylene oxide 15 moles)

Binder 1) (PEG 1000): Polyethylene glycol with average added mole number of ethylene oxide 1000

Binder 2) (PEG 4000): Polyethylene glycol, having an average added mole number of ethylene oxide of 4000.

Binder 3) (PEG 6000): Polyethylene glycol, which has an average number of moles of ethylene oxide 6000.

Oil absorbent: zeolite P (trade name Daucil A24 from Crossfield)

Example 1 Preparation of Complex Salt Granules by Type of Cationic Surfactant

According to the above preparation example, a photobleaching component-containing granule was prepared in the following composition while changing the type of cationic surfactant.

ingredient A B C D E Complexation Cationic Surfactants 1) 8 Cationic Surfactant 2) 7 Cationic Surfactants 3) 8 Cationic Surfactants 4) 9 Cationic Surfactants 5) 8 Photobleaching Ingredients 1) 5 5 5 5 5 Nonionic surfactant 1) 15 16 15 14 15 Zeolite P 42 42 42 42 42 sulphate of soda 30 30 30 30 30

Example 2 Preparation of Mixed Granules by Contents of Cationic Surfactants

According to the preparation example, the photo-bleaching component-containing granules were prepared in the following composition while changing the content of the cationic surfactant.

ingredient F G H I J Complexation Cationic Surfactant 1) 4 12 4 Cationic surfactant 2) 3 12 4 Photobleaching Ingredients 1) 5 5 5 5 5 Nonionic surfactant 1) 19 12 18 14 15 Zeolite P 42 43 44 42 42 sulphate of soda 30 28 30 27 30

Example 3 Preparation of Granules by Type and Content of Nonionic Surfactants

According to the preparation example, the photobleaching component-containing granules were prepared with the following composition while changing the type and content of the nonionic surfactant.

ingredient K L M N O Complexation Cationic Surfactant 1) 8 8 8 4 Cationic surfactant 2) 4 8 Photobleaching Ingredients 1) 5 5 5 5 5 Nonionic surfactant 2) 18 15 Nonionic surfactants 3) 16 14 Nonionic surfactants 4) 13 Zeolite P 42 43 44 44 45 sulphate of soda 27 28 30 28 28

Example 4 Preparation of Granules by Type and Content of Binder

According to the preparation example, the photobleaching component-containing granules were prepared in the following composition while changing the type and content of polyethylene glycol (PEG) as a binder.

ingredient P Q R S T Complexation Cationic Surfactant 1) 8 8 8 4 Cationic surfactant 2) 4 8 Photobleaching Ingredients 1) 5 5 5 5 5 Binder 1) (PEG 1000) 16 15 Binder 2) (PEG 4000) 17 14 Binder 3) (PEG 6000) 14 Zeolite P 44 42 44 44 45 sulphate of soda 27 28 29 28 28

Example 5 Preparation of Granules by Oil Type and Content

According to the preparation example, the light-bleaching component-containing granules were prepared in the following composition while changing the type and content of the oil absorbent.

ingredient P Q R S T Complexation Cationic Surfactant 1) 10 10 10 10 10 Photobleaching Ingredients 1) 5 5 5 3 3 Photo-bleaching ingredients 2) 5 5 Nonionic surfactant 1) 18 8 8 8 8 PEG 4000 8 10 10 10 Zeolite P 38 42 39 42 42 Sodium carbonate 28 26 21 21 sulphate of soda 27 Protease ¹⁾ One One One One One

1) Savinase 12T (Novozymes A / S)

Example 6 Detergent Application of Complex Salt Granules

In order to apply the complex salt granules containing the photobleaching component prepared above to a detergent, first, anionic detergent and nonionic detergent having the composition of Table 6 were prepared as follows.

ingredient Detergent I Detergent II Linear alkylbenzene sulfonates 18 Alphaolefin Alkyl Sulfonate 16 Polyoxy ethylene alkyl ether 20 (Ethylene oxide 7mol) Sodium carbonate 28 30 sulphate of soda 5 Zeolite A 25 40 moisture 6 3 sulphate of soda 2 7

To each of the granular detergents I and II thus prepared, each of the complex salt granules prepared in Examples 1 to 5 was added and mixed so that the content of the photobleaching component (Tibalux company Tinolux BMC) in the total detergent was 0.05% by weight. It was used for the following comparative experiments.

