JPS5842699A - Detergent composition for clothes - Google Patents

Abstract

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

Description

[Detailed description of the invention]

-, the present invention relates to a laundry detergent composition. More specifically, the present invention relates to a laundry detergent composition containing a specific heptad-merocyanide complex and a specific fluorescent dye as essential components, and is suitable for enhancing and maintaining the desirable white discoloration of white goods. Recently, I-9 phosphate, which has traditionally been used as a building block for detergents, has become subject to stricter regulations due to its impact on environmental pollution. Ki1gK instead of 4
The current situation is that the cleaning performance of detergents is gradually decreasing. When white clothes are washed in 41, they are not finished white and it is recognized that the cleaning performance of the detergent has deteriorated. Conventionally, as a means of compensating for such a decrease in cleaning performance, a bleaching effect is imparted by adding an oxygen bleaching agent such as sodium perborate or soda percarbonate to a detergent composition. However, since these oxygen-based bleaches are unstable to water, heavy metal ions, heat, etc., it is not possible to obtain a detergent composition that stably maintains the Illllll properties, and the washing S white is always In addition, such oxygen-based bleaches are used as cleaning effect-enhancing ingredients because they promote enzyme separation and are used in detergent-acid based detergents containing snt. In addition, as a whitening agent component, JP-A No. 48-9100 contains sulfone bizinc fouricyanine, etc.
The s-ttpiat issue contains sulfonated aluminum phthalocyanine, a photosensitizer with a bleaching effect, and a koji detergent combination acid.However, since these photosensitizers act sufficiently, It requires a large amount of light, and if the amount of light irradiation is small, the bleaching effect will not be achieved, and the green to W color hue of the photosensitizer itself will remain, making it difficult to wash clothes. It has the disadvantage of impairing the whiteness of the upper garment.In general, white fabrics are treated with fluorescent dyes to increase their whiteness, but some of the fluorescent dyes disappear when they are made into actual clothing and washed. It is known that when exposed to sunlight, chemical decomposition occurs and the whitening effect is no longer exhibited.Ninth, to compensate for this, fluorescent dyes are included in detergent compositions to improve the washing process. It has been conventional practice to sometimes replenish fluorescent dyes to clothing. However, in addition to the fact that fluorescent dyes do not have good light resistance, even if a large amount of fluorescent dyes is used, the fluorescent dyes may Even if the color of the detergent itself is gray and its harmful effects are not affected, the amount added to the detergent composition is limited (for economic reasons), and its whitening effect or whitening replenishment effect is not necessarily satisfactory. In view of the technical problems associated with these heavy-duty laundry detergents, the present inventors have developed a laundry detergent composition that has whitening and bleaching effects sufficient to compensate for the decline in cleaning effectiveness of recent detergents. As a result of intensive research into the development of white goods, we have found that by containing a specific 7-U cyanine compound and a specific fluorescent dye as essential ingredients within a specific range of amounts, the whitening of white clothing can be significantly enhanced. However, it was discovered that a laundry detergent and a composition that can stably maintain the white discoloration were obtained, leading to the present invention.That is, the laundry detergent composition according to the present invention has the following ) sulfonated aluminum 7 talocyanine 0
．． 0001 to 0.2% by weight and the following formula (1), (
1) One or more compounds selected from the group consisting of compounds (a) to (e) shown in (1, (V), (6)) or F12
Tob, the sulfonated aluminum? The weight ratio of talocyanine and fluorescent dye is preferably 1:1 to 1:500 (in the formula -(
EiO is a sulfone group or a sulfonate group substituted on the benzene nucleus of riharathalocyanine, X is H or an alkali metal ion or an ammonium ion, sb,
n is the number of substituents, n=1 to 4 (preferably S
~4). In the formula, + is the charge of A7m), and I is its counter ion (oj-, etc.). ] (a) 4.4'-bis-(2-sulfostyryl)-biphenyl (M in the formula represents a hydrogen atom, an ammonium ion, an alkali metal ion or an amine residue) (b) 4.4'-
bis-(4-chloro-3-sulfos (the wing in the formula has the same meaning as above) fi2-(styrylphenyl)naphthothiazo-(in the formula R
yo is hydrogen or chlorine, M#i, same as in l-)) 4.
