JPH0153300B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a novel distyrylbenzene, a process for its preparation, its use for the fluorescent brightening of organic materials, and detergents containing the novel distyrylbenzene. For example, water-soluble 1,4-distyrylbenzenes substituted in the benzene nucleus are known from documents such as DE 1923267 and DE 2721730. However, these known compounds have no affinity with cationically active fiber processing aids. Furthermore, water-soluble cationically substituted 1,4-distyrylbenzenes are known from DE 23 64 396 A1. However, due to its cationic properties, this known compound
Unsatisfactory results are obtained when used in cationic media. According to the present invention, distyrylbenzene which does not have the above drawbacks has been discovered. Among the distyrylbenzenes of the present invention, particularly recommended is distyrylbenzene represented by the following formula (2). In the formula, X ₁ means a direct bond, _- SO ₂ NH _- at m-position with respect to oxygen, sulfur or styryl group, and Y ₁ and Y′ ₁
independently means C _1-4 -alkylene, and R″ ₁ and R″ ₂ each independently represent C _1-4 -alkyl, or both together represent a pyrrolidine ring or a piperidine ring. or form a morpholine ring or together with R′ ₃ form a piperidine ring, R′ ₃ means hydrogen, C _1-4 -alkyl or together with R″ ₁ and R″ ₂ form a pyridine ring forming, R ₅ means hydrogen, chlorine, C _1-4 -alkyl, C _1-3 -alkoxy, R ₆ means hydrogen, chlorine, C _1-4 -alkyl, C _1-3 -alkoxy , R ₇ means hydrogen, n and n' are each independently a number of 0 or 1, and A means a colorless anion. Preferred distyrylbenzenes included in formula (2) to formula (5) below are those that satisfy the following conditions. Those that are symmetrical, i.e. Y ₁ = Y ₁ ′, n=
n′: Quaternized, ie, n and n′ are both 1; R ₃ and R′ ₃ represent C _1-3 -alkyl. Of interest within the range of preferred distyrylbenzenes of formula (2) above are those represented by the following formula: (wherein, X ₂ means oxygen, sulfur or _{-SO 2} NH at m-position, Y ₂ means C _1-4 -alkylene, R ₁ means unsubstituted C _1-4 -alkyl) or together with R ₂ to form a pyrrolidine ring, piperidine ring or morpholine ring, or together with R ₂ and R ₃ to form a pyridine ring, R ₂ means unsubstituted C _1-4 -alkyl or together with R ₁ to form a pyrrolidine ring, piperidine ring or morpholine ring, or together with R ₁ and R ₃ to form a pyridine ring, R ₃ means hydrogen, unsubstituted C _1-4 -alkyl or together with R ₁ and R ₂ form a pyridine ring, n is a number of 0 or 1, and A means a colorless anion); and (wherein, X ₁ is a direct bond, oxygen, sulfur or m-position
_- SO ₂ NH _- , Y ₁ means C _1-4 -alkylene, R″ ₁ and R″ ₂ each independently mean C _1-4 -alkyl, or both together forming a pyrrolidine ring, piperidine ring or morpholine ring, or together with R′ ₃ to form a pyridine ring, R′ ₃ means hydrogen, C _1-4 -alkyl or together with R″ ₁ and R″ ₂ together form a pyridine ring, R ₅ means hydrogen, chlorine, C _1-4 -alkyl, C _1-3 -alkoxy, R ₆ means hydrogen, chlorine, C _1-4 -alkyl, C _1-3 - means alkoxy, _R7 means hydrogen, n is a number of 0 or 1, and A means a colorless anion); and (In the formula, X ₃ means a direct bond, oxygen, sulfur or -SO ₂ NH- at the m-position, Y ₃ means C _1-4 -alkylene, and R ₁ and R ₂ are mutually independent) C _1-4 -alkyl or both together represent a pyrrolidine ring,
to form a piperidine ring or a morpholine ring or together with _R'3 to form a pyridine ring, _R'3 stands for hydrogen, _C1-4 -alkyl or together with _R1 and _R2 to form a pyridine ring; forming, R′ ₅ is hydrogen, chlorine, C _1-4 -alkyl or C _1-3
-alkoxy, n is a number of 0 or 1 and A means a colorless anion); and (In the formula, Y ₄ means C _2-4 -alkylene, R ₁ 〓 means C _1-3 -alkyl, or
together with R ₂ 〓 form a pyrrolidine ring, piperidine ring or morpholine ring, R ₂ 〓 means C _1-3 -alkyl or
together with R ₁ 〓 form a pyrrolidine ring, piperidine ring or morpholine ring, R″ ₃ is hydrogen or C _1-3 -alkyl, n is a number of 0 or 1, and A means a colorless anion) The distyrylbenzenes of the following formulas are important: (In the formula, X ₄ means oxygen, sulfur or _{-SO 2} NH _- at m-position, Y ₅ means C _2-4 -alkylene, R ₁ 〓 means unsubstituted C _1-4 -alkyl or together with R ₂ 〓 to form a pyrrolidine ring, piperidine ring or morpholine ring, R ₂ 〓 means unsubstituted C _1-4 -alkyl or together with R ₁ 〓 to form a pyrrolidine ring, forming a piperidine ring or a morpholine ring, _R3 means hydrogen or unsubstituted _C1-4 -alkyl, A means a colorless anion, and n means a number of 0 or 1); and (In the formula, Y ₅ means C _2-4 -alkylene, R ₁ 〓 means unsubstituted C _1-4 -alkyl, or together with R ₂ 〓 represents a pyrrolidine ring, a piperidine ring or a morpholine ring. R ₂ 〓 means unsubstituted C _1-4 -alkyl or together with R ₁ 〓 form a pyrrolidine ring, piperidine ring or morpholine ring, R ₃ is hydrogen or unsubstituted C _{1- 4} -alkyl, A is a colorless anion, and n is a number of 0 or 1); and (In the formula, Y ₅ means C _2-4 -alkylene, R ₁ 〓 means unsubstituted C _1-4 -alkyl, or together with R ₂ 〓 represents a pyrrolidine ring, a piperidine ring or a morpholine ring. R ₂ 〓 means unsubstituted C _1-4 -alkyl or together with R ₁ 〓 form a pyrrolidine ring, piperidine ring or morpholine ring, R ₃ is hydrogen or unsubstituted C _{1- 4} -alkyl, A is a colorless anion, and n is a number of 0 or 1). Particularly important distyrylbenzenes are represented by the following formulas. (In the formula, R ₁ 〓=R ₂ 〓 and each means methyl or ethyl, R ₃ 〓 means hydrogen, methyl or ethyl, A is CH ₃ OSO ₃ , C ₂ H ₅ OSO ₃ or

[Formula], n is a number of 0 or 1, and m is a number of 2 or 3); and (In the formula, R ₁ 〓=R ₂ and each means methyl or ethyl, R ₃ 〓 means hydrogen or methyl, A″ means CH ₃ OSO ₃ or

[Formula] and n is a number of 0 or 1); and and and and Distyrylbenzene of formula (2), in which X represents a direct bond, oxygen or sulfur, and n and n' are the number 0, is produced as follows by a method known per se. That is, in the presence of a strong base, the formula A compound with the formula in a molar ratio of 1:2 with either one of the compounds or a mixture of both, and then the resulting formula is prepared by quaternization or protonation in a manner known per se with 1 to 2 molar equivalents of an alkylating agent or acid of the formula R' ₃ -A. In addition, in each of the above formulas, X ₁ means a direct bond, oxygen or sulfur, and Y ₁ , Y ₁ ′, R ₁ ″,
R ₂ ″, R ₃ ′, R ₅ , R ₆ , R ₇ and A have the abovementioned meanings, and Z ₁ and Z ₂ mean one of them an OCH- group and the other

[expression] or

[Formula] (wherein, D ₁ means a substituted or unsubstituted alkyl group, aryl group, cycloalkyl group, or aralkyl group). Z ₂ is preferably an OCH- group. The condensation is advantageously carried out in a solvent which does not take part in the reaction. Examples of such solvents include hydrocarbons such as toluene and xylene or alcohols such as methanol, ethanol, isopropanol, butanol, glycols, glycol ethers such as 2-methoxyethanol, hexanol, cyclohexanol and cyclooctanol, and also ethers. Examples include diisopropyl ether, tetrahydrofuran and dioxane as well as dimethyl sulfoxide, formamide and N-methylpyrrolidone. Particularly suitable are polar organic solvents such as dimethylformamide and dimethylsulfoxide. Furthermore, some of the reactions can also be carried out in the form of aqueous solutions. The temperature at which this reaction is carried out can vary within a wide range. The reaction temperature is determined by the following conditions: α the stability of the solvent used with respect to the substances participating in the reaction, especially strongly basic alkaline compounds, β the reactivity of the condensation reaction partners, and γ the solvent-base pair as the condensing agent. The degree of action of the combination. In practice, temperatures in the range of about 10 to 100°C are generally contemplated. When dimethylformamide is used as the solvent, the preferred temperature range is 20 to 60°C.