Comparative Example 1

To each of the detergents I and II of Example 6, the photobleaching component Tinolux BMC of Ciba-Geigy Co., Ltd. was sprayed and mixed in an amount of 0.05 wt% based on the total detergent weight.

Experimental Example

(1) dye test

In order to test the possibility of fiber dyeing claims under the wrong washing habits of consumers, the following experiments were conducted.

Three sheets of white cloth (6cm × 6 cm, Korea Apparel Testing Institute standard white cotton cloth) are piled up and placed in a petri dish, and then 10 g of each detergent of Example 2 containing the photobleaching component granules is evenly sprayed on the cotton cloth.

Pour 100ml of tap water and leave for 30 minutes, 1 hour, 2 hours, 4 hours, 8 hours, 12 hours.

After each time, the white cotton cloth is rinsed in running water and dried in a hot air drier for 50 ° C. for 30 minutes.

The degree of dyeing is determined as follows.

5 points | pieces: The upper surface, the middle surface, and the lower surface are all dyed.

4 points | pieces: The upper side is dyed severely, the middle side is dyed, and the underside is slightly dyed.

3 points | pieces: The top surface is dyed, the middle surface is dyed a little, and the bottom side is hardly dyed.

2 points | pieces: The top surface is dyed a little, and the middle side and the back side are not dyed at all.

1 point: The top, middle and back sides are not dyed at all

Dye test result Granular detergent Complexation 30 minutes 1 hours 2 hours 4 hours 8 hours Example 6 Detergent I A One One One 2 2 Detergent I B One One 2 3 4 Detergent I C One 2 2 3 3 Detergent I D One One One 2 4 Detergent I E One One 2 2 2 Detergent I F One 2 3 3 3 Detergent I G One 2 2 2 3 Detergent I H One One 2 2 2 Detergent I I One One One 2 2 Detergent I J One 2 2 2 3 Detergent I K One 2 3 3 3 Detergent I L One One One 2 2 Detergent I M One One 2 2 3 Detergent I N One One 2 2 2 Detergent I O One 2 3 3 4 Detergent I P One One 2 3 3 Detergent I Q One 2 3 3 4 Detergent I R One 2 2 3 3 Detergent I S One 2 3 3 3 Detergent I T One 2 3 3 4 6 to implementation Detergent II A One One One 2 2 Detergent II B One One 2 3 4 Detergent II C One One One 2 2 Detergent II D One One One 2 3 Detergent II E One One 2 2 2 Detergent II F One One One 3 3 Detergent II G One One 2 2 3 Detergent II H One One 2 2 2 Detergent II I One One One 2 2 Detergent II J One 2 2 2 2 Detergent II K One One 2 2 2 Detergent II L One One One One 2 Detergent II M One One 2 2 3 Detergent II N One One 2 2 2 Detergent II O One 2 3 3 3 Detergent II P One One 2 3 3 Detergent II Q One 2 2 2 2 Detergent II R One One 2 3 3 Detergent II S One One 2 3 3 Detergent II T One One One 2 2 Comparative Example 1 Detergent I 0.05% Tinolux BMC Spray 4 5 5 5 5 Comparative Example 1 Detergent II 0.05% Tinolux BMC Spray 4 5 5 5 5

It can be seen that the use of a nonionic surfactant in the composition in the granules containing a complex salt as shown in Table 7 is slightly superior to polyethylene glycol.

In addition, it can be seen that the detergent base is slightly better when the complexing granules are applied to detergent II than detergent I.

However, in all cases, it can be seen that the complexing granules are significantly superior to the case where the photoactivator is sprayed onto the detergent as it is.

(2) photobleaching component effect test

Bleaching force test cloth (BC-1) to be tested was cut to 7 × 7 cm, and washed with a detergent standard use amount (0.67 g / L) for 10 minutes using a cleaning force tester (Terg-o-tometer). Washing conditions were washed for 10 minutes at a temperature of 25 ℃, agitator rotation speed of 120rpm. After washing, each contaminated cloth was left to stand under an illumination of 17000 LUX incandescent lamp, and then dried for 2 hours, and sprayed with sufficient moisture every 10 minutes during drying, and after drying, each test cloth was measured with a colorimeter (DataColor International, SF500). ) Was used to measure the ΔY value, which is the change in Y value before and after washing.

Five repeated washings were evaluated to determine the effect of the photobleaching component on the repeated washing.

