JP2859263B2 - Stable liquid detergent composition containing a hydrophobic brightener - Google Patents

Abstract

Stable isotropic liquid laundry detergents containing a surfactant and a hydrophobic brightener to reduce brightener staining of fabrics. Suitable species of preferred hydrophobic brighteners include disulfonated tetra-anilino naphthotriazolyl stilbene brighteners.

Description

Description: TECHNICAL FIELD The present invention relates to a stable whitening agent containing a specific hydrophobic disulfonate brightener that reduces or eliminates fabric whitening while maintaining an excellent level of whitening. And preferably a single-phase, isotropic liquid laundry detergent. Disulfonated tetra-anilinonaphthotriazolyl stilbene brighteners are particularly preferred. In some embodiments, the hydrophobic brighteners of the present invention may be combined with variable amounts of conventional liquid detergent brighteners to further improve and optimize the overall fabric appearance. If such mixed brighteners are used, the hydrophobic brighteners of the present invention should make up at least about 40% of the total brightener to provide the desired performance benefits. Optical brighteners, also known as fluorescent brighteners, are commonly used in laundry detergents. The brightener adheres to the fabric where it absorbs ultraviolet radiant energy and re-emits as blue. This reduces or eliminates the yellowish tint to the fabric and gives the fabric a more brightened appearance. However, undesirable whitening stains can occur when the liquid detergent comes into direct contact with the line-containing fabric. The present invention
Such smearing is reduced or eliminated while maintaining an acceptable level of fabric whitening. BACKGROUND ART Substantial efforts have been directed toward using asymmetric monosulfonated naphthotriazolyl stilbene brighteners (MSB) to overcome and reduce unwanted brightener stains. A representative example of these technical work is a series of published patents. GB 2,028,365 discloses a builder liquid detergent containing an anionic surfactant and one or more whitening agents including MSB. U.S. Pat. No. 3,812,041 discloses a builder-free liquid detergent containing a nonionic surfactant and an anionic surfactant in a weight ratio of at least one nonionic surfactant body anionic surfactant. . Optional whitening agents
MSB type can be mentioned. U.S. Pat. No. 3,959,157 discloses a liquid detergent containing a nonionic surfactant, a quaternary ammonium softener and also an optional brightener, including MSB. U.S. Pat. No. 4,430,236 discloses a liquid detergent containing a non-ionic surfactant, an optional anionic surfactant, hydrogen peroxide, a whitening agent, preferably a quaternary ammonium softening compound. The MSB is specified as useful. JP 4917004 discloses a liquid detergent containing MSB, which is said to be stable to light. German Patent Application No. 2543998 discloses a clear liquid detergent containing a specific diphenyldistyryl brightener. Examples 1 and 2 relate to liquid detergents containing a mixture of MSB and disulfonated brightener. EP-A-85200988.5, filed June 21, 1985, describes the use of MSB for the purpose of reducing unwanted brightener deposits, optionally with the usual di-anilinodi-morpholinodidistilbene brighteners. It is taught to be used together. While these prior art attempts can provide significant improvements over conventional brighteners in reducing stains, their cleaning performance, e.g., maintaining whiteness, is not compatible with current disulfonate brighteners. No better than that obtained from the agent. The main object of the present invention is to provide a whitening agent-containing heavy-duty liquid detergent composition which does not show the inconvenience of whitening agent during use while providing at least equivalent whiteness maintenance as compared with ordinary detergent whitening agents. Is to prescribe things. These and other objects can now be achieved by incorporating a disulfonated brightener in a heavy duty liquid detergent that is more hydrophobic than current disulfonated brighteners. SUMMARY OF THE INVENTION The present invention relates to a composition comprising: (a) a surfactant selected from anionic surfactants, nonionic surfactants, and mixtures thereof, by weight;