4'-bis(triazol-2-yl)stilbene derivative (in the formula, M is the same as above) (e) Bis(triazinylamino)stilbene disulfonic acid derivative (M is the same as above) For clothing according to the present invention In addition to the above-mentioned sulfonated aluminum phthalocyanino and fluorescent dye, the detergent composition may contain the following detergent ingredients, but there are no particular restrictions on these, and nine combinations may be made depending on the purpose. good. [1] Surfactant ・ 1) Straight chain or branched chain alkylbenzene sulfonate having an alkyl group having an average carbon number of 10 to 16 2) Straight chain or branched chain alkyl group or alkenyl having an average carbon number of 10 to 20 group, with an average of 0.5・~ in one molecule
8-@ru' ethylene oxide or propylene oxide or butylene oxide or ethylene oxide/propylene oxide = 0.1/9.9~
9.9/0. '1 ratio or ethylene content/butylene oxide = 0.1/9.9~? ,9/
9 Alkyl or alkenyl ether sulfate added in a ratio of 0.1 3) Alkyl or alkenyl sulfate having an alkyl group or alkenyl group having an average of 10 to 20 carbon atoms Containing an average of 10 to 20 carbon atoms in one molecule Sulfur olefin sulfone 11 salt S) Alkanesulfonate having an average of 10 to 20 carbon atoms in one molecule 6) Electrophase or unsaturated fatty acid salt having an average of 10 to 24 carbon atoms in one molecule 7) Ethylene oxide or butylene oxide or butylene oxide or ethylene oxide/propylene oxide having an alkyl group or alkenyl group having an average of 10 to 20 carbon atoms and an average of 0.5 to 1 mol per molecule At a ratio of 0.1/9.9 to 9.910.1, the ratio is ethylene oxide/butylene oxide = 0.1/9.9 to 9.9? ,? / 0,
9 alkyl or alkenyl ether cardanate added in a ratio of 1.) α-sulfo 11g acid salt or ester R-0100, represented by the following formula: go, z Here, the counter ions of the anionic surfactant include alkali metal ions such as sodium and potassium, calcium,
Examples include alkaline earth metal ions such as magnesium, ammonium ions, and alkanolamines having 1 to 5 alkanol groups having 2 or 5 carbon atoms (e.g., monoethanolagin, diethanolaine, triethanolamine, triisopropanolamine, etc.) be able to. 9) An adenanoic acid surfactant represented by the following general formula (where R' is an alkyl or alkenyl group having 8 to 24 carbon atoms, and R≦ is hydrogen or an alkyl group having 1 to 2 carbon atoms) , R2 represents an amino acid residue, and X represents an alkali metal or alkaline earth metal ion.) M2 R,'-00-M-(OIl,)n-0001
1°R3・<R; , R; and X are as described above. n represents an integer of 1 to 5. ). (〈 is the above-mentioned cram school. m is an integer from 1 to 6 - O) <R; , Curse and X are the above-mentioned depletion. R4 represents hydrogen, an alkyl group having 1 to 2 carbon atoms, or a hydrodialkyl group. ), (R;, R; and X are as described above. R8 represents a β-hydroxyalkyl or β-hydroxyalkenyl group having 6 to 28 carbon atoms.) Rlsl. 3 (Suzuki, R5 and ! are as above). ) 10) Phosphate ester activator A1 Alkyl (or alkenyl) acidic phosphate ester (R'O)n, -P-(OH), (R' is an alkyl group having 8 to 24 carbon atoms, or an alkenyl group, nI+wl=s, nI=1-2) Todoroki 2 Alkyl (or alkenyl) phosphate ester (R'O) n#-, P-(OR). (As mentioned above, R' is n#+♂=5, ll'==,
~5) M5 Alkyl (or alkenyl) phosphate ester salt 0 (fo)n, -P-(01g'). (R', ♂, m7 are as mentioned above, M' is Ma. Indigo, 0a) 11) Sulfonic acid type amphoteric surfactant 1 ''13 represented by the following general formula (here, R is a carbon number of 8 to 24 represents an alkyl or alkenyl group, R represents an alkyl group having 1 to 4 carbon atoms, R represents an alkyl group having 1 to 5 carbon atoms, and 14 represents an alkyl or hydroxyalkyl group having 1 to 4 carbon atoms. ) 2 16 (Here, R and R□1 are as described above. R represents an alkyl or alkenyl group having 8 to 24 carbon atoms or 1 to S.) as (0,H40) n1M (Here, R, □ and "14" are the notifications mentioned above. n is 1 to 2.