It is. As strongly basic alkaline compounds, in particular hydroxides, amides and alcoholates of alkali metals (preferably alcohols having 1 to 4 carbon atoms) come into consideration, in which case the alkali metals are mainly for economic reasons lithium, sodium and Advantageously, it is potassium. However, in principle and in special cases it is also possible to use alkali sulfides, alkali carbonates, aryl alkal compounds such as phenyl-lithium or strongly basic amines (including ammonium bases) such as trialkyl ammonium hydroxides. , you can get good results. The starting compounds of formulas (17) and (18), in which Z ₂ is an aldehyde group, can be prepared in organic solvents which do not participate in the reaction, such as alcohols, dialkylamides of aliphatic carboxylic acids, and with basic alkali or alkaline earth compounds, such as sodium by alkylation of hydroxyl benzaldehyde with dialkylaminoalkyl chloride in the presence of alcoholate (see Example 3), potassium carbonate, sodium carbonate, calcium carbonate, magnesium oxide, sodium hydride, potassium hydroxide or sodium hydroxide. You can get it. Particularly suitable is the use of anhydrous solvents, which can also be used in the next step, namely for the preparation of compounds of formula (19), for example when dimethylformamide is used, formulas (17) and There is no longer a need to isolate the compound (18). formula (wherein X ₁ means _{-SO 2} NH _- in the m-position with respect to the styryl group), the distyrylbenzene of
2039993) by known methods and which has the formula H ₂ N-Y
-N (R ₁ ″) (R ₂ ″) or HO-Y-N (R ₁ ″)
Produced by reacting with a compound of (R ₂ ″). Formula (In the formula, X ₁ means a direct bond, _- SO ₂ NH _- at the m-position with respect to oxygen, sulfur or styryl group, and Y ₁ and Y′ ₁
independently means C _1-4 -alkylene, and R″ ₁ and R″ ₂ each independently represent C _1-4 -alkyl, or both together represent a pyrrolidine ring or a piperidine ring. or form a morpholine ring or together with R′ ₃ form a pyridine ring, R′ ₃ means hydrogen, C _1-4 -alkyl or together with R″ ₁ and R″ ₂ form a pyridine ring forming, R ₅ means hydrogen, chlorine, C _1-4 -alkyl, C _1-3 -alkoxy, R ₆ means hydrogen, chlorine, C _1-4 -alkyl, C _1-3 -alkoxy , R ₇ means hydrogen, n and n' are independently the numbers 0 or 1, and A means a colorless anion), which can be prepared by the formula ( 19)
One molar equivalent of distyrylbenzene is expressed by the formula R′ ₃ −A
It is produced by quaternization or protonation with 1 to 2 molar equivalents of an alkylating agent or acid (wherein R' ₃ and A have the above-mentioned meanings). Suitable quaternizing or protonating agents R' ₃ -A are, for example, the following compounds: alkyl halides such as methyl iodide, ethyl iodide, ethyl bromide butyl bromide or benzyl chloride, dimethyl sulfate or sulfuric acid. Dialkyl sulfates such as diethyl, sulfonic acid esters such as toluene- or methyl- or -ethyl benzenesulfonate, alkylene oxides such as ethylene oxide or propylene oxide, or upichlorohydrin, formula (wherein B means methyl, ethyl, propyl, butyl or phenyl) or a compound of formula (22) (In the formula, R ₃ is alkyl having 1 to 4 carbon atoms, D ₂ is hydrogen, unsubstituted alkyl, or hydroxy, cyano, or alkyl moiety has 1 to 4 carbon atoms, respectively)
Phosphites or phosphonates of alkyl substituted by alkylcarbonyloxy or _{alkoxycarbonyl} having 1 to 4 carbon atoms; The quaternization of the compound of formula (19) to the compound of formula (21) using an alkyl halide, dialkyl sulfate or sulfonic acid ester is preferably carried out in a solvent inert to the alkylating agent.
Examples of suitable solvents are hydrocarbons such as benzene, toluene and xylene; halogenated aliphatic or aromatic hydrocarbons such as chloroform, ethylene chloride, chlorobenzene and dichlorobenzene;
Alcohols such as ethanol, butanol, ethylene glycol and ethylene glycol monomethyl ether; ethers such as ethylene glycol dimethyl ether and dioxane; or amides such as dimethylformamide and N-methylpyrrolidone. It has been found to be advantageous in some cases to use the quaternizing agent also as a solvent. Quaternization using the alkylating agents exemplified above is advantageously carried out at temperatures of 0 to 180°C, preferably 30 to 140°C. Quaternization of formula (19) to compound of formula (21) with alkylene oxide, epichlorohydrin or formula (wherein B has the meaning given above), the quaternization is carried out in the presence of an organic acid such as formic acid, acetic acid, propionic acid or lactic acid in an acidic medium at the temperatures mentioned above. It is advantageous to do so. However, it is also possible to use inorganic acids for this purpose, such as sulfuric acid, phosphoric acid or hydrohalic acid. These inorganic acids can be used in their usual concentrated commercially available forms, as dilute aqueous solutions or mixed with the above-mentioned organic solvents, optionally with the addition of water. If the reaction is carried out in the presence of an organic acid, said acid is in most cases used in concentrated form, optionally in admixture with said organic solvent. Examples of preferred phosphites and phosphonates are listed below. Dimethyl phosphite, diethyl phosphite, dimethyl-methanephosphonate, diethylmethanephosphonate, methyl-ethyl-methanephosphonate,
Methyl-propyl-methane-phosphonate, methyl-butyl-methanephosphonate, methyl-hexyl-methanephosphonate, methyl-octyl-
Methanephosphonate, Methyl-decyl-methanephosphonate, Methyl-dodecyl-methanephosphonate, Dimethyl-β-methoxycarbonylethane-phosphonate, Dimethyl-β-cyanoethane-
Phosphonate. The reaction is carried out in water and/or organic solvents, preferably at temperatures between 60 and 190°C.
Suitable examples of the organic solvent in this case include methanol, ethanol, propanol, isopropanol, butanol, glycol, glycol-methyl ether, glycol-dimethyl ether, glycol butyl ether, diglycol methyl ether,
Methyl ethyl ketone, methyl butyl ketone, dimethylformamide, sulfolane, oxypropionitrile, toluene, xylene, benzyl alcohol, phenoxyethanol, benzyloxypropionitrile, and the like. If a liquid compound of formula (22) is used, the reaction can be carried out without the additional presence of a solvent. If a protonated compound of formula (21) is desired, ie if an acid addition salt is desired, mineral acids are especially used as protonating agents.