%, And (b) from about 0.01% to about 1% of a hydrophobic disulfonated brightener of the formula comprising at least 40% of the total brightener in the composition: About: (Wherein R ₁ , R ₂ , R ₃ and R ₄ are independently selected and represent anilino, cyclohexylamino, piperazino, phenylenediamino, toluenediamino, morpholino, and aminophenol, provided that the brightener is 1 or less Morpholino group). DETAILED DESCRIPTION OF THE INVENTION The compositions of the present invention comprise 3% to 60% of a surfactant and 0.01% to about 1% of a hydrophobic brightener. The essential components of the present invention and optional components that can be desirably incorporated into the composition of the present invention are described below. Percentage designations mean "% by weight" throughout the specification unless otherwise indicated. The hydrophobic brightener of the present invention has the formula: (Wherein R ₁ , R ₂ , R ₃ and R ₄ are independently selected and represent anilino, cyclohexylamino, piperazino, phenylenediamino, toluenediamino, morpholino, and aminophenol, provided that the brightener is 1 or less Morpholino group). If less than one morpholino group is present, suitable brightener species include any possible combination of R _1-4 moieties. Examples of preferred brightener species are tetra-anilino, tetra-piperazino, tetra-cyclohexylamino and combinations thereof, such as di-anilinodipiperazino; and dianilino-dicyclohexylamino species. The following formula: 4,4'-bis ((4-anilino-6-anilino-s-
Tetraanilino derivatives with triazin-2-yl) amino) -2,2'-stilbene disulfonic acid sodium salt (A) are highly preferred because they minimize brightener stain. Preferred whitening systems in the context of the present invention are at least 40% (detergent whitening) of the specific hydrophobic whitening agents mentioned above in combination with conventional detergent whitening agents, for example disulfonated dianilinodidimorpholinostilbene whitening agents. (Based on the total amount of the agent). Conventional detergent brighteners for use with the hydrophobic species include common detergent brighteners, including: 4- (2H) -naphtho (1,2-d) triazole-2-.
Yl) -2-stilbenesulfonic acid sodium salt;
(I) 4,4'-bis ((4-anilino-6 (N-2-hydroxyethyl-N-methylamino) -s-triazine-2
-Yl) amino) -2,2'-stilbene disulfonic acid disodium salt; (ii) 4,4'-bis ((4-anilino-6-morpholino-s
(Triazin-2-yl) amino) -2,2'-stilbene disulfonic acid sodium salt; (iii) 2,2 '-(4,4'-biphenylenedivinylene) -dibenzenesulfonic acid disodium salt; (iv ) 4,4'-bis (4-phenyl-2H-1,2,3-triazol-2-yl) disodium salt; (vi) 4,4'-bis ((4-anilino-6-morpholino-1) ,
3,5-Triazin-2-yl) amino) -2-stilbenzenesulfonic acid sodium salt (vii) The hydrophobic whitening agent will make up at least 40% of the total whitening agent, but the amount is usually It will be understood that these can be varied depending on the specific nature of the brightener. As an example, the tetra-anilino hydrophobic brightener can desirably comprise 55% to 80% of the total brightener if the conventional brightener is represented by (i). Surfactants can be formed by anionic surfactants, nonionic surfactants and mixtures thereof.
Surfactants are usually from 3% to 60%, preferably from 10% to 50%.
Make up%. Suitable anionic surfactants are described in U.S. Pat.
No. 285,841 and U.S. Pat. No. 3,929,678. Useful anionic surfactants include water-soluble salts of organic sulfuric acid reaction products having an alkyl group having about 10 to about 20 carbon atoms and a sulfonate or sulfate group in their molecular structure, especially alkali metal Salts, ammonium salts and alkylol ammonium salts (eg, monoethanolammonium or triethanolammonium salts) are included (the term "alkyl" includes the alkyl portion of the aryl group). Examples of this class of synthetic surfactants are by sulphating alkyl alcohols, especially higher alcohols (C ₈ -C ₁₈ carbon atoms) such as those obtained by reducing the glycerides of tallow or coconut oil. And alkyl benzene sulfonates in which the alkyl group has from about 9 to about 15 carbons in a straight or branched configuration, such as those described in U.S. Pat.
It is of the type described in the specifications of EP 099 and 2,477,383. Of particular value are linear linear alkyl benzene sulfonates having an average number of carbon atoms in the alkyl group of about 11 to 14. Other anionic surfactants of the present invention contain from about 8 to about 9 carbon atoms.