Indicates an integer of 0. )' 12) A betaine disc amphoteric activator "as" represented by the following general formula (where R2 is an alkyl or alkenyl group having 8 to 24 carbon atoms, or a β-hydroxyalkyl group, or a β-hydroxyalkenyl group, and R is a carbon (0, H, 0) nII31 (In this ζ, '81 and R25 are as described above. IIJI is 1
Indicates an integer from ~20. ) (ζHere, R8□ and R2,s are as described above. "R4 represents a carboxyalkyl group or a hydroxyalkyl group having 2 to 5 carbon atoms.) 13) An alkyl group having an average carbon number of 10 to 20, or Polyoxyethylene alkyl or alkenyl ether having an alkenyl group and having 1 to 20 moles of ethylene oxide added to it 14) Having an alkyl group with an average carbon number of 6 to 12, 1
Polyoxyethylene alkyl phenyl ether with ~20 moles of ethylene oxide added 15) Polyoxypropylene alkyl or alkenyl ether with an average of 10 to 20 carbon atoms, and with 1 to 20 moles of propylene oxide added. Alkenyl ether 16) Average carbon number 10-20C > Polyoxybutylene alkyl or alkenyl pre-terminated with 1-20 moles of ethylene oxide having an alkyl group or alkenyl group 17) Average carbon number It is recommended to add ethylene oxide and propylene oxide or ethylene oxide and butylene oxide with a total of 1 to sO molecules to form an ionic activator (ethylene oxide and propylene oxide or butylene oxide) having 10 to 20 alkyl or alkenyl groups. The ratio with oxide is 0.1/?, 9-9.91
0,1) 18) Higher fatty acid alkanolamide or its alkylene oxide adduct R', 8, represented by the following general formula. 1m 19) Cicarbonate fatty acid ester consisting of a fatty acid with an average prime number of 10 to 2o and sucrose 20) Fatty acid glycerin heptanoester consisting of a fatty acid with an average number of carbon atoms of 10 to 2o and glycerin 21) Pulkyrucolate expressed by the following general formula (22) A cationic surfactant represented by the following general formula (wherein at least one of R'l, R1, R's, R' is an alkyl or alkenyl group of carbon as-Qz a, etc. indicates an alkyl group having 1 to 5 carbon atoms. 1 indicates a halogen.) (In this ζ, *, , d, and 7 are as described above. u% is an alkylene group having 2 to 5 carbon atoms, and n4 is 1 (Indicates an integer of 20 to 20.) It is preferable that the composition contains at least 10 by weight of one or more of the above surfactants. [2] Divalent metal ion scavenger 1 of the following various alkali metal salts and alkanolamine salts
It is also possible to contain from 0 to SO weight of the species or two or more virgoo components. 1) Phosphates such as orthophosphate, pyrophosphate, tripolyphosphate, metaphosphate, hexametaphosphate, and phytate. 2) Ethane-1,1-/phosphonic acid, ethane-1゜2
) Q phosphonic acid, ethane-1-, hydroxy-1,1
-diphosphonic acid and its 114 form, ethane hydroxy-
Phosphonate salts such as 1,1,2-triphosphonic acid, ethane-1,2-dicarpoxy-1,2-diphosphonic acid, and methanehydroquinicphosphonic acid. 3) 2-phosphonobutane-1,2-dicarboxylic acid, 1-
