JPH0233695B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a new distyryl biphenyl, a process for its preparation and its use as a fluorescent agent for organic materials. Water-soluble distyrylbiphenyl in which the benzene nucleus is anionically substituted is known from the literature, for example, German Patent Publication No. 1793482. However, this known compound has no affinity with cationically active fiber finishing aids. Certain cationically substituted distyrylbiphenyls are also known, but because of their cationic properties, they give unsatisfactory results when used in cationic media. According to the present invention, distyrylbiphenyl has now been discovered which does not have the above-mentioned drawbacks. That is, the present invention relates to a novel distyrylbiphenyl represented by the following formula (2). (In the above formula, X ₁ means a direct bond, oxygen, sulfur, -OCO- or -COO-, Y ₁ and Y′ ₁ independently of each other mean C _1-4 -alkylene or hydroxypropylene. , R″ ₁ and R″ ₂ independently represent C _1-4 -alkyl, or together they form a pyrrolidine ring, piperidine ring or morpholine ring, or
together with R′ ₃ forms a pyridine ring, R′ ₃ is hydrogen, C _1-4 -alkyl or together with R″ ₁ and R″ ₂ forms a pyridine ring, R ₅ is hydrogen, Chlorine, C _1-4 -alkyl, C _1-3 -alkoxy, R ₆ means hydrogen, chlorine, C _1-4 -alkyl, C _1-3 -alkoxy, n and n′ are mutually exclusive. independently a number of 0 or 1 and A means a colorless anion. Among the above formula (2), preferred distyrylbiphenyl satisfies the following conditions. symmetric, i.e. Y ₁ =Y′ ₁ and n=
n'; X ₁ does not mean -COO-; quaternized, i.e. n and n' are numbers 1; X ₁ is in the 2-position and R' ₃ C _1-3 -It is an alkyl. In distyrylbiphenyl of formula (2), the substituent
The alkyl and alkoxy groups represented by R ₅ and R ₆ are preferably methyl and methoxy. Particularly preferred are distyrylbiphenyls of the following formulas (3), (4) and (5): (In the above formula, X ₂ means oxygen, sulfur, -OCO- or -COO-, Y ₂ means C _1-4 -alkylene, R ₁ means C _1-4 -alkyl or _R2
together with 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 C _1-4 -alkyl or R ₁
together with form a pyrrolidine ring, piperidine ring or morpholine ring, or together with R ₁ and R ₃ form a pyridine ring, R ₃ means hydrogen, C _1-4 -alkyl, or R ₁ and R together with ₂ to form a pyridine ring, n is a number of 0 or 1, and A means a colorless anion; benzene nuclei B and C can be further replaced by non-chromophores), (In the formula, X ₁ means a direct bond, oxygen, sulfur, -OCO- or -COO-, Y ₁ means C _1-4 -alkylene or hydroxypropylene, R″ ₁ and R″ ₂ are Each independently represents C _1-4 -alkyl, or together they form a pyrrolidine ring, piperidine ring, or morpholine ring, or together with R′ ₃ they form a pyridine ring, R′ ₃ is 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, C _1-3 -alkoxy , R ₆ means hydrogen, chlorine, C _1-4 -alkyl, C _1-3 -alkoxy, n is a number of 0 or 1 and A means a colorless anion), (In the formula, X ₁ means a direct bond, oxygen, sulfur, -OCO- or -COO-, Y ₁ means C _1-4 -alkylene or hydroxypropylene, and R ₁ and R ₂ are mutually independently represents C _1-4 -alkyl, or together they form a pyrrolidine ring, piperidine ring or morpholine ring, or together with R′ ₃ they form a pyridine ring, R′ ₃ is hydrogen, C _{1 -4} -alkyl, or together with R ₁ and R ₂ form a pyridine ring, 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). In formulas (3), (4), (5) and (6), X ₁ and X ₂ are preferably in the 2-position and R′ ₃ and
R″ ₃ is C _1-3 -alkyl, n is 1, A is CH ₃ OSO ₃ ,
_C2H5OSO3 , _Cl , Br, _{CH3COO ,}
HCOO or