In principle all organic or inorganic acids from strong to medium strong are suitable for this purpose. Suitable solvents in which the protonation can be carried out are generally all inert solvents. Preferred are solvents in which the starting materials dissolve and from which the desired product readily precipitates. For example, the following solvents are included. Aromatic hydrocarbons such as benzene, toluene and xylene; halogenated hydrocarbons such as trichloroethane, tetrachloroethane, chlorobenzene or dichlorobenzene; nitro compounds such as nitromethane, nitropropane, nitrobenzene, alkanols and ring-opening or ring-closing ethers. For example, butanol, dibutyl ether, ethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, anisole or dioxane; ketones such as cyclohexanone or methylethyletone;
Aliphatic amides such as dimethylformamide or dimethylacetamide; sulfoxides such as dimethylsulfoxide and carboxylic acid esters such as acetate or acetate-butyl ester. Distyrylbenzene of formula (6) has the formula A compound with the formula in a molar ratio of 1:2 and, if desired, the resulting formula It is produced by quaternizing or protonating a compound of the formula R″ ₃ -A with 2 molar equivalents of an alkylating agent or acid. In each of the above formulas, Y ₄ , R ₁ 〓 , R ₂ 〓,
R″ ₃ and A have the meanings given above and Z ₁ and Z ₂
means that one side is OCH- group and the other side is of formula

[expression] or

[Formula] (herein, D ₁ means a substituted or unsubstituted alkyl group, aryl group, cycloalkyl group, or aralkyl group). The novel compounds defined above exhibit remarkable fluorescence in a dissolved or finely dispersed state, although the degree varies depending on the type. The novel compounds can therefore be used for the fluorescent brightening of various synthetic, semi-synthetic or natural organic materials or substances containing such organic materials. The organic material to be fluorescently brightened can belong to different processing stages (raw material, semi-finished product or finished product). The compounds according to the invention are used in particular for textile organic materials,
It is particularly important for the treatment of textile and knitted fabrics. Depending on the type of brightener compound used, it may prove advantageous to carry out the processing operation in a neutral or alkaline or acidic bath. The novel fluorescent brighteners according to the invention can also be used for the fluorescent brightening of paper pulp, especially in the presence of cationic retention agents and other additives. The novel fluorescent brighteners according to the invention can be used in the following usage forms. a. Mixed with dyes (for nuance) or pigments (colored pigments or especially white pigments) or as additives in dyeing baths; b. Mixed with wetting agents, softeners, swelling agents or antioxidants; c. Various. Fiber finishing methods such as flame retardant processing,
In combination with softening, sun protection or antistatic or insect repellent treatments; d. in coatings, impregnations or binders (solutions, dispersions, emulsions) for textiles, fleece, paper, leather; incorporated in dissolved or dispersed form in polymer carriers (polymerization products, polycondensation products or polyaddition products) for use in; e. in various industrial products to increase their commercial value (e.g. (for improving the appearance of soaps, detergents, laundry rinse agents, and textile treatment agents); (f) in combination with other substances that have a fluorescent luster; (g) use in spinning bath preparations; . i.e. as an additive to the spinning bath, such as used to improve the lubricity for the next processing step of the synthetic fiber yarn, or as a treatment bath for the yarn leaving the particular bath before drawing the yarn or e.g. Added to after-treatment baths of wet-spun polyacrylic fiber yarns in the so-called gel state; h For various purposes in photographic technology, such as for electrophotographic reproduction or supersensitization; i Depending on the type of substituent. Also used as a laser coloring material. When the brightening method of the present invention is combined with fiber treatment or finishing, the combined treatment involves pre-preparation of a stable formulation containing the present fluorescent brighteners at a concentration that achieves the desired brightening effect. It is often convenient to work with the formulations that have been prepared. The amount of the novel fluorescent brighteners according to the invention relative to the material to be brightened can vary within a wide range. A clear and durable gloss effect can be achieved with amounts as low as 0.0001 weight percent in some cases. However, amounts up to about 0.8 weight percent and sometimes up to about 2 weight percent may also be used. 0.0005 to 0.5 weight percent is the preferred usage range for most practical applications. For various reasons, it is often advantageous to use the present brighteners not as such, ie, as brighteners alone, but in admixture with various auxiliaries and extenders. The novel fluorescent brighteners are particularly suitable as additives to laundry baths or as commercial or household detergents and laundry after-treatment agents. In this case, the present brighteners can be added in various ways. When added to washing baths, it is advantageous to add them as solutions in water or organic solvents, or alternatively as finely dispersed aqueous dispersions in water. It can be conveniently added to commercial or household detergents at any stage of the detergent manufacturing process. The addition can be carried out in the form of solutions or dispersions dissolved or dispersed in water or other solvents, and it can also be added as dry powder fluorescent brighteners without auxiliaries. The present brighteners can, for example, be dissolved in or mixed with the laundry actives, kneaded or drawn together, so that they can be pre-blended into the finished detergent. However, the brighteners can also be subsequently sprinkled onto the finished detergent in the form of a solution or dispersion. The compounds according to the invention can also be used in post-rinse baths, which are commonly used for purposes such as imparting a soft feel, providing anti-static action, providing sun protection, providing fragrance, etc. . In particular, the compounds according to the invention are suitable for use in addition to laundry after-treatment agents containing cationic softeners. The new brighteners are particularly suitable as brighteners for concentrated liquid detergents containing nonionic surfactants and cationic softeners or surfactants. The invention therefore also relates to detergents which are preferably in liquid form and which, in addition to the novel distyrylbenzenes and the customary additives, additionally contain nonionic surfactants and cationic fabric softeners. As nonionic surfactants, all those known and commonly used in the art are considered, such as water-soluble products obtained by adding reactive hydrogen of a hydrophobic compound to alkylene oxide or an equivalent compound. be considered. The sulfuric organic products can be heterocyclics and in particular aliphatic or aromatic compounds. Preferred are higher fatty alcohols and alkylphenols, but others such as carboxylic acids, carboxamides, mercaptans, sulfamides, etc. can also be used. Preferred nonionic compounds are addition products of ethylene oxide with higher fatty alcohols having 6 to 50 or more carbon atoms. The amount of ethylene oxide can vary within a wide range, but generally at least 5 moles of ethylene oxide are used per mole of hydrophobe. Other lower alkylene oxides such as propylene oxide or butylene oxide can also be used in place of all or part of the ethylene oxide. Other non-ionic compounds that may be used include: a. Polyoxyalkylene esters of organic acids such as higher fatty acids, resin acids, tall oil acids and acids of petroleum oxidation products. In this case, the ester has as a rule 10 to 22 carbon atoms in the acid moiety and contains about 12 to 30 moles of ethylene oxide or its equivalent. b Alkylene oxide adduct of higher fatty acid amide.