Paraffin sulfonic acid, alkyl glyceryl ether sulfonic acid having 24 (preferably about 12-18), especially C
Ethers of _8-18 alcohols (such as those derived from tallow and coconut oil) contain from about 1 to about 4 units of ethylene oxide per molecule and contain about 10 to 10
Water-soluble salts of alkyl phenol ethylene oxide ether sulfates having up to about 20 carbon atoms. Other anionic surfactants useful in the present invention include alpha-sulfonated fatty acids having about 6 to about 20 carbon atoms in the fatty acid group and about 1 to 10 carbon atoms in the ester group. Water-soluble salts of esters of the formula: water-soluble salts of 2-acyloxyalkane-1-sulfonic acids having about 2 to 9 carbon atoms in the acyl group and about 9 to about 23 carbon atoms in the alkane moiety A water-soluble salt of an olefin sulfone salt having about 12 to 24 carbon atoms; and β- having about 1 to 3 carbon atoms in the alkyl group and about 8 to 20 carbon atoms in the alkane moiety. Alkyloxyalkanesulfonates are mentioned. Preferred anionic surfactants are C ₁₀ -C ₁₈ alkyl sulfates, C ₁₁ -C ₁₃ linear alkylbenzene sulfonates, and mixtures thereof containing alkyl sulfate per mole average 0 to about 4 ethylene oxide units. Nonionic surfactants are notably well known in the art and many can be represented by known ones that have found extensive commercial acceptance. Ethoxylated nonionic surfactants suitable for use in the present invention are of the formula R
¹ (OC ₂ H ₄ ) _n OH wherein R ¹ is a C ₁₀ -C ₁₆ alkyl group or C
₈ -C ₁₂ alkyl phenyl radical, n has from about 3 to about 9), the non-ionic surfactant having a HLB (hydrophilic lipophilic balance) from about 10 to about 13. These surfactants are described in detail in U.S. Pat. Nos. 4,285,841 and 4,284,532. C ₁₂ -C ₁₅ Alcohol 1
Condensates of about 3 to about 8 moles of ethylene oxide per mole, such as an alcohol per mole to about 6.5 moles of C ₁₂ -C ₁₃ alcohols engaged ethylene oxide condensed is particularly preferred. The well-known nonionic surfactant used in the present invention is C ₁₂
Can be represented by amine oxide surfactants such as -C ₁₆ alkyl dimethyl amine oxide. Amine oxide surfactants are often from 0.5% to 4% in combination with conventional ethoxylated nonionic surfactants.
Used in% amount. In such nonionic systems, amine oxides include:
The weight ratio of nonionic ethoxylate is often from 1: 8
Within the range of 1:50. The compositions can be based on all anionic surfactants or all non-ionic surfactant combinations, but often include anionic and non-ionic surfactants in a weight ratio of 1: 1 to 3: 1. It is desirable to use them in a ratio. In this weight ratio expression, the nonionic surfactant can be represented by a mixture of a nonionic ethoxylate and an amine oxide surfactant. The composition may also contain, in addition to the above essential surfactants, optionally other synthetic surfactants known in the art, such as cationic surfactants, zwitterionic surfactants and amphoteric surfactants. These optional surfactants can be used in additive amounts and should generally make up less than 40% of the total surfactant in the formulation. Preferred examples of these optional surfactants include:
It is disclosed in U.S. Pat. Nos. 4,285,841 and 3,929,678. The composition is an aqueous composition and, depending on the relative amounts of the essential components and the possible amounts of the optional components, contains an amount of water which constitutes the balance to 100%. In some preferred heavy duty liquid formulations of the present invention, the amount of water is
% Can be in the range of 20%. Compositions of the invention often have a pH in the neutral to mildly alkaline range, as measured in a 1% aqueous solution at 20 ° C., ie, pH
6.5 to 9. In addition to the above essential ingredients, the compositions often contain a series of optional ingredients that are used in conventional amounts for their known functions. These optional ingredients generally increase and enhance the detergent performance of the composition. Examples of such optional ingredients include fragrances, dyes, opacifiers, bactericides, antioxidants; antifoaming agents such as silicones, hydrogenated fatty acids; builders such as tartrate monosuccinic acid, sodium tripolyphosphate and pyrophosphoric acid Sodium; citric acid; fully hydrated zeolites having a particle size of 1-10 microns; and alkenyl succinates having 10-16 carbon atoms in the alkenyl moiety. Still other optional components include soil release agents such as polyethylene glycol terephthalate, performance enhancers such as tetraethylenepentamine having 15 to 19 EO, corrosion inhibitors such as aminosilane, enzymes, cationic surfactants, and fabric softeners. Examples include agents such as quaternary ammonium salts and bentonite clay, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, fatty acids, alkylene polyaminopolyalkylene phosphonic acids, enzyme stabilizing systems, and liquid matrix components such as water and suitable solvents. Suitable saturated or unsaturated fatty acids have 10
It has up to 18 carbon atoms. Unsaturated species having 12 to 18 carbon atoms in the alkyl chain are preferred, with oleic acid being most preferred. The corresponding soap can be used equally. Optional fatty acids / soaps are used in amounts up to 20%, often from 5% to 15%. Detergent enzymes generally facilitate and increase certain stain removal. Suitable enzymes are proteases, amylases,
It can be represented by lipase, glucose-oxidase, cellulase or a mixture thereof. Peptases and amylases are preferably used in the liquid concentrate compositions of the present invention. They are often from about 0.01% to about 2%.