Phosphonocarboxylic acid salts such as phosphonobutane-2,3,4-) dicarboxylic acid and α-methylphosphonosuccinic acid. 4) Amino acid salts of aspartic acid 1 and glutamate 2). 5) A(nopolyacetate salts such as nitrilotriacetate, ethylenethiadentetraacetate, diethylenetriaminepentaacetate, etc.) 6) Polyacrylic acid, polyaconitic acid, polyitaconic acid, polycitraconic acid, polyfumaric acid, polymaleic acid, Polyitaconic acid, poly-α-hydroxyacrylic acid,
Polyvinylphosphonic acid, sulfonated poly! Leic acid, maleic anhydride-diisobutylene copolymer, anhydrous! Leic acid-styrene copolymer, maleic anhydride-methyl vinyl ether copolymer, maleic anhydride-ethylene copolymer, maleic anhydride-ethylene crosslink copolymer,
Maleic anhydride-vinyl acetate copolymer, maleic anhydride-acrylonitrile copolymer, maleic anhydride-acrylic ester copolymer, maleic anhydride-butadiene copolymer, maleic anhydride-isoprene copolymer, maleic anhydride Poly-β-ketocarboxylic acid derived from acid and element monoxide, itaconic acid-ethylene copolymer, itaconic acid-aconitic acid copolymer, itaconic acid-maleic acid copolymer, itaconic acid-acrylic acid copolymer Polymer, malonic acid-methylene copolymer, methaconic acid-7 malic acid copolymer, ethylene glycol-ethylene terephthalate copolymer, vinylpyrrolidone-vinyl acetate copolymer, 1-butene-2
, S, 4-tricarboxylic acid-itaconic acid-acrylic acid copolymer, polyester polyaldehyde carboxylic acid having quaternary ammonium group, aim- of epoxysuccinic acid
isomer, polyCM, M-bis(carboxymethyl)acrylamide], poly(oxycarboxylic acid), starch succinic acid or maleic acid or terephthalic acid ester, terephthalic acid ester, dicarboxy starch, dimethyl starch in dicarpo, cellulose succinic acid Polyelectrolytes such as esters 0 7) Polyethylene glycol, polyvinyl alcohol,
Non-dissociable polymers such as polyvinylpyrrolidone, cold water soluble, polyvinyl alcohol. 8) Diglycolic acid, oxydisuccinic acid, carboxymethyloxydisuccinic acid, cyclopair p y -1,2,
3,4-tetracarboxylic acid, tetrahydrofuran-1,
2,is,4-tetracarboxylic acid,tetrahydro7:7
- Carboxymethylated products of 2.2,5.5-tetracarboxylic acid, citric acid, lactic acid, tartaric acid, lactose, lactose, raffinose, etc., carboxymethylated products of pentaerythritol, carboxymethylated products of gluconic acid,
Condensates of polyhydric alcohols or sugars and maleic anhydride or succinic anhydride, condensates of oxycarboxylic acids and maleic anhydride or succinic anhydride, benzene polycarboxylic acids represented by mellitic acid, ethane-1,1 ，
2,2-tetracarboxylic acid, ethene-1.1,212-
Tetracarboxylic acid, butane-1,2,5,4-tetracarboxylic acid, propane-1,2,5-tricarboxylic acid,
Organic acid salts such as butane-1,4-dicarboxylic acid, citric acid, sulfosuccinic acid, decane-1,10-dicarboxylic acid, sulfotricarballylic acid, sulfoitaconic acid, malic acid, oxydisuccinic acid, gluconic acid%0M0B, Builder Mfk, etc. . 9) Alinosilicate Mu1 Crystalline aluminosilicate x' (M a O or M2O) - Mu j203 written y '
(B i O2) ・* (Ha O) (In the formula, V is an alkali metal atom, M# is an alkaline earth metal atom that can be exchanged with calcium, and "+7' @ W" is the number of moles of each component. However, in general, 0.7≦X'≦1.5.