In this case, the fatty acid portion is in principle 8 to
It has 22 carbon atoms and is combined with 10 to 50 moles of ethylene oxide. The corresponding carboxamides and sulfamides can also be used equivalently. When producing liquid detergent concentrates, it is preferred to use oxyalkylated higher fatty alcohols as nonionic surfactants. In this case, the fatty alcohol has at least 6 and preferably at least 8 carbon atoms. Preferred alcohols are lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol and oleyl alcohol, which alcohols are condensed with at least 6 moles of ethylene oxide. A representative nonionic product is an addition product of about 6.5 moles of ethylene oxide to a fatty alcohol having 12 to 13 carbon atoms. The corresponding alkylmercaptans can similarly be used as nonionic surfactants after addition condensation with ethylene oxide. Alkoxylated higher fatty alcohols are particularly suitable for household detergents. This is because this alcohol is easily biodegradable and has good compatibility with cationic surfactants and fabric softeners and other commonly used additives. Among the cationic fabric softeners, quaternary derivatives of ammonia and/or imidazolines with two long-chain aliphatic residues are particularly suitable. For example, 1-methyl-1-oleylamidoethyl-2
-oleyl-imidazolinium.X, 1-methyl-1-stearylamidoethyl-2-stearyl-imidazolinium.X, di-stearyl-
Dimethyl-ammonium.X and formula It is a compound of In the above, Q means C _14-16 -alkyl and X means chloride, bromide, methyl sulfate, ethyl sulfate, methane, ethane or toluenesulfonate anion. The quaternary fiber softeners that can be used according to the invention, and in particular the softeners exemplified above, impart a soft, fluffy feel to the fiber fabric and at the same time impart wetting resistance. This fabric softener is important for textiles, as it has the effect of preventing static loads and preventing wrinkles, thus making ironing easier and making the textile more comfortable. shall be. The liquid medium for the detergents according to the invention is aqueous and can consist only of water or of water and additional solvents for certain additives. Additional solvents may be used up to 20% of the total solvent content, preferably up to 15%. Examples of such additional solvents are lower alkanols or lower diols or polyols, such as ethanol, isopropanol, ethylene glycol, propylene glycol and glycerin. Furthermore, etherified polyols such as diethylene glycol, ethylene glycol dimethyl ether and ethylene glycol monoethyl ether can also be used as additional solvents. Liquid detergents according to the invention may contain a variety of selected compatible additives. For example, it may contain anti-fouling agents or anti-graying agents such as polyvinyl alcohol and hydroxypropyl methyl cellulose; anti-foaming agents such as sodium benzoate; preservatives; UV-absorbers and fragrances. Of course, these additives are selected on the condition that they have an affinity with the main components of the detergent. The nonionic surfactants are used in an amount of 10 to 70% by weight, preferably 60% by weight. The concentration of fabric softener is from 1 to 30% by weight, preferably from 2 to 21% by weight. The aqueous solvent, preferably water (which may further contain monohydric, dihydric or polyhydric alcohols or similar solvents), is 5 to 60% by weight.
used in amounts of The final finished detergent in solution or powder form contains from 0.005 to 3% by weight of the compounds according to the invention.
Contain in an amount of Other content is 5% by weight of detergent
It is preferable that it is below. This is because using larger amounts of auxiliary agents can affect the properties of the liquid detergent. Although the preferred laundry active preformulation according to the invention is a stable clear liquid, suitable opacifying agents can be added thereto to give it an opaque appearance if desired. The detergents according to the invention can be used in both soft and moderately hard water at elevated temperatures. Furthermore, the detergent can be used for washing textiles even in very hard water at low temperatures. Therefore,
The hard content of the water can be from 0 to 300 ppm or more, calculated as calcium carbonate, and the washing temperature can be from 4 to 60°C. The detergent according to the invention dissolves very easily in cold or hot wash water, has a high degree of cleaning, eliminates electrostatic charges and softens the laundry without making it hydrophobic. Preferred detergents according to the invention are in the form of clear and stable liquids whose activity and homogeneity remain unchanged over long periods of time.
In order to produce clear liquid detergents, the concentration of the active substance can only be varied within certain ranges. That is, if it is desired to obtain a clear liquid detergent, the concentration of fabric softener, for example, should not be higher than 30%. The compounds according to the invention are based on the weight of the finished detergent or textile treatment agent in liquid or powder form.
It is blended in an amount of 0.005 to 1% or more.
The washing bath/treatment bath containing the brightener of the present invention in this predetermined amount can be made of cellulose fibers, polyamide fibers,
When washing textiles made of high-grade cellulose fibers, polyester fibers, wool, etc.
The textile product is given a shiny appearance with the image light. The washing process is carried out, for example, as follows: A washing bath is prepared containing from 0.1 to 10 g/Kg of synthetic detergent and from 20.01 to 1% of the brightener of the invention, based on the weight of the detergent. A given textile product is washed in this washing bath at a temperature of 20 to 100°C for 1 to 30 minutes.
Wash for minutes. The liquor ratio can be from 1:3 to 1:50. After washing, rinse and dry as usual. Examples of the present invention are shown below. In the examples, parts are parts by weight and percentages are percent by weight, unless otherwise specified. Melting points and boiling points are uncorrected unless otherwise noted and are often blurred. In particular, the melting points and boiling points of quaternized compounds do not appear sharply. Example 1 4.2g of the compound of the following formula (100) was added to 300ml of methanol.
Suspend in ml. After adding 6.9 ml of dimethyl sulfate, heat to boiling temperature with stirring and boil under reflux for 7 hours. After cooling to room temperature, the crystallized product is filtered off with suction, washed with methanol and dried in vacuo. Extraction with toluene yields 4.7 g of the compound of the following formula (101) as light yellow crystals with a melting point of 145-147°C. The compound of formula (100) can be produced as follows. 37.3 g of the compound of the following formula (102) is suspended in 455 ml of chlorobenzene at room temperature. After adding 1.3 ml of dimethylformamide to this suspension, 14.5 ml of thionine chloride is added dropwise over 20 minutes. It is then heated to 95-105°C with stirring and kept at this temperature with continued stirring for 4 hours. 120 ml of thionyl chloride and chlorobenzene are distilled off, cooled to 5°C and 21.4 g of calcium soda are added slowly. A solution of 14.4 g of 3-dimethylamino-1-propylamine in 17 ml of chlorobenzene was added to the resulting bright yellow suspension at 5-10°C.
dropwise over a period of 30 minutes, heated to 106° C. and, after dilution with 300 ml of chlorobenzene, stirred at this temperature for 7 hours. The temperature is lowered to 95° C. and the product is filtered off with suction, washed with chlorobenzene and dried under vacuum. Successive recrystallization from methanol and toluene yields 14.7 g of the compound of formula (100) as bright yellow crystals with a melting point of 190-192°C. The compound of formula (102) can be obtained as follows. 18.9 g of p-xylylene-diphosphonic acid-tetraethyl ester and 4-chloro- in 200 ml of dimethyl sulfoxide at a temperature of 40°C under a nitrogen atmosphere.
Dissolve 25.2 g of benzaldehyde-3-sulfonic acid sodium salt (96% purity). Then 40-45℃
Sodium ethylate (97.3% pure) at a temperature of
7.2 g are added over 20 minutes and stirring is continued for a further 4 hours at 40-45°C. After this, 100 ml of salt-removed water is added while cooling. Aspirate the crystalline product at 15 °C and add 2000 ml first, then 1500 ml
Recrystallize twice from water. 15.3 g of the compound of formula (102) is obtained by vacuum drying at 85°C. UV-spectrum: λmax: 363 mm Measured in dimethylformamide/water (1:1). Example 2 Add 3.6 g of the compound of formula (100) to 25 ml of toluene, add 5 ml of methylphosphonic acid-dimethyl ester, and boil under reflux while stirring for 5 hours. After cooling to room temperature, the product is filtered off with suction and dried under vacuum. Thus, 4.4 g of a compound represented by the following formula (200) was obtained. Example 3 1,4-bis- in 300ml of dimethylformamide
(diethoxyphosphonomethyl)-benzene 75.7g
and 96.9 g (96% purity) of the compound of formula (300) are dissolved. 88.6 g of a 30.5% methanol solution of sodium methylate is added dropwise to the above solution with stirring under a nitrogen atmosphere while ensuring that the temperature does not exceed 40°C. After maintaining the temperature at 40-45°C for 2 hours, cooling with ice-cold water and adding 600 ml of water to the reaction mixture. The precipitated product is filtered off with suction, washed repeatedly with water and dried under vacuum over calcium chloride. Thus, 96.4 g of a compound of the following formula (301) is obtained as bright, bright yellow crystals with a melting point of 90-91°C (after recrystallization from hexane and isopropanol). The starting compound of formula (300) is prepared as follows. Salicylaldehyde in 2000ml of chlorobenzene
244g and 2-diethylamino-ethyl chloride hydrochloride
Suspend 344g. To this suspension, 732 g of a 30.7% methanol solution of sodium methylate is added dropwise with stirring under a nitrogen atmosphere. During this time the suspension becomes yellow and dense. Gradually increase the temperature to about 131℃
and remove methanol. 4 more
After being maintained at this temperature for an hour, it is cooled, 500 ml of water are added, the two layers are separated and the organic phase is dried over sodium sulfate. The solvent is then evaporated off under a water jet vacuum and the residue is fractionally distilled under high vacuum. After separating a small amount of the distillate, the purity is 96%.