Used in% amount. All generally known enzyme stabilization systems can be used in the compositions in art-established amounts. Examples of suitable stabilizing systems, optionally in combination with a polyol, a short chain C _{1 to 4} carboxylic acid, Tokunigisan (in combination with small amounts of calcium), boric acid, and their water-soluble salts . Suitable alkylene-polyaminopolyalkylenephosphonic acids for use in the present invention include ethylenediaminetetramethylenephosphonic acid, diethylenetriaminepentamethylenephosphonic acid, or salts thereof. These polyphosphonates are advantageously from 0.1% to 3%.
%, Preferably from 0.4% to 1.2%; and also preferred tetra- and penramethylene phosphonate species, in combination, for example, a 3: 1 weight ratio of tetra to penta.
Available from 1: 3. Detergent foaming agents that can be used in the present invention include hydrogenated fatty acids having 16 to 22 carbon atoms in the alkyl chain and alkylated polysiloxanes such as dimethylpolysiloxane. Fatty acid antifoams are often used in amounts of 0.5 to 5%, while silicones are effectively used at 0.05 to 5%.
It can be used in an amount in the range of 0.5%. The foam control agent can also be formed by a combination of a hydrogenated fatty acid and silicone. In the presence of oxidizing substances, the composition may also contain art-established amounts, i.e. 0.01% to 0.25% (based on the total composition) of known antioxidants. These antioxidants are often introduced together with unsaturated organic acids.
Many suitable antioxidants are readily known and available for that purpose, but 2,6-di-t-butyl-p-cresol, more commonly known as butylated hydroxytoluene BHT, and 2-t -Butyl-4-hydroxyanisole is particularly preferred for use in the composition. Other suitable antioxidants are 4,4'-thiobis (6-tert-butyl-m
-Cresol) and 2-methyl-4,6-dinonylphenol. Builders such as sodium tripolyphosphate, sodium pyrophosphate, tartrate monosuccinic acid, citric acid, C ₁₂ -C ₁₆ alkenyl succinate, zeolite A, or combinations thereof which are fully hydrated having a particle size 1~10μ is , Often used in an amount of 2% to 25%. Chelating agents such as alkylene polyamino-polyalkylenes of the polycarboxylic and / or polyphosphonic acid type are often used in amounts of 0.1 to 3%. Known fabric softeners such as ditallow dimethyl ammonium and imidazolinium salts and bentonite clays (such as those known from DE-PS 2334899) are also
It can be used depending on the intended function of the composition. Softeners, if present, can typically comprise 2% to 8%. The liquid matrix component is yet another optional component in the composition. This component, together with the water, can constitute a solvent matrix for, for example, a concentrated liquid formulation. Suitable component types include 2-6 carbon atoms and 1-3
Lower aliphatic alcohols having one hydroxyl group, ethers of diethylene glycol and lower aliphatic monoalcohols having 1 to 4 carbon atoms. Specific examples of phase modifiers are ethanol; n-propanol; isopropanol; butanol; 1,2-propanediol; 1,3-propanediol; monomethyl ether, ethyl ether, propyl ether and monobutyl ether of diethylene glycol. The liquid matrix components can be used in different amounts depending, for example, on the total amount of the components in the composition. In the concentrated HDL formulations of the present invention, the liquid solvent is between 5% and 3%.