0.8≦y'≦6, w' is any positive number. )42
As the detergent builder, those represented by the following general formula are particularly preferred. 11a20・A7,03・n510Q-vHQO (here, n represents a number from 1,8 to jO, and w represents a number from 1 to 6) As Amorphous aluminosilicate X(M2O)・Ad represented by the following formula, O,-7(810,)-W(11
,0) (In the formula, M represents a sodium and/or potassium atom, and X, 7, and W represent the number of moles of each component within the following marginal value range) 0.7≦X≦ 1.2 1.6≦y≦2.8 W is any positive number including 0) 44 Amorphous aluminosilicate X (Ma O)・AJ$103・Y (B i Oa)
・Z(Pa'%s)・#(HaO) (In the formula, M ha
ia also ha K t, 'X, Y, Z. Excellent represents the number of moles of each component within the following numerical range. 0.20≦x≦1.10.0.20≦I≦4.00.0
．． 001≦2≦0.80, #: Any positive number including 0) [5] Alkaline agent or inorganic electrolyte Further, as an alkaline agent or inorganic electrolyte, one or more of the following various alkali metal salts are used. The composition may contain from 1 to 50% by weight, preferably 40% by weight. Silicates, carbonates, sulfates. Nine, as organic alkali agents, triethanolamine, diethanolamine, monoethanolamine, triisopropylamine, etc. [4] Re-staining preventive agent Furthermore, one or more of the following compounds as a re-staining preventive agent
The above can be included in the composition from KO11 to S-. Polyethylene glycol, polyvinyl alcohol, polyvinylpyrrolidone, carboxymethyl cellulose, etc. [5] Bleach agents such as sodium percarbonate, sodium percarbonate, sodium sulfate hydrogen peroxide adduct, F chloride hydrogen peroxide adduct, etc. (It is an enzyme.) Classified based on the reactivity of the enzyme, it is classified into human I2lases, hydrases, oxidoreductors, desmolases,
Examples include transferases and isomerases, and any of them can be applied to the present invention.Hydrolases are particularly preferred, including proteases, nisft-ases,
Includes carbohydrases and nucleases. Specific examples of proteases include pepsin, trypsin, trypsin, collagenase, keratinase (, elastase, sptilici/, BPN1 papain, propalin,
Examples of carboxypeptidase and B1 adenopeptidase, aspergylopeptidase and B. . Carbohydrases include cellulase, maltase, saccharase 1, adenase, pectinai, lysozyme, α
, -glycosidase and β-glycosidase. [A] Blue tinting rules Various blue tinting agents can be added as needed. , an aliphatic amino group which may be substituted with a hydroxyl group, a sulfonic acid group, a carboxylic acid group, an alkoxy group, a halogen atom, a hydroxyl group, a sulfonic acid group, a carboxylic acid group, a lower alkyl group, a lower alkoxy group. R is a hydrogen atom or a lower alkyl group 〇9, or R represents a hydrogen atom, and - Rua ki) When representing a group and ■X and! When either one is a hydroxyl group and the other is an alkanolamino group, n represents an integer of 2 or more. ) (In the formula, D represents a blue to purple azo or anthra non-based dye residue, and X and Y represent the same or different alkanol amino residues or hydroxyl groups.) [8] Anticaking agent powder In the case of detergents, the following K-Young inhibitors can also be added. para-toluene sulfonate, xylene sulfonate, acetate, sulfosuccinate, Merck, finely powdered silica, clay, calcium-silicate (e.g. 'ro
hns-Man 111 company's microphone 4 cells, etc.), calcium carbonate, oxidation! Gnesiu five and so on.

[9] Antioxidant 5-butylhydroxytoluene, 4. ,．． 4'-Butylidenebis-(6-5th-butyl-5-methylphenol)
, 2.2'-butylidene bis=(6-tert-butyl-4-
Antioxidants such as methylphenol), monostyrenated cresol, distyrenated cresol, monostyrenated phenol, distyrenated phenol, 1,1'-bis-(4-hydroxyphenyl)cyclohexane, etc. Laundry detergent composition according to the present invention If you wash your clothes using this, your laundry will come out beautifully, and your white clothes in particular will come out surprisingly white. The first reason for this whitening effect is presumed to be the synergistic whitening improvement effect due to the coexistence of sulfonated aluminum phthalocyanine with the above-mentioned specific fluorescent dye, which is a bluish colored substance. Does it enhance the fluorescent whitening effect of the specific fluorescent dye mentioned above?