%, 327.5 g of a thin reddish liquid with a boiling point of 105 DEG -118 DEG C./0.06 mbar are obtained. In a similar manner, 1,4-bis-(diethoxyphosphonomethyl)-benzene was reacted with the corresponding aldehyde to obtain the compound shown in the table of formula (302) below.

【table】

[Table] The aldehyde of the following formula (316) required for the production of the compound of formula (314) can be produced as follows: About 85% dimethylamino-ethanothiol hydrochloride (100 g) was added to a mixture of 61.7 g of 88% potassium hydroxide and 60 ml of dimethyl sulfoxide in 54.3 g of water with vigorous stirring under a nitrogen atmosphere and with cooling.
Add at a temperature that does not exceed 20°C. Then 0-
Drop 57.2 g of chlorbenzaldehyde and
2 hours at 80°C and 2 hours at 80°C.
After cooling to room temperature, add 300ml of methylene chloride and water.
300 ml, mix well, separate the two layers and dry the organic phase with sodium sulfate. The solvent is evaporated and the residue is fractionally distilled under high vacuum. After separating the distillate, 18.6 g of a yellow liquid with a purity of 79.3% and a boiling point of 97-106°C/0.03 mbar was obtained.
is obtained. Example 4 Instead of a single aldehyde in Example 3,
Mixture of the following two isomeric aldehydes (400)
was used.

[expression] and

[Formula] As a result, an isomer mixture (401) of two symmetrical compounds of the following formulas (401a) and (401b) and an asymmetrical compound of the formula (401c) were obtained. Melting point:
50-70℃ (after recrystallization from hexane). The isomer mixture of aldehyde of formula (400) is produced by reacting salicylaldehyde and 2-chloro-1-dimethyl-aminopropane hydrochloride according to Example 3, production of formula (300). . Example 5 4.85 g of the compound of formula (303) is dissolved in 50 ml of methyl ethyl ketone, and 2.5 ml of dimethyl sulfate is added dropwise to the solution while stirring at about 70°C. After heating under reflux for a further 1 hour, it is cooled, the precipitated product is filtered off with suction and washed repeatedly with methyl ethyl ketone.
Compound 7.2 of the following formula (600) was dried under vacuum at 100℃.
g (96% of theory). This product contains approximately 1/2 mole of water of crystallization, exhibits the form of bright yellow crystals, and has a melting point of 254°C.
(unclear). Chlorobenzene can also be used instead of methyl ethyl ketone as a solvent. In this example, the amount of dimethyl sulfate used was
When reducing from 2.5 ml to 1.0 ml, a mixture of a symmetric compound of formula (600) and an asymmetric compound of formula (600a) below is obtained. From the compound of formula (301) and the compounds listed in the table, the following formula (601) can be obtained by the same method as above.
The brightener compounds listed in the table are obtained.

【table】

Table: For the preparation of the compound of formula (611), 100 ml of 1,2-dichloroethane are used instead of methyl ethyl ketone. During the preparation of compounds of formula (605) and (612), a further small amount of dimethylformamide is added to the complete solution of the starting material. Example 6 By quaternizing the isomer mixture of formula (401) according to Example 5, an isomer mixture of formula (700) was obtained. This mixture has a melting point of 240℃ (unclear)
It contains about 1/2 mole of water of crystallization and is an isomer mixture consisting of the following two symmetrical compounds (700a) and (700b) and an asymmetrical compound (700c). Example 7 Compound of the following formula (800) in 50 ml of chlorobenzene
Dissolve 4.7g. 5.5 g of trimethylamine are introduced into this solution over a period of 10 minutes while stirring at a temperature of 90°C. After stirring for a further 15 minutes at this temperature, the precipitated product is filtered off with suction at about 60°C, washed repeatedly with methyl ethyl ketone and dried under vacuum at 100°C. Compound of the following formula (801)
Obtain 5.0g. In this example, instead of trimethylamine
By adding 3.2 ml of pyridine and using 50 ml of methyl ethyl ketone as a solvent and further operating at reflux temperature (1 hour), the compound of the following formula (802) was prepared.
3.8g was obtained. The compound of formula (800) required as a starting material is produced as follows. 21.5 g of terephthalaldehyde and 158.2 g of the compound of the following formula (803) are dissolved in 500 ml of dimethylformamide. The temperature of this solution is increased while stirring under a nitrogen atmosphere.
126.6 g of a 30.7% methanol solution of sodium methylate is added dropwise while ensuring that the temperature does not exceed 40°C.
The temperature is maintained at 40-45° C. for 2 hours, then cooled and 150 ml of water are added to the reaction mixture. Introduce carbon dioxide until saturation or add dry ice to neutralize to pH 8. At this time, a yellow colored reaction product precipitates. This precipitate is filtered by suction,
Wash repeatedly with water, dry under vacuum and recrystallize from methyl ethyl ketone. However, the following formula (804)
13.8 g of the compound is obtained. 12.6 g of this compound of formula (804) is stirred under reflux in 40 ml of chloroacetyl chloride overnight. Finally, a complete solution is obtained. Add cyclohexane to this solution.
Add 40 ml, cool, and suction filter the precipitated product.
Wash repeatedly with cyclohexane and vacuum dry at 80°C. Recrystallized from nonane, melting point 146-149℃
11.6 g of the compound of formula (800) are obtained in the form of pale yellow crystals. Example 8 A bleached cotton fabric was treated in a dyeing device using an aqueous bath at a bath ratio of 1:20. The aqueous bath used contained a brightener of formula (101), (200), (600), (602) to (606) or (700) at 0.1% based on the weight of the cotton fabric.
and 5 g/containing sodium sulfate. The temperature program for the treatment was as follows. 20-50°C/15 minutes 50°C/15 minutes The cotton fabric was then rinsed in running softened water for 20 seconds and dried in a drying chamber at a temperature of 70°C. The cotton fabric treated as described above showed an excellent gloss effect. Example 9 A bleached cotton fabric was brightened using an aqueous bath at room temperature. The aqueous bath used contained 1 g/b of brightener of formula (101) or (200). The squeeze rate was 75%. Then, it was dried using a heat fixing device at a temperature of 130° C. for 30 seconds. The cotton fabric treated as described above showed an excellent gloss effect. Example 10 A polyacrylonitrile fabric (trade name "Orlon 75") was treated in a dyeing apparatus using an aqueous bath with a bath ratio of 1:20. The aqueous bath used contained the following components: formulas (101), (200), (301), (303) to (307),
(401), (600), (602) to (606) or (700)
Brightener: 0.1% (based on fabric weight), 35% ethylene oxide per mole of stearyl alcohol
Adduct with moles added...1g/, 85% formic acid...1.5ml/. The temperature program for the treatment was as follows: 40-97°C/30 minutes 97%/30 minutes 97-40°C/15 minutes The polyacrylonitrile fabric was then rinsed in softened running water for 20 seconds. and dried in a drying room at a temperature of 70°C. Fabrics treated in this way showed excellent gloss effects. Example 11 A polyacrylonitrile fabric (Courtelle) was treated in a dyeing apparatus using an aqueous bath with a bath ratio of 1:20. The aqueous bath used contained the following components: Formulas (301), (303) to (307), (401), (600) to
(606) or (700) brightener
...0.1% (based on the weight of the fabric) Oxalic acid ...1 g / Sodium-hexametaphosphate ...0.25 g / Sodium-metabisulfite ...0.125 g / The treatment temperature program was as follows. 40-100℃/30 minutes 100℃/30 minutes 100-40℃/15 minutes The polyacrylonitrile fabric was then rinsed with softened running water for 30 minutes, centrifuged, and ironed at 150℃. Dry. Fabrics treated in this way showed excellent gloss effects. Example 12 Bleached cotton fabrics were treated for 15 minutes in an aqueous softening rinse bath heated to 30°C at a bath ratio of 1:20.