0% can be achieved. The concentrated heavy-duty liquid compositions of the present invention constitute a preferred formulation of the present technology. These compositions can have the following formula: Example I The tendency of various brighteners to stain fabric is evaluated in the following compositions. Ingredient wt% C ₁₂ linear alkyl benzene sulfonate 10.0 C _{12 to 14} alkyl sulfate 3.0 C _{14 to 15} alcohol polyethoxylate (7 EO) 12.0 C _{12 to 14} fatty acids 11.0 Oleic acid 4.0 Citric acid (anhydrous) 1.0 Diethylenetriamine pentamethylene phosphonic acid 0.8 triethanolamine 6.0 sodium hydroxide to pH 7.7 3.4 propylene glycol 1.6 ethanol 6.0 alkaline protease (1.5AU / g) 0.9 formic acid 0.66 alpha-amylase (300KAU / g) 0.1 brightener 0.175 trace ingredients and water remaining portion 100 Apply the undiluted (as is) detergent sample containing the laundry whitening agent to an unwhitened 100% cotton swatch and let stand for 10 minutes. The samples are then washed with the same detergent solution (1% product concentration, 30 ° C., mild stirring) and tumbled dry. The samples are then graded under UV light for brightener stain using the following scale. 0 No visible stain T Traces of stain 1.0 Very slight stain 1.5 Minor stain 2.0 Medium stain 2.5 Medium stain 3.0 Heavy stain The results are as follows. The above results confirm the reduced brightener stain of the tetra-anilino brightener (A) of the present invention on a wide variety of fabrics. The superiority of brightener deposition during the washing operation is demonstrated in a complementary manner by brightener build-up measurements. Brightener accumulation refers to the rate at which the brightener deposits on brightened and unbleached swatches. The accumulation measurement is performed as follows. Test conditions: Miele W765, short cycle at 60 ° C, product usage 180 ml (1% product concentration), ballast load = bleached (9
Washed with perborate / STPP at 0 ° C), 2 kg 100% non-whitened cotton. Tracer: Unblanched terry = perborate / S by 90 ° C
Unbleached unbrightened terry bleached by one wash with TPP; bleached terry = bleached brightened terry washed 5 times with HDD at 90 ° C. Measurement: re-emission 440 nm unbrightened terry start: 83.88 re-emission 440 nm blush terry start: 149.13 Result: re-emission 440 nm Example II An additional liquid composition according to the present invention contains the following ingredients: % By weight C ₁₂ linear alkylbenzene sulfonic acid 6 C ₁₃ -C ₁₅ oxo alcohol 3 C ₁₂ -C ₁₄ fatty diethanolamide 2 sodium tripolyphosphate 23 carboxymethyl cellulose 0.3 carboxymethyl cellulose 0.3 hydrogenated fatty acid (C ₁₈ -C ₂₂ 1) Polydimethylsiloxane 0.2 Brightener (see below) 0.15 to 0.20 Proteolytic enzyme (1.5 AU / g standard) 0.5 Glycerin 5 Sodium tetraborate 2 Sodium hydroxide (1% solution) to adjust pH as right 9.0 Optional Ingredients such as Fragrances and Whitening Agents 1 Brighteners are (a) A, (b) a mixture of A and vii (1: 1 by weight) and (c) a mixture of A and iii (9 by weight) :
Represented by 1). (1) Details are described in European Patent No. 85202053.6 filed on December 12, 1985.

   ────────────────────────────────────────────────── ─── Continuation of front page    (72) Inventor John, Richard, Walker               Waterloo, Abnu, Belgium               De, petit, shan, 34                (56) References JP-A-58-132099 (JP, A)

Claims (1)

(57) [Claims] (A) about 3% to about 60 surfactant comprising a mixture of anionic surfactant and nonionic surfactant in a weight ratio of anionic surfactant: nonionic surfactant of 1: 1 to 3: 1.