[Formula]. The following distyryl biphenyls are important: A) Formula: (In the formula, Y ₃ means C _2-4 -alkylene, R〓 ₁ means C _1-3 -alkyl, or R ₂ 〓 ₂
together with to form a pyrrolidine ring, piperidine ring or morpholine ring, R〓 ₂ means C _1-3 -alkyl or R〓 ₁
together with to form a pyrrolidine 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 means a colorless anion), B) The following formula (wherein, X ₂ means oxygen, sulfur, or -COO-, Y ₂ means alkylene having 2 to 4 carbon atoms, and R ₁ ^v means alkyl having 1 to 4 carbon atoms. or together with R ₂ ^v to form a pyrrolidine ring, piperidine ring or morpholine ring, R ₂ ^v means alkyl having 1 to 4 carbon atoms, or together with R ₁ ^v to form a pyrrolidine ring , forming a piperidine ring or a morpholine ring, R〓 ₃ means hydrogen or alkyl having 1 to 4 carbon atoms, A is the equivalent of a colorless anion, and n is a number of 0 or 1, and a benzene nucleus B and C may be further substituted by a non-chromophore), C) the following formula (In the formula, X ₂ , Y ₂ , R ₁ ^v , R ₂ ^v , R〓 ₃ , A and n, and the benzene nuclei B and C have the above meanings), and D) The following formula Distyrylbiphenyl (wherein Y ₂ , R ₁ ^v , R ₂ ^v , R ₃ , A , n and benzene rings B and C have the above meanings). The following formula is particularly advantageous: (where A′ is CH ₃ OSO ₃ or C ₂ H ₅ OSO ₃
and R′ ₃ means methyl or ethyl), (In the formula, A′ is CH ₃ OSO ₃ or C ₂ H ₅ OSO ₃ ,
and R′ ₃ means methyl or ethyl) and (where A′ is CH ₃ OSO ₃ or C ₂ H ₅ OSO ₃
and R′ ₃ means methyl or ethyl) distyrylbiphenyl. The preparation of distyrylbiphenyl of the formula (1), in which X is a direct bond, oxygen or sulfur, and n and n' are the numbers 0, is carried out by methods known per se as follows. That is, in the presence of a strong base, the formula The compound and the formula below

[expression] and

[Formula] [In each of the above formulas, benzene nuclei B and C may be further substituted by a non-chromophore, X ₁ means a direct bond, oxygen or sulfur, and Y ₁ , Y' ₁ ,
R″ ₁ and R ₂ each have the abovementioned meaning, and Z ₁ and Z ₂ each have a COH- group and the other has the formula

【formula】

【formula】

[expression] or

[Formula] (where D ₁ is a substituted or unsubstituted alkyl group,
(meaning an aryl group, a cycloalkyl group or an aralkyl group) or a mixture of both in a molar ratio of 1:2, and the resulting formula The compound (wherein X ₁ , Y ₁ , Y′ ₁ , R″ ₁ and R″ ₂ have the abovementioned meanings and the benzene nuclei B and C can be further substituted by a non-chromophore) is then one of the alkylating agents or acids of the formula R′ ₃ —A, where R′ ₃ and A have the meanings given above, in a manner known per se.
or quaternized or protonated in an amount of 2 to 2 molar equivalents. Distyrylbiphenyl of formula (6) is produced as follows. In other words, in the presence of a strong base, the formula A compound with the formula [In each of the above formulas, Y ₃ , R ₁ ^v and R ₂ ^v have the above meanings, and one of Z ₁ and Z ₂ represents an OCH- group and the other represents a formula