This bath contains quaternary dimethyl distearyl ammonium chloride per 1 bath solution.
0.2 g and 0.01 g of a brightener of formula (101), (200), (600) or (602). The cotton fabric was then rinsed for 5 seconds under running potable water and dried in a drying chamber at a temperature of 70°C. Cotton fabrics treated in this way showed excellent gloss effects. Example 13 Bleached cotton fabrics were washed for 15 minutes using an aqueous bath heated to 40° C. in a bath ratio of 1:20. The aqueous bath used contained the following components per bath: 1 mole of stearyl alcohol to 10 ethylene oxides.
Adduct with added moles...0.5g, Formula (101), (200), (600), (602) to (606) brightener...0.01g. The cotton fabric was then rinsed with running potable water for 20 seconds and dried in a drying chamber at a temperature of 70°C. Cotton fabrics treated in this way showed excellent gloss effects. The same treatment was carried out by adding 0.2 g of active chlorine in the form of sodium hypochlorite to the above bath.
Similar excellent brightening effects were obtained using brighteners of formula (600). Example 14 A piece of polyamide fiber tricot cloth was washed in an aqueous bath at 40° C. for 15 minutes at a bath ratio of 1:20. Each aqueous bath contained the following substances in the following amounts. 1 mole of stearyl alcohol to 10 ethylene oxide
Mol adduct...0.5 g Brightener of formula (101) or (200)...0.01 g The cloth pieces were then rinsed under running drinking water for 20 seconds and dried in a drying chamber at a temperature of 70°C. . The polyamide-tricot fabric pieces treated in this way showed an excellent gloss effect. Example 15 A polyamide-6 fiber fabric was brightened in a bath containing the following ingredients. Brightener of formula (301), (303) to (306), (313) or (401)...1g/1 mole of stearyl alcohol to 35% of ethylene oxide
Adduct obtained by adding moles of ethylene oxide to 1 mole of P-tert-octylphenol...1 g/ Ethanol (95%)...90 ml Sodium phosphate buffer solution...0.5 g/ Bath absorption rate of this fabric It was squeezed to 85% and placed in a dyeing apparatus containing an amount of water such that the bath ratio was 1:25. The temperature program for dyeing was as follows. 50-100℃/10 minutes 100℃/20 minutes 100-50℃/5 minutes After this, rinse the fabric with cold soft water.
It was centrifuged and dried by ironing with an iron heated to 180°C. The polyamide-6 fabric treated in this way showed an excellent gloss effect. Example 16 A polyamide-6 fiber fabric was brightened in a bath containing the following substances in the following amounts. Brightener of formula (600), (602) to (606) or (700)...1g/1 mole of stearyl alcohol to 35% ethylene oxide
Adduct obtained by adding 8 moles of ethylene oxide to 1 mol of p-tert-octylphenol...1 g/Ethanol (95%)...90 ml Sodium tripolyphosphate...2 g/. The fabric was squeezed to a bath absorption of 85% and the fabric thus treated was then placed in a dyeing apparatus containing water in an amount giving a bath ratio of 1:25. The temperature program for dyeing was as follows. 30-60℃/10 minutes 60℃/20 minutes After this, it was rinsed with cold soft water, centrifugally dehydrated, and dried with an iron heated to 180℃.
The polyamide-6 fabric treated in this way showed an excellent gloss effect. Example 17 A bleached cotton fabric was brightened in a bath containing the following substances in the following amounts. Brightener of formula (600), (602) to (606) or (700)...1g/1 mole of stearyl alcohol to 35% ethylene oxide
Adduct obtained by adding 8 moles of ethylene oxide to 1 mol of p-tert-octylphenol...1 g/Ethanol (95%)...90 ml Sodium tripolyphosphate...2 g/. This cotton cloth was wrung out to absorb 75% of the bath. The cotton fabric thus treated was placed in a dyeing apparatus containing water in an amount such that the bath ratio was 1:25. Dyeing was carried out using the following temperature program. 30-70°C/10 minutes 70°C/20 minutes The cloth was then rinsed with cold soft water, centrifuged, and dried by ironing with an iron heated to 155°C. Cotton fabrics treated in this way showed excellent gloss effects. Example 18 5 g of pulp (consisting of bleached sulfite cellulose and bleached beech cellulose 1:1) are suspended in 50 ml of water and mixed with 150 ml of brightener solution in a mixer for 15 g.
Mix well for a minute. The brightener solution is expressed by the formula (101),
(200) or (600) brighteners were contained in an amount of 4 mg, corresponding to a 0.08% concentration. Lime, such as 1.5% by weight of Bowoidleim and 2.5% by weight of aluminum sulfate (both based on the weight of the pulp) were then added and diluted to a volume of 1000ml with approximately 10° dH water. When paper was made using this pulp liquid, the paper obtained showed an excellent gloss effect. Example 19 5 g of pulp (consisting of bleached sulfite cellulose and bleached beech cellulose 1:1) are suspended in 150 ml of water containing 5 mg of cationically active polyether amine and mixed for 15 minutes with 50 ml of brightener solution in a mixer. Mixed. This brightener solution contains 5 brighteners of formula (200) or (600) corresponding to a concentration of 0.08%.
It was contained in the amount of mg. After mixing lime for example
Bewoidlim 1.5% by weight, aluminum sulfate 2.5% by weight and cationically active polyetheramine 01%
(Both are based on pulp weight and approx.