%; However, the anionic surfactant, C ₈ -C ₁₈ alkyl sulfates, C ₉ -C ₁₅ alkyl benzene sulfonates, C ₈ -C ₂₄ paraffin sulfonates, C ₈ -C ₁₈ alkyl glyceryl ether sulfonates, C ₁₀ -C ₂₀ alkylphenyl ether sulfate, α-sulfonated C ₆ -C ₂₀
Fatty esters, having 2 to 9 carbon atoms in the acyl group and having carbon atoms of 9-23 in the alkane moiety 2- acyloxyalkanesulfonate 1-sulfonate, C ₁₂ -C ₂₄ olefin sulfonates, the alkyl group Β-alkyloxyalkanesulfonates having 1 to 3 carbon atoms and 8 to 20 carbon atoms in the alkane moiety, or mixtures thereof, wherein the nonionic surfactant is an ethoxylated C _10- C ₁₆ fatty alcohols, ethoxylated C ₈ ~
C ₁₂ alkylphenol, C ₁₂ -C ₁₆ alkyl amine oxides, or mixtures of these; about hydrophobic disulfonated brightener of the formula which forms at least 40% of the total brightener in and (b) compositions 0.01% to about 1%; a liquid aqueous heavy-duty detergent composition comprising: (Wherein R ₁ , R ₂ , R ₃ and R ₄ are independently selected and represent alinino, cyclohexylamino, piperazino, phenylenediamino, toluenediamino, morpholino or aminophenol, provided that the brightener is 1 or less Morpholino group). 2. The hydrophobic brightener wherein the R _1-4 moieties are represented by those selected from the group of tetra-anilino, tetra-piperazino, tetra-cyclohexylamino, dianilino-dipiperazino, and dianilino-dicyclohexylamino. A composition according to claim 1. 3. 2. The composition according to claim 1, wherein the surfactant comprises 10 to 50% by weight. 4. 4. The composition according to claim 3, wherein the hydrophobic brightener is represented by a tetra-anilino derivative present in an amount of 0.07 to 0.3% by weight. 5. The nonionic surfactant is represented by a combination of nonionic ethoxylate and amine oxide in a weight ratio of ethoxylate to amine oxide of 50: 1 to 8: 1,
The composition according to claim 1. 6. The whitening agent is represented by a mixture of a hydrophobic whitening agent and a conventional detergent whitening agent, and the hydrophobic whitening agent is a total whitening agent;
That is, at least 40 of the sum of the hydrophobic brightener and the normal brightener.
2. The composition according to claim 1, wherein the composition constitutes% by weight. 7. The usual brightener is 4,4'-bis ((4-anilino-
6-morpholino-1,3,5-triazin-2-yl) amino) -2-stilbene sulfonic acid sodium salt,
7. The composition according to claim 1 or claim 6. 8. The following formula: Surfactant 10-50% by weight Builder 2-25% by weight Chelating agent 0.1-3% by weight Enzyme (a) Protease 0.1-1.5% by weight (b) Amylase 0.05-0.8% by weight Hydrophobic brightener 0.01 to 1% by weight Water 70 to 20% by weight Solvent 3 to 30% by weight, characterized by having a liquid concentrated heavy duty detergent composition: wherein the surfactant is an anionic surfactant: nonionic surfactant the weight ratio of the agent from 1: 1 to 3: consists of a mixture of one anionic surfactant and a nonionic surfactant, the anionic surfactant herein may, C ₈ -C ₁₈ alkyl sulfates, C ₉ ~ C ₁₅ alkylbenzene sulfonates, C ₈ -C
₂₄ paraffin sulfonate, C ₈ -C ₁₈ alkyl glyceryl ether sulfonate, C ₁₀ -C ₂₀ alkyl phenyl ether sulfate, α-sulfonated C ₆ -C ₂₀ fatty acid ester, having 2 to 9 carbon atoms in the acyl group, and 2 acyloxyalkanesulfonate 1-sulfonate having carbon atoms of 9-23 in the alkane moiety, C ₁₂ -C ₂₄ olefin sulfonates having 1 to 3 carbon atoms in the alkyl group and the alkane moiety 8-20 β- alkyloxy alkane sulfonates carbon atoms, or selected from a mixture thereof, said nonionic surfactants are ethoxylated C ₁₀ -C ₁₆ fatty alcohols, ethoxylated C ₈ -C ₁₂ alkylphenols, C ₁₂ ~ Selected from C ₁₆ alkylamine oxides, or mixtures thereof; and the hydrophobic brightener is a hydrophobic brightener of the formula Disulfonated brighteners are: (Wherein R ₁ , R ₂ , R ₃ and R ₄ are independently selected and represent anilino, cyclohexylamino, piperazino, phenylenediamino, toluenediamino, morpholino or aminophenol, provided that the brightener is 1 or less Morpholino group). 9. 9. The composition according to claim 8, wherein the hydrophobic brightener is represented by a tetra-anilino derivative present in an amount of 0.07 to 0.3% by weight.