【formula】

【formula】

[expression] or

[Formula] (where D ₁ is a substituted or unsubstituted alkyl group,
(meaning an aryl, cycloalkyl or aralkyl group) in a molar ratio of 1:2 and, if desired, the resulting formula (wherein Y ₃ , R〓 ₁ and R〓 ₂ have the above-mentioned meanings) by alkylation of the compound of the formula R″ ₃ -A (wherein R″ ₃ and A have the above-mentioned meanings) quaternize or protonate with 2 molar equivalents of agent or acid. 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, alcohols such as methanol, ethanol, isopropanol, butanol, glycols, glycol ethers such as 2-methoxyethanol, hexanol, cyclohexanol and cyclooctanol, and ethers such as cyclooctanol. Diisopropyl ether, tetrahydrofuran and dioxane and 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 aqueous solvent form. The temperature at which the reactions are 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 as condensing agent. The effectiveness of base combinations. 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 alkali compounds, 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 also in special cases, alkali sulfides, alkali carbonates, aryl-alkali compounds such as phenyl-lithium or strongly basic amines (including ammonium bases) such as trialkyl ammonium hydroxides can also be used and are suitable. You can get results. The starting compound of formula (14) or (15), in which Z ₂ is an aldehyde group, can be prepared in an organic solvent which does not participate in the reaction, such as alcohol, dialkylamides of aliphatic carboxylic acids, 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 1), 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, i.e. for the preparation of compounds of formula (16), for example if dimethylformamide is used, of formula (14) or There is no longer a need to isolate the compound (15). formula Distyrylbiphenyl (in which X ₁ means -COO-) is prepared from the corresponding acid by a method known per se (see German Patent Publications No. 1793482, No. 2209128). That is, it is produced by producing the acid halide by a known method and reacting the acid halide with a compound of HOY-N(R ₁ )(R ₂ ). formula (In the above formula, X ₁ means a direct bond, oxygen, sulfur, -OCO- or -COO-, Y ₁ and Y′ ₁ independently mean C _1-4 -alkylene, R″ ₁ and R″ ₂ independently represent C _1-4 -alkyl, or together they 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 means hydrogen, C _1-4 -alkyl or together with R″ ₁ and R″ ₂ to form a pyridine ring A is a colorless anion, n is a number of 0 or 1, and the benzene nucleus B and C form a ring.
and further substituted by a non-chromophore) can be prepared by methods known per se.
The distyrylbiphenyl of formula (16) is _expressed as
X ₁ , Y ₁ , Y′ ₁ , R″ ₁ , R″ ₂ , R′ ₃ , n and A have the above meanings)
It is produced by quaternization or protonation in 2 to 2 molar equivalents. 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 Dialkyl toluene sulfate, such as diethyl sulfate, or sulfonic acid esters, such as methyl benzenesulfonate or ethyl ester, alkylene oxides or epichlordohydrin, such as ethylene oxide or propylene oxide, formula (wherein B means methyl, ethyl, propyl, butyl or phenyl). formula (In the formula, R″ ₃ is alkyl having 1 to 4 carbon atoms,
D ₂ is hydrogen, unsubstituted alkyl or hydroxy,
Phosphites or phosphonates of cyano, alkyl substituted by alkylcarbonyloxy or alkoxycarbonyl each having 1 to 4 carbon atoms in the alkyl moiety and D ₃ meaning alkyl of 1 to 4 carbon atoms. The quaternization of the compound of formula (16) to the compound of formula (2) using an alkyl halide, dialkyl sulfate or sulfonic acid ester is preferably carried out in a solvent inert towards 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; 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 performed at temperatures between 0 and 180°C, preferably
It is advantageously carried out at temperatures between 30 and 140°C. Quaternization of formula (16) to a compound of formula (2) using alkylene oxide, epichlorohydrin or (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 the form of a concentrated acid, optionally mixed 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-
Methanesulfonate, methyl-decyl-methanephosphonate, methyldodecyl-methanephosphonate, dimethyl-β-hydroxy-ethanephosphonate, dimethyl-β-acetoxy-ethanephosphonate, 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 are methanol, ethanol, propanol, isopropanol, butanol, glycol, glycol-methyl ether, glycol-dimethyl ether, glycol butyl ether, diglycol methyl ether, methyl ethyl ketone, methyl butyl ketone,
These include dimethylformamide, sulfolane, oxypropionitrile, toluene, xylene, benzyl alcohol, phenoxyethanol, benzyloxypropionitrile, and the like. If a liquid quaternizing agent is used, the reaction can be carried out without the additional presence of a solvent. If a protonated compound of formula (2) is desired, ie an acid addition salt, 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 which dissolve the starting material 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 methyl ethyl ketone;
Fatty acid amides such as dimethylformamide or dimethylacetamide; sulfoxides such as dimethylsulfoxide and carboxylic acid esters such as acetate or acetate-butyl ester. Distyrylphenyl of the formula (2) in which X ₁ means -OCO- and n=n' means the number 1 can be prepared, for example, by starting from the corresponding phenol and reacting it with a halogen-acyl halide. and quaternization of the resulting reaction product with a trialkylamine or pyridine of the formula N(R ₁ )(R ₂ )(R ₃ ). In addition, here Y ₁
=Y′ ₁ , R ₁ =R″ ₁ , R ₂ =R″ ₂ and R′ ₃ has the above meaning. The quaternization is advantageously carried out in an inert solvent at a temperature of 50 to 160°C, preferably 80 to 130°C, using at least 2 moles of the amine. 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 furthermore 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) in admixture with dyes (for nuance) or pigments (colored pigments or especially white pigments) or as additives in dyeing baths; b) in admixture with wetting agents, softeners, swelling agents or antioxidants; c) in combination with various textile finishing methods, such as flame retardant, softening, sun protection or antistatic or insect repellent treatments; d) coatings for textiles, fleece, paper, leather; Impregnating or binding agent (solution, dispersion,