Also, for comparison, washing was performed only with water without detergent and detergent II alone without photobleaching component.

Light bleaching effect test result (cow drying test result) 1 time Episode 2 3rd time 4 times 5 times Detergent I A 0.65 1.45 3.65 4.85 6.15 B 0.68 1.5 3.36 4.89 6.2 C 0.62 1.49 3.45 4.86 6.12 D 0.63 1.53 3.52 4.98 6.03 E 0.64 1.49 3.46 5.03 6.26 F 0.68 1.52 3.36 5.01 6.23 G 0.59 1.56 3.65 4.85 6.07 H 0.62 1.53 3.52 4.78 6.05 I 0.64 1.6 3.46 4.89 6.29 J 0.63 1.53 3.55 4.98 6.25 K 0.64 1.62 3.47 4.86 6.14 L 0.62 1.49 3.67 4.79 6.32 M 0.64 1.56 3.54 4.87 6.15 N 0.64 1.57 3.36 4.96 6.25 O 0.6 1.53 3.48 4.92 6.18 P 0.67 1.53 3.49 4.77 6.25 Q 0.62 1.52 3.52 4.86 6.22 R 0.64 1.55 3.69 4.72 6.3 S 0.67 1.48 3.59 4.76 6.2 T 0.63 1.52 3.64 4.79 6.12 Detergent II A 0.65 1.45 3.45 4.64 6.15 B 0.63 1.46 3.65 4.7 6.2 C 0.62 1.49 3.63 4.95 6.12 D 0.62 1.45 3.78 4.85 6.12 E 0.64 1.47 3.68 4.69 6.25 F 0.63 1.45 3.58 4.97 6.08 G 0.65 1.46 3.64 5.03 6.15 H 0.6 1.48 3.56 4.65 6.13 I 0.61 1.53 3.25 4.85 6.17 J 0.59 1.52 3.45 4.69 6.13 K 0.6 1.52 3.33 4.98 6.09 L 0.65 1.49 3.15 4.79 6.07 M 0.63 1.46 3.47 4.85 6.15 N 0.62 1.49 3.45 4.67 6.25 O 0.61 1.52 3.37 4.52 6.15 P 0.64 1.55 3.35 4.85 6.13 Q 0.64 1.54 3.46 4.62 6.18 R 0.64 1.59 3.65 4.72 6.07 S 0.62 1.46 3.25 4.88 6.14 T 0.63 1.48 3.62 4.92 6.19 Wash with water only without detergent 0.42 0.95 2.11 3.19 4.4 Detergent I single wash 0.62 1.33 2.5 4.02 5.4 Detergent II only washing 0.64 1.35 2.65 4.12 5.49 Detergent I + 0.05% Tinolux BMC Spray 0.65 1.45 3.25 4.79 6.05 Detergent II + 0.05% Tinolux BMC Spray 0.6 1.47 3.45 4.82 6.13

As shown in Table 8, the effect of the photoactivator under general washing conditions is almost similar to that of the conventional spraying, so that the granules applied with the complex salt are dissolved and the photoactivator is uniformly dyed on the fiber surface to exert the effect. Able to know.