Alternatively, considering that sulfonated aluminum phthalocyanine is effective in the presence of only one amount, it may be that it has a special effect on the specific fluorescent dye molecule, such as electronic interaction, but the mechanism is unknown. It is. The second brightening effect is presumed to be due to the properties of sulfonated aluminum phthalocyanine as a known photobleaching agent. It is thought that this photosensitizer absorbs and transmits the prior light energy to oxygen in the atmosphere to remove activated oxygen, and the activated oxygen oxidizes and decomposes the colored stain. On the other hand, other heptalocyanin compounds of the same type, such as sulfonated zinc heptalocyanine, cannot exhibit the remarkable whitening effect of the present invention even when used together with a fluorescent dye. This is probably due to the fact that this photosensitizer has poor light resistance and decomposes during drying in the sun or even during subsequent exposure to light,1 and thus cannot exhibit the first synergistic whitening effect described above. Conceivable. Further, it is desirable that the fluorescent dye used in the present invention has good light resistance like the phthalocyanine compound, and the piphenyl dye represented by the above formula (1) or (10) is preferable for 41. 1. In carrying out the present invention, the amounts of these photosensitizers and fluorescent dyes to be incorporated into detergent compositions should be 0.001 to 0.02 weight bags of sulfonated aluminum tuthalocyanine, and formula (Xuan). - contains 0.05 to 1.0 weight of 91 or more types of fluorescent dye selected from the group consisting of compounds represented by formula (6), and the ratio of the sulfonated aluminum phthalocyanine to the cough fluorescent dye It is particularly preferable that the weight ratio is 1:20 to 1:200.In carrying out the present invention, the method of blending the sulfonated aluminum phthalocyanine into the detergent composition is the same as that used for various usual detergent ingredients. Any method can be adopted, but the rounding method that achieves the effect of the present invention with good S&
The sulfonated aluminum phthalocyanine can be easily dissolved by attaching the sulfonated aluminum phthalocyanine to the surface of detergent particles, or by granulating it with other highly soluble materials such as sulfur salt. The tonal effects achieved by the compositions of the present invention are listed below. (1) When the essential ingredients according to the present invention are included, the whitening effect is significantly improved, and it is possible to create a circular saw phosphorus or a low phosphorus detergent composition. In this case, if the following builders are used, it is possible to obtain a detergent with particularly excellent whitening and bleaching effects, but this is presumed to have the effect of dispersing the photosensitizer and adsorbing it uniformly to the clothing. be done. That is, 2'trilotriacetic acid, ethylenediaminetetraacetic acid, citric acid and salts thereof, and aluminosilicate X(M,O)・AjaO3・Y(810,)・W(H2
O) (in the formula, M is Ha or X, X is 0.7 to 1.5, Y
represents a number from 0.8 to 6.0, and W represents any positive number including 0. ) and other non-phosphate building blocks. One or more non-phosphate building blocks selected from these groups are present in the detergent composition in an amount of 1 to 60 weight-1, preferably 2 to 40 weight-1.
More preferably 5-w! io weight - compounded. (2) When the essential components according to the present invention are included, bleaching or whitening performance can be extremely effectively imparted to enzyme-containing detergents. That is, while oxygen bleaching agents decompose enzymes, sulfonated aluminum phthalocyanine is a bleaching agent that does not act on enzymes. Therefore, a detergent composition containing the essential ingredients of the present invention and containing an enzyme is a detergent with extremely excellent round performance that also uses the action and effect of an enzyme, and is effective against all types of dirt. Among the enzyme-containing detergents containing the essential components of the present invention, those containing hydrolytic enzymes such as protease, amylase, lipase, etc. exhibit excellent 4IK performance. These hydrolytic enzymes are incorporated into cleaning compositions in required amounts depending on the purpose, but in terms of purified enzymes, the amount is 0.001.
It is desirable to blend S to 5% by weight (preferably 0.02 to 0.02% by weight). From the viewpoint of producing a detergent composition, it is preferable to use the enzyme as a crude enzyme or as an enzyme granule obtained by warmly mixing the crude enzyme with other components in the detergent composition and granulating it in advance. . In this case, crude enzyme or granules are used as the purified enzyme in an amount of 0.001 to 5% by weight, for example, the amount used is 0.002 to 10% by weight, preferably 0.1 to 5% by weight. The present invention will be explained in detail with reference to the following examples in which a model enzyme is diluted. Table 1 shows the formulations of the detergent compositions used in Examples 1 to 4. Table 2 shows the amount of fluorescent dye added to the cleaning composition shown in Table 1. Table-2 Furthermore, 0,0055 units of sulfo/aluminum phthalocyanine i were added to each of [mu] to [7] in this table-2, respectively [mu] I (B] *(') *
('') 1 [l] * [7), (A) and CH2
K sulfonated zinc 7 taro 7 ani/o, oos respectively
s-Let the additions be [Mu] and [River], respectively. In addition, the fluorescent dye formula (IO' in the table means the one in which M in the above formula (16) is Ma, and the formula (b)' means that in the formula (2) where M is Ml. Therefore, the above prescriptions [mu] ~ (G) and prescription [mu]. [mu] t (B) are comparative examples.
[1] belongs to the product of the present invention. Example 1 In this experiment, (1) in the combination of Table 1 and Table 2 was used.