It was diluted to 1000ml by adding 10°dH water. When paper was made using this pulp liquid, a paper sheet showing a good gloss effect was obtained. Example 20 5 g of pulp (consisting of bleached sulfite cellulose and bleached beech cellulose 1:1) were suspended in 150 ml of water containing 5 mg of polyethyleneimine and mixed with the brightener solution in a mixer for 15 minutes. This brightener solution contained a brightener of formula (200) or (600) in an amount of 4 mg, corresponding to a 0.08% concentration. Lime such as 1.5% by weight of Bewoidleim, 2.5% by weight of aluminum sulfate and 0.1% of polyethyleneimine (all based on the weight of the pulp) were then added and diluted to 1000ml with approximately 10° dH of water. When paper was made using this pulp liquid, a paper sheet having an excellent gloss effect was obtained. Example 21 A concentrated liquid detergent was prepared by blending the following ingredients. Weight% Ethoxylated alcohol 60.0 (65 moles of ethylene oxide added _C12 - _C13 alcohol) 1-methyl-1-oleylamide ethyl-
2-Oleylimidazolinium-methosulfate 26.7 Compound of formula (101), (200), (600), (602) to (606) or (700) 0.3 Water 12.0 Common additives 1.0 Add 5 kg of bleached cotton fabric to the above detergent Washing was carried out in water 60 containing 50-60 g of 100 ppm hard matter at a temperature of 50° C. for 10 minutes. After rinsing and drying, the fabric exhibited a strong shine effect and a soft feel. Similar results were obtained when a liquid detergent having the following composition was used instead of the above. Weight% Ethoxylated alcohol 55.0 (6.5 moles of ethylene oxide added _C12 - _C13 alcohol) 1-Methyl-1-stearylamide-ethyl-
2-stearylimidazolium-methosulfate 26.0 Compounds of formula (101), (200), (600), (602) to (606) or (700) 0.3 Water 13.0 Isopropanol 5.0 Common additives 0.7 Also, other nonionic interfaces Liquid detergents containing active agents and cationic substances, such as “Perwoll liquid” or “Samtess liquid” sold on the market
Similar results were obtained when the brightener of the present invention was blended with the brightener of the present invention. Example 22 A liquid detergent was prepared by blending and mixing the following components. Weight % Ethoxylated alcohol 12.0 (C ₁₄ -C ₁₅ alcohol with 7 moles of ethylene oxide added) Ethoxylated alcohol 12.0 (C ₁₂ -C ₁₃ alcohol with 6.5 moles of ethylene oxide added) Uncured di-stearyl-dimethyl ammonium chloride 6.4 Ethanol 15.0 Sodium bicarbonate 0.25 Compound of formula (600), (602) to (606) or (700) 0.41 Commonly used additives 0.41 Water 53.53 Cotton fabrics washed with the above liquid detergent in the same manner as in Example 21 had a strong gloss effect. It had a smooth and soft feel. Example 23 100 parts polyvinyl chloride, stabilizer (AdvastatBD
100: Ba/Cd complex) 3 parts, titanium dioxide 2 parts,
59 parts of dioctyl phthalate and formula (301),
The compounds (303) to (306) or (401) were intimately mixed and the mixture was rolled into a foil in a calender at a temperature of 150-155°C. The resulting opaque polyvinyl chloride foil exhibited a substantially higher degree of whiteness than the foil that did not contain the fluorescent brightener of the invention.

Claims (1)

[Claims] 1 formula (In the formula, X ₁ means a direct bond, _- SO ₂ NH _- at m-position with respect to oxygen, sulfur or styryl group, and Y ₁ and Y′ ₁ are each independently C _1-4 -alkylene R″ ₁ and R″ ₂ each independently represent C _1-4 -alkyl, or together they form a pyrrolidine ring, piperidine ring or morpholine ring, or together with R′ ₃ to form a pyridine ring, R′ ₃ means hydrogen, C _1-4 -alkyl or together with R″ ₁ and R″ ₂ form a pyridine ring, R ₅ represents hydrogen, chlorine, C _{1- 4} -alkyl, _C1-3 -alkoxy, _R6 means hydrogen, chlorine, _C1-4 -alkyl, _C1-3 -alkoxy, _R7 means hydrogen, n and n' and A means a colorless anion). 2 formulas (In the formula, X ₂ means oxygen, sulfur or _{-SO 2} NH _- at the m-position, Y ₂ means C _1-4 -alkylene, and R ₁ represents unsubstituted C _1-4 -alkyl. or together with R ₂ to form a pyrrolidine, piperidine or morpholine ring, or together with R ₂ and R ₃ to form a pyridine ring, R ₂ represents unsubstituted C _1-4 -alkyl or together with R ₁ to form a pyrrolidine ring, piperidine ring or morpholine ring, or together with R ₁ and R ₃ to form a pyridine ring, R ₃ is hydrogen, unsubstituted C _1-4 -alkyl or together with R ₁ and R ₂ form a pyridine ring, n is a number of 0 or 1 and A is a colorless anion). 3 formulas (wherein, X ₁ is a direct bond, oxygen, sulfur or m-position
_- SO ₂ NH _- , Y ₁ means C _1-4 alkylene, R″ ₁ and R″ ₂ each independently represent C _1-4 -alkyl, or both together represent pyrrolidine. form a ring, a piperidine ring or a morpholine ring, or together with R′ ₃ form a pyridine ring, R′ ₃ means hydrogen, C _1-4 -alkyl or together with R″ ₁ and R″ ₂ to form a pyridine ring, R ₅ means hydrogen, chlorine, C _1-4 -alkyl, C _1-3 -alkoxy, R ₆ means hydrogen, chlorine, C _1-4 -alkyl, C _1-3 - Distyrylbenzene according to claim 1, wherein R ₇ is hydrogen, n is a number of 0 or 1, and A is a colorless anion. 4 formula (where X ₃ is a direct bond, oxygen, sulfur or m-position
_- SO ₂ NH _- , Y ₃ means C _1-4 -alkylene, R ₁ and R ₂ each independently represent C _1-4 -alkyl, or both together form a pyrrolidine ring. ,
form a piperidine ring or a morpholine ring or together with R ₃ ' form a pyridine ring, R' ₃ means hydrogen, C _1-4 -alkyl or together with R ₁ and R ₂ form a pyridine ring; forming, R′ ₅ is hydrogen, chlorine, C _1-4 -alkyl, or
Distyrylbenzene according to claim 3 of C _1-3 -alkoxy, n is the number 0 or 1 and A means a colorless anion. 5 formula (In the formula, Y ₄ means C _2-4 -alkylene, R ₁ 〓 means C _1-3 -alkyl, or
together with R ₂ 〓 form a pyrrolidine ring, piperidine ring or morpholine ring, R ₂ 〓 means C _1-3 -alkyl or
together with R ₁ 〓 form a pyrrolidine ring, piperidine ring or morpholine ring, R ₃ ″ is hydrogen or C _1-3 -alkyl, n is a number of 0 or 1, and A means a colorless anion) Distyrylbenzene according to claim 3 of the formula 6. (In the formula, X ₄ means oxygen, sulfur or -SO _{2 NH - at} m-position, Y ₅ means C _2-4 -alkylene, R ₁ 〓 means unsubstituted C _1-4 -alkyl or together with R ₂ 〓 to form a pyrrolidine ring, piperidine ring or morpholine ring, R ₂ 〓 means unsubstituted C _1-4 -alkyl or together with R ₁ 〓 to form a pyrrolidine ring, forming a piperidine ring or a morpholine ring, _R3 means hydrogen or unsubstituted _C1-4 -alkyl, A means a colorless anion, and n means a number of 0 or 1). Distyrylbenzene according to Range 2. 7 formula (In the formula, Y ₅ means C _2-4 -alkylene, R ₁ 〓 means unsubstituted C _1-4 -alkyl, or together with R ₂ 〓 represents a pyrrolidine ring, a piperidine ring or a morpholine ring. R ₂ 〓 means unsubstituted C _1-4 -alkyl or together with R ₁ 〓 form a pyrrolidine ring, piperidine ring or morpholine ring, R ₃ is hydrogen or unsubstituted C _{1- 4} -alkyl, A is a colorless anion, and n is a number of 0 or 1). 