Light bleaching effect test result (light bulb drying test result) 1 time Episode 2 3rd time 4 times 5 times Detergent I A 0.81 2.65 5.36 7.98 10.52 Detergent I B 0.83 2.82 5.36 8.02 10.23 Detergent I C 0.79 2.95 5.55 7.92 10.02 Detergent I D 0.85 2.65 5.32 8.05 10.52 Detergent I E 0.92 2.78 5.36 8.12 10.25 Detergent I F 0.86 2.98 5.46 7.95 9.96 Detergent I G 0.90 2.62 5.56 8.03 10.62 Detergent I H 0.91 2.91 5.65 7.85 10.71 Detergent I I 0.82 2.85 5.32 7.92 10.21 Detergent I J 0.86 2.79 5.66 7.92 10.62 Detergent I K 0.85 2.98 5.46 7.86 9.85 Detergent I L 0.91 2.91 5.65 8.10 10.25 Detergent I M 0.88 2.86 5.75 8.09 10.65 Detergent I N 0.80 2.95 5.24 8.05 10.25 Detergent I O 0.79 2.96 5.36 7.96 9.89 Detergent I P 0.80 2.86 5.36 7.83 10.32 Detergent I Q 0.81 2.65 5.67 7.92 9.89 Detergent I R 0.82 2.89 5.55 7.93 10.25 Detergent I S 0.91 2.85 5.46 8.09 10.85 Detergent I T 0.87 2.65 5.36 8.12 10.21 Detergent II A 0.92 2.65 5.35 7.92 9.85 Detergent II B 0.95 2.87 5.26 8.02 10.2 Detergent II C 0.89 2.92 5.52 7.93 9.86 Detergent II D 0.9 2.65 5.32 7.92 10.25 Detergent II E 0.85 2.75 5.36 7.85 10.12 Detergent II F 0.92 2.98 5.46 8.05 10.52 Detergent II G 0.88 2.65 5.35 7.91 10.35 Detergent II H 0.87 2.79 5.7 7.69 10.65 Detergent II I 0.82 2.86 5.65 8.05 10.67 Detergent II J 0.85 2.65 5.47 7.95 10.45 Detergent II K 0.82 2.93 5.65 7.93 10.25 Detergent II L 0.87 2.75 5.56 7.65 9.89 Detergent II M 0.86 2.67 5.35 8.02 9.99 Detergent II N 0.91 2.69 5.42 7.96 10.25 Detergent II O 0.89 2.65 5.32 7.86 10.36 Detergent II P 0.87 2.63 5.24 7.95 10.75 Detergent II Q 0.82 2.85 5.36 7.82 10.37 Detergent II R 0.92 2.65 5.25 7.93 10.26 Detergent II S 0.79 2.68 5.32 7.94 10.42 Detergent II T 0.82 2.54 5.36 7.99 10.25 Wash with water only without detergent 0.72 1.16 2.33 3.48 4.78 Detergent I alone 0.61 2.06 3.99 6.17 8.27 Detergent II only 0.68 2.09 4.2 6.15 8.35 Detergent I + 0.05% Tinolux BMC Spray 0.81 2.6 5.35 7.95 10.1 Detergent II + 0.05% Tinolux BMC Spray 0.79 2.57 5.27 7.8 9.9

Table 9 was performed to compare the effect of the photoactivator in the sunlight, drying process of the actual consumer and Table 8, as shown in the table, the effect of the photoactivator in general washing conditions is almost similar to the conventional spraying Accordingly, it can be seen that the granules to which the complex salt is applied are dissolved and the photoactivator is uniformly dyed on the fiber surface to exert the effect.

(3) solubility test

1 g of the photo-bleaching ingredient-containing granules was placed in 1 L (1% concentration, 15 ° C.) of each detergent solution of Terg-O-tometer and stirred at 120 rpm. The sample solution was taken every minute and the absorption wavelength was measured at 672 nm with a spectrophotometer.

In the present invention, the soluble photobleaching component-containing granules have a dissolution rate of 90% or more within 3 minutes.

Solubility Test Results Granule composition Dissolution rate (3 minutes) (%) Detergent I A 95 Detergent I B 98 Detergent I C 95 Detergent I D 96 Detergent I E 98 Detergent I F 94 Detergent I G 93 Detergent I H 98 Detergent I I 97 Detergent I J 95 Detergent I K 94 Detergent I L 98 Detergent I M 95 Detergent I N 91 Detergent I O 98 Detergent I P 95 Detergent I Q 92 Detergent I R 96 Detergent I S 97 Detergent I T 92 Detergent II A 89 Detergent II B 91 Detergent II C 90 Detergent II D 93 Detergent II E 96 Detergent II F 92 Detergent II G 90 Detergent II H 91 Detergent II I 94 Detergent II J 92 Detergent II K 91 Detergent II L 90 Detergent II M 94 Detergent II N 91 Detergent II O 91 Detergent II P 90 Detergent II Q 91 Detergent II R 93 Detergent II S 92 Detergent II T 95

As shown in Table 10, it can be seen that most of the complex salt granulation compositions have excellent dissolution rates within 3 minutes, and in the case of the detergent base, the application of the detergent I is superior to that of the detergent II.

The detergent composition of the present invention comprises a complex salt produced by the reaction of the photobleaching component with a cationic surfactant, and more specifically, dissolves uniformly and quickly under general washing conditions while preventing the photobleaching component from dyeing into the fiber. It provides a detergent composition with enhanced adsorptivity to the fiber can be usefully used in a variety of laundry applications.