/(mu) I [1) / (:B) e [1) /
(0], [1)/CD) I (1)/(1) I
(1)/(F) , (1)/(mu). (1)/CB) t (1)/[0) l [1)/C
D) I [1] / [ll) t [1] / CF)
Twelve types of detergents were used. The test cloth used was clean white cotton knitted underwear.
After washing 1 all times under the washing conditions shown below, the finished whiteness of the test fabric was compared with a pair of V-ex using Nakaya's modified method, and evaluated by visual judgment using a spring two according to the following criteria. Shie. +5-Very white +2=Clearly white □ +1 Nirya Autobiography 0: Equivalent whiteness -1: Slightly not white -2: Obviously white (not present -s: Not very white <Cleaning conditions>) Two-tank type Law 41 elm used 20'C tap water used Bath ratio: Cotton knitted underwear 14/Joj Detergent concentration: 0.1j!i% (401/5oJ) Washing 1
0 minutes dehydration 1 minute → 9th rinse 3 minutes → dehydration 1 minute - 9th rinse S minutes → drying 0 * Two series of drying were carried out for ζζ: Kameno by sun drying and one by electric drying lsK. Teeth, evaluation is also this 2
Table 9 shows the results of this experiment in black.The numerical values in the table represent the main effect values obtained by repeating the above visual judgment and using a modified method of Pairwise Comparison. Table 3 shows that this value is quite true and shows that the product feels whiter than the other. The values in the middle are relative values within each evaluation system. Therefore, although comparisons can be made within the same system, direct comparisons between different systems cannot be made using the above values.) From the results in Table 5. It can be seen that, although sulfonated aluminum phthalocyanine alone has almost no whitening effect, when the product of the present invention is used in coexistence with the above-mentioned fluorescent dye, a whitening effect that far exceeds that obtained when the fluorescent dye is mixed alone can be obtained. Furthermore, 411 in which fluorescent dyes (1) and/or (2) and sulfonated aluminum phthalocyanine are co-existed exhibits a stable and high whitening effect even when dried in the sun. Other fluorescent dyes show almost the same whitening effect as (B), and in order to exhibit the same effect as (Xun and (7)), it is necessary to increase the amount of them added. Example 2 In this experiment, (1
) / (A) S (1] / (A)"I (1)
/ (Mu). (1)/(B) I (1)/CG) I (j,)/
(B)"I(1]/[B)*0 Using seven types of detergents, evaluations were conducted in exactly the same manner as in Example 1. However, the drying method was only the sun drying system. 0 Table 4 showing the results of the experiment From the results in Table 4, it was found that no whitening effect of 41 Furthermore, it can be seen that even if the fluorescent dye is used alone in an increased amount, it cannot achieve the whitening effect of the present invention product (1)/CB)'' detergent. Example Black A black tea-stained fabric was washed with the same seven detergents as used in Example 2 under the following conditions, and the bleaching rate was determined. Washing conditions: Soak in black tea liquid, boil, taint, dry and wash nine cotton cloths.
0x10aIrl'1 cut into 5 pieces each! Add 20 times the weight of the contaminated fabric (bath ratio 1:20) to a concentrated detergent solution (0.8%) prepared using 20°C tap water in a glass beaker, and after 4 hours of immersion exposure during the day, remove the cloth using a targotometer. After washing for 10 minutes, rinsing with running water, press drying, and using the reflectance at 460 mm VC, the washing bleaching rate (-) was calculated using the following formula, and the average value of 5 sheets was determined. Washing bleaching rate (*) Table - Table 5 Showing the results of the 5K Honyi experiment.
It can be seen that detergents containing photoactivators (photoactivators) have a high cleaning and bleaching rate, and among them, the invention product (13/CB)
It can be seen that the value is the highest. Example 4 A cloth contaminated with black tea prepared in the same manner as that used in Example S was coated with hot oil at 0.1-booting temperature, and then stored in a dark place for one month.