8 formula In the formula, Y ₅ means C _2-4 -alkylene, R ₁ 〓 means unsubstituted C _1-4 -alkyl, or together with R ₂ 〓 form a pyrrolidine ring, piperidine ring or morpholine ring. , R ₂ 〓 means unsubstituted C _1-4 -alkyl or together with R ₁ 〓 forms a pyrrolidine ring, piperidine ring or morpholine ring, R ₃ is hydrogen or unsubstituted C _1-4 -alkyl, A is a colorless anion, and n is a number of 0 or 1). 9 formula (In the formula, R ₁ 〓=R ₂ 〓 and each means methyl or ethyl, R ₃ 〓 means hydrogen, methyl or ethyl, A′ is CH ₃ OSO ₃ , C ₂ H ₅ OSO ₃ or [ Distyrylbenzene according to claim 7 having the formula: n is a number of 0 or 1, and m is a number of 2 or 3. 10 formula (In the formula, R ₁ 〓=R ₂ 〓 and each means methyl or ethyl, R ₃ 〓 means hydrogen or methyl, A″ means CH ₃ OSO ₃ or [formula], and n is Distyrylbenzene according to claim 9 of the following formula: 12 Distyrylbenzene according to claim 8 of the following formula: 13 Distyrylbenzene according to claim 8 of the following formula: 14 Distyrylbenzene according to claim 8 of the following formula: 15 formula (In the formula, X ₁ means a direct bond, _- SO ₂ NH _- at m-position with respect to oxygen, sulfur or styryl group, and Y ₁ and Y′ ₁ are each independently C _1-4 -alkylene R″ ₁ and R″ ₂ each independently represent C _1-4 -alkyl, or together they form a pyrrolidine ring, piperidine ring or morpholine ring, or together with R′ ₃ to form a pyridine ring, R′ ₃ means hydrogen, C _1-4 -alkyl or together with R″ ₁ and R″ ₂ form a pyridine ring, R ₅ represents hydrogen, chlorine, C _{1- 4} -alkyl, _C1-3 -alkoxy, _R6 means hydrogen, chlorine, _C1-4 -alkyl, _C1-3 -alkoxy, _R7 means hydrogen, n and n' is a number of 0 or 1 independently of each other, and A means a colorless anion), in the method for producing distyrylbenzene of the formula (wherein, X ₁ , Y ₁ , Y ₁ ′, R ₁ ″, R ₂ ″, R ₅ , R ₆ and R ₇ have the above meanings), one molar equivalent of distyrylbenzene of the formula R ₃ ′- A production method characterized by quaternizing or protonating A (wherein A and R ₃ ' have the above meanings) with 1 or 2 molar equivalents of an alkylating agent or acid. 16 formula (In the formula, Y ₄ means C _2-4 -alkylene, R ₁ 〓 means C _1-3 -alkyl or
together with R ₂ 〓 form a pyrrolidine ring, piperidine ring or morpholine ring, R ₂ 〓 means C _1-3 -alkyl or
together with R ₁ 〓 form a pyridine ring, piperidine ring or morpholine ring, R ₃ ″ means hydrogen or C _1-3 -alkyl, n is a number of 0 or 1, and A represents a colorless anion. In the method of claim 15 for producing distyrylbenzene having the formula A compound with the formula [In both of the above formulas, Y ₄ , R ₁ 〓 and R ₂ 〓 have the above-mentioned meanings, and Z ₁ and Z ₂ mean that one of them represents an OCH- group and the other represents the formula [Formula] or [Formula] (where D ₁ is a substituted or unsubstituted alkyl group,
aryl, cycloalkyl or aralkyl) in a molar ratio of 1:2 and, if desired, the resulting formula (In the formula, Y ₄ , R ₁ 〓, R ₂ 〓 have the above meanings)
A process characterized by quaternizing or protonating a compound of the formula R ₃ ″-A with 2 molar equivalents of an alkylating agent or acid of the formula R 3 ″-A, in which R ₃ ″ and A have the meanings given above. Law. 17 formula (In the formula, X ₁ means a direct bond, _- SO ₂ NH _- at m-position with respect to oxygen, sulfur or styryl group, and Y ₁ and Y′ ₁ are each independently C _1-4 -alkylene R″ ₁ and R″ ₂ each independently represent C _1-4 -alkyl, or together they form a pyrrolidine ring, piperidine ring or morpholine ring, or together with R′ ₃ to form a pyridine ring, R′ ₃ means hydrogen, C _1-4 -alkyl or together with R″ ₁ and R″ ₂ form a pyridine ring, R ₅ represents hydrogen, chlorine, C _{1- 4} -alkyl, _C1-3 -alkoxy, _R6 means hydrogen, chlorine, _C1-4 -alkyl, _C1-3 -alkoxy, _R7 means hydrogen, n and n' is a number of 0 or 1 independently of each other, and A means a colorless anion). Fluorescent glossing method. 18. Process according to claim 17 for fluorescently brightening polyacrylonitrile and cellulose as organic materials. 19 formula (In the formula, X ₁ means a direct bond, _- SO ₂ NH _- at m-position with respect to oxygen, sulfur or styryl group, and Y ₁ and Y′ ₁ are each independently C _1-4 -alkylene R″ ₁ and R″ ₂ each independently represent C _1-4 -alkyl, or together they form a pyrrolidine ring, piperidine ring or morpholine ring, or together with R′ ₃ to form a pyridine ring, R′ ₃ means hydrogen, C _1-4 -alkyl or together with R″ ₁ and R″ ₂ form a pyridine ring, R ₅ represents hydrogen, chlorine, C _{1- 4} -alkyl, _C1-3 -alkoxy, _R6 means hydrogen, chlorine, _C1-4 -alkyl, _C1-3 -alkoxy, _R7 means hydrogen, n and n' and A means a colorless anion). 20 10 to 70% by weight of nonionic surfactant and 1
A detergent according to claim 19, comprising from 30% by weight of a cationic fabric softener. 21 10 to 70% by weight of a nonionic surfactant;
1 to 30% by weight of a quaternary derivative of ammonia and/or imidazoline with two long-chain aliphatic saturated or unsaturated residues as a cationic fiber softener and also a solvent to impart a liquid form. A detergent according to claim 20, comprising: 22 As cationic fiber softeners, 1-methyl-1-oleylaminoamidoethyl-2-oleyl-imidazolium.X, 1-methyl-1-stearylamidoethyl-2-stearyl-imidazolium.X, di- Stearyl-dimethyl-ammonium.X or formula (wherein Q means C _14-16 -alkyl and in the formula and above X ^- is chloride ion,
22. A detergent according to claim 21, which contains a compound of bromide ion, methyl sulfate ion, ethyl sulfate ion, methanesulfonate ion, ethanesulfonate ion or toluenesulfonate ion. 23 formula (In the formula, X ₁ means a direct bond, _- SO ₂ NH _- at m-position with respect to oxygen, sulfur or styryl group, and Y ₁ and Y′ ₁ are each independently C _1-4 -alkylene R″ ₁ and R″ ₂ each independently represent C _1-4 -alkyl, or together they form a pyrrolidine ring, piperidine ring or morpholine ring, or together with R′ ₃ to form a pyridine ring, R′ ₃ means hydrogen, C _1-4 -alkyl or together with R″ ₁ and R″ ₂ form a pyridine ring, R ₅ represents hydrogen, chlorine, C _{1- 4} -alkyl, _C1-3 -alkoxy, _R6 means hydrogen, chlorine, _C1-4 -alkyl, _C1-3 -alkoxy, _R7 means hydrogen, n and n' is a number of 0 or 1 independently of each other, and A means a colorless anion). 24 formula (In the formula, X ₁ means a direct bond, _- SO ₂ NH _- at the m-position with respect to oxygen, sulfur or styryl group, and Y ₁ and Y′ ₁ each independently represent C _1-4 -alkylene R″ ₁ and R″ ₂ each independently represent C _1-4 -alkyl, or together they form a pyrrolidine ring, piperidine ring or morpholine ring, or together with R′ ₃ to form a pyridine ring, R′ ₃ means hydrogen, C _1-4 -alkyl or together with R″ ₁ and R″ ₂ form a pyridine ring, R ₅ represents hydrogen, chlorine, C _{1- 4} -alkyl, _C1-3 -alkoxy, _R6 means hydrogen, chlorine, _C1-4 -alkyl, _C1-3 -alkoxy, _R7 means hydrogen, n and n' is a number of 0 or 1, and A means a colorless anion), and a cationic fabric softener.