1 is a view showing the absorbance of the complex salt preparation prepared according to Example 1,

2 is a view showing the absorbance of the complex salt preparation prepared according to Example 2,

3 is a view showing the absorbance of the complex salt preparation prepared according to Example 3,

Figure 4 is a view showing the absorbance of the zinc phthalocyanine tetrasulfonate sodium salt aqueous solution for comparison.

Claims (10)

A granulation composition for preventing dyeing stains for granular detergent addition, comprising a complex salt obtained by reacting a photobleaching component having a water-soluble anionic substituent and a cationic surfactant, and a binder. The granular composition for granular detergent anti-staining laundry according to claim 1, wherein the photobleaching component having a water-soluble anionic substituent is a metal porphyrin, a metal phthalocyanine, a metal naphthalocyanine, or a mixture thereof. The granular composition for granular detergent addition anti-staining laundry according to claim 2, wherein the metal phthalocyanine components are zinc phthalocyanine sulfonate and aluminum phthalocyanine sulfonate. According to claim 1, wherein the cationic surfactant is quaternary ammonium represented by the following general formula (1), (2) or 3, granular detergent additives stain-free laundry granules composition for washing. <Formula 1> (Wherein R ₁ is a substituted or unsubstituted alkyl group or alkenyl group having 8 to 22 carbon atoms, R ₂ is a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms, X is a halogen atom, acetate, phosphate, nitrate, Or methylsulfate) <Formula 2> Wherein R ₁ and X are as defined above. <Formula 3> Wherein R ₃ is hydrogen or a substituted or unsubstituted alkyl group or alkenyl group having 1 to 22 carbon atoms, R ₄ is a substituted or unsubstituted alkyl group or alkenyl group having 8 to 22 carbon atoms, R ₅ and R ₆ are carbon atoms 1-4 alkyl groups, X represents a halogen atom, acetate, phosphate, nitrate, or methylsulfate) The anti-detergent staining laundry of claim 1, wherein the cationic surfactant is an ester of a quaternary ammonium compound and has at least one long-chain hydrophobic alkyl or alkenyl group substituted by a carboxyl group. Granule composition for. The method according to claim 1, wherein the cationic surfactant is 1-methyl-1-[(steroylamido) ethyl] -2-octadecyl-4,5-dihydroimidazolinium chloride, 1-methyl- 1-[(oleylamido) ethyl] -2-oleyl-4,5-dihydroimidazolinium methyl sulfate, 1-methyl-1-[(tallowamido) ethyl] -2-tallow- 4,5-imidazolinium chloride, 1-methyl-1-[(palmitoylamido) ethyl] -2-octadecyl-4,5-dihydroimidazolinium chloride, 1-methyl-1- [ (Steroylamide) ethyl] -2-octadecyl-4,5-dihydroimidazolinium chloride or 1-methyl-1-[(hydrogenamido) ethyl] -2-hydrogen tallow-4 , 5-imidazolinium chloride, granular detergent additives stain preventing stain for washing granules, characterized in that at least one selected from the group consisting of. The method of claim 1, wherein the cationic surfactant is selected from the group consisting of tallow trimethyl ammonium chloride; Ditallow dimethyl ammonium chloride; Ditallow dimethyl ammonium methyl sulfate; Dihexadecyl dimethyl ammonium chloride; Di (hydrogenated tallow) dimethyl ammonium chloride; Dioctadecyl dimethyl ammonium chloride; Distearyldimethylammonium chloride; Diicosyl dimethyl ammonium chloride; Didocosyl dimethyl ammonium chloride; Di (hydrogenated tallow) dimethyl ammonium methyl sulfate; Dihexadecyl diethyl ammonium chloride; Dihexadecyl dimethyl ammonium acetate; Ditallow dipropyl ammonium phosphite; Ditallow dimethyl ammonium nitrate; And di (coconut-alkyl) dimethyl ammonium chloride. At least one selected from the group consisting of granular detergents. According to claim 1, wherein the oil absorbent is at least one selected from the group consisting of sulphate, carbonate, silicate, and clay granule detergent additives stain preventing stain for washing granules composition. The nonionic surfactant of claim 1, wherein the binder is a nonionic surfactant. Granules composition for preventing granular detergent additives, characterized in that at least one selected from the group consisting of polyethylene glycol. The granules composition for dye-staining anti-staining laundry of claim 1, further comprising at least one detergent auxiliary component selected from the group consisting of a fluorescent brightener and an antifoaming agent.