Washing was performed using 0° C., 8° DH hard water under the same conditions as in Example S, and the washing bleaching rate was determined. Table 6 shows the results of this experiment. In the table, detergents [1], I, and [2] have all surfactants that are anionic (Lum8.mu8), and [5] contains Mu18 and nonionic surfactants. Also, [1] contains 20-phosphate, whereas [2) * (s)
is a so-called low-phosphorus detergent that contains only 596 phosphates. From the results in Table 6, the product of the present invention has a particularly low phosphorus detergent when removing mixed stains of oil and medium-sized stains with hard water. It can be seen that in phosphorus washing 1, it is preferable to use an activator with excellent hard water resistance such as Muko B or nonionic surfactant group. Example 5 Using 20°C tap water, detergent concentration [0, 15!S-11
111'JK Kanuma Gardening Akaoh soil at 120℃ and 5℃ for 4 hours.
r After drying, crush and 150 me@h (1'OO, u)
Mud 2 after drying the 7's at 120℃ Soil S℃ for 2 hours
．． 51 was well dispersed using ultrasonic waves, 5 sheets of 110x10a white cotton cloth were put in, the cloth was taken out after stirring for 10 minutes with a turgotometer, and the whiteness of the treated cloth was carried out as in Example 1 by rinsing with running water and press drying. The ones evaluated in the same way as the circles. □The results are shown in Table-7. Table 7 From Table 7, even if it is a non-rinsing detergent, zeolite), MT
If a product that uses sodium citrate as a building block contains sulfonated aluminum phthalocyanine and a fluorescent dye, it is possible to obtain a white finish equivalent to that of Kuyurin detergent by adding a sulfonated aluminum phthalocyanine compound and a fluorescent dye. Recognize. The performance of those including 4IK and IT systems is remarkable. Tables 8 and 9 show the formulations of detergent compositions used in Examples 6 and 7. Table 8 Example 6 A cleaning test was conducted on detergents A to H in Table 9 under the following conditions. Contaminated cloth with 0 blood stains, dyed cloth by soaking cotton in a mixture of horse blood and milk at a ratio of 1:1 and contaminating it and drying; . Washing conditions Detergent once: 0.8 ls, 40℃ tap water bath
Ratio @ 1/20 *Results of 4-hour immersion exposure Calculate the bleaching rate (total) using the following formula and show it in Table 10. Bleach cleaning rate (For blood-contaminated cloth and black tea-contaminated cloth, the reflectance of both was measured at the wavelength that shows the moth's large absorption. Table 10 Table 10 Detergent 1 containing sodium perborate The bleaching effect of detergent G containing sodium percarbonate and enzymes is small when washed at 40℃. In contrast, only the product of the present invention, which contains sulfonated arunomphthalocyanine and an enzyme, is effective against both blood-contaminated cloth and black tea-contaminated cloth. It can be seen that the detergents IC, F, G, and II tested in Example 6 were left in cartons indoors (without air conditioning) for K-years. A blood-stained cloth and a black tea-stained cloth were washed under the same conditions as in Example 1, and the respective bleaching and cleaning rates at the time of death were determined.The results are shown in Table-11.Table-11 Table-11 The product H of the present invention is a detergent that uses other bleaching agents.
It can be seen that it does not interfere with the storage stability of enzymes in detergents like GO and GO, and maintains a high bleaching and cleaning rate even after long-term storage.

Claims (1)

[Scope of Claims] 1 Sulfonated aluminum chloride represented by the following formula (!) 0.0001-o, double * ) to (e)
1. A laundry detergent composition comprising, as an essential component, one or more of the following with a weight of 0.01 to 2.0.゛ 5 [In the formula, -(gorsz) is a sulfone group or sulfonate group substituted on the benzene nucleus of the 7-talocyanin product,
X engineering is H or 7-potassium metal ion or ammonium ion, n is the number of its substituents, and n is 1-4. In addition, Equation 11 f+ is h) with the charge of Muj(1), and Yma
is its counterion. ] (a) 4.4'-bis-(
2-Melphostyryl, )-bi,7el (the wing in the formula represents a hydrogen atom, an ammonium ion, an alkali metal ion, or an amine residue) (b) 4,4'
-bis-(4-chloro-5-sulfo (wings in the formula have the same meaning as above), 7f→ 2-(styrylphenyl)
Nut, thiazole derivative (in the formula, R□ is hydrogen or chlorine, and the wings are the same as above) 4
, 4'-bis(triazol-2-yl)stilbene derivative (in the formula, M is the same as above) ■ Bix()IJ azinylamino)stilbene disulfonic acid derivative, where M is the same as above)