e) blending in dissolved or dispersed form in a polymer carrier (polymerization product, polycondensation product or polyaddition product) for use in an emulsion; as an additive for enhancing (e.g. to improve the appearance of soaps, detergents, laundry rinsing agents and textile treatment agents); f) in combination with other substances having a fluorescent shine effect; g) spinning bath preparations; Use in liquid. 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 the post-treatment bath 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) type of substituents; In some cases, it is 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. Amounts as small as 0.0001 weight percent in some cases can be achieved with a clear and durable gloss effect. However, amounts up to about 0.8 weight percent and sometimes up to about 2 weight percent may also be used. In most practical applications
A preferred usage range is 0.0005 to 0.5 weight percent. 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 for washing baths or as additives for commercial or household detergents and after-wash treatments. 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 be dissolved in or mixed with the laundry actives, kneaded or mixed together, and thus 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 after-rinse baths, which are commonly used for purposes such as imparting a soft feel, antistatic effect, sun protection, 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 invention therefore also relates to detergents which are preferably liquid and which, in addition to the novel distyryl biphenyl and the customary additives, also 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. This hydrophobic organic product can be a heterocyclic compound and especially an aliphatic or aromatic compound. 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 nonionic compounds that can 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
It has from 22 carbon atoms and is condensed 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 prevents static charges and prevents 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 antifouling agents or antigraying agents such as polyvinyl alcohol and hydroxypropyl methylcellulose; antifoaming 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 component 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 (and may also contain monohydric, dihydric or polyhydric alcohol or similar solvent), is 5 to 60% by weight.
used in amounts of The final finished detergent in liquid or powder form contains from 0.005 to 3% by weight of the compounds according to the invention.
Contain in an amount of The content of other auxiliaries is 5% of the detergent.
It is preferably less than % by weight. 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 fairly hard water at low temperatures. Therefore, the hard content of water is calculated as calcium carbonate and ranges from 0 to
It can be 300 ppm or more and the wash 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 be varied only 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 compound according to the invention is 0.005% based on the weight of the finished detergent or textile treatment agent in liquid or powder form.
It is blended in an amount of 1% to 1% or more. A laundry bath containing the brightener of the present invention in this predetermined amount/
The treatment bath imparts a daylight shine appearance to textile fabrics made of cellulose fibers, polyamide fibers, high finish cellulose fibers, polyester fibers, wool, etc. when washed. The washing treatment is carried out, for example, as follows: A washing bath is prepared containing 0.1 to 10 g/Kg of synthetic detergent and 0.05 to 1% of the brightener of the invention, based on the weight of the detergent. The given textiles are washed in this washing bath at temperatures of 20 to 100° C. for 1 to 30 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. The melting points and boiling points of quaternized compounds do not appear sharply. Example 1 20.6 g of 4,4'-bis-(dimethoxy-phosphono-methyl)-biphenyl (96.9% purity) and the formula Dissolve 24.2 g of the compound (purity 96%) in 230 ml of dimethylformamide, replace the air in this solution with nitrogen, and stir while making sure the temperature does not rise above 40°C to dissolve 30.4 g of sodium methylate.
% methanol solution is added dropwise. The temperature is maintained at 40 DEG-45 DEG C. for 2 hours, then cooled with ice-cold water and 23 ml of water are added to the reaction temperature. The precipitated product is filtered off with suction, washed repeatedly with methanol and water and dried under vacuum at 90°C. Therefore, the compound of the following formula
Obtain 27.6g. The compound exhibits a brilliant light yellow crystalline form with a melting point of 127-128°C (after recrystallization from nonane and n-propanol). The compound of formula (100) above is produced as follows: 244ml of salicylaldehyde is added to 200ml of chlorobenzene.
g and 344 g of 2-diethylamino-ethyl chloride hydrochloride are suspended, and 732 g of a 30.7% methanol solution of sodium methylate is added dropwise to this suspension while stirring under a nitrogen atmosphere. During this time, the suspension becomes yellow and thick. Gradually increase the temperature to approx.
The temperature is raised to 131°C and the methanol is removed by evaporation. After maintaining this temperature for a further 4 hours, allow to cool and add 500 ml of water. Two layers separate and the organic phase is dried with sodium sulfate.
The solvent is then evaporated off in a water jet vacuum and the residue is fractionally distilled under high vacuum. After separating a small amount of precursor distillate, 327.5 g of a pale pink liquid
is obtained. Boiling point 105-118℃/0.06mbar,
Content 96%. Similarly, 4,4'-bis(dimethoxyphosphonomethyl)-biphenyl was reacted with the corresponding aldehyde to obtain the compounds shown in the table below.

【table】

[Table] The aldehyde of the following formula (117) required for the production of the compound of formula (114) can be produced as follows. A mixture of 61.7 g of 88% potassium hydroxide and 60 ml of dimethyl sulfoxide in 54.3 g of water was heated under a nitrogen atmosphere with vigorous stirring and cooled to a temperature of 20°C.
Add 100 g of about 85% dimethylaminoethanethiol hydrochloride, taking care not to overcrowd.
Thereafter, 57.2 g of 0-chlorobenzaldehyde is added dropwise and kept first at 60°C for 2 hours and then at 80°C for 2 hours. After that, cool to room temperature, add 300ml of methylene chloride and 300ml of water, mix well, and
Separate the layers and dry the organic layer with sodium sulfate. The solvent is evaporated off and the residue is fractionally distilled under high vacuum. After removing the pre-distillate, the purity is 79.3
%, yellow liquid with boiling point 97-106°/0.03 mbar
18.6g is obtained. Example 2 The following mixture of two isomeric aldehydes is used instead of the single aldehyde of Example 1. and This yields an isomer mixture of two symmetrical compounds of formulas (201a) and (201b) and an asymmetrical compound of formula (201c), with a melting point of 122 to 130°C (after reconsolidation from nonane). The isomer mixture of aldehyde of formula (200) was obtained by converting salicylaldehyde to 2-chloro-1-dimethyl- in the same manner as in the case of the compound of formula (100) in Example 1.
Obtained by reaction with aminopropane hydrochloride. Example 3 Dimethylformamide was prepared in the same manner as in Example 1.
20.6 g of 4,4'-bis-(dimethoxyphosphonomethyl)-biphenyl (purity 69.9%) and 20.9 g of the compound of the following formula (300) were reacted with 150 ml. After recrystallization from xylene, 22.5 g of the compound of the following formula (301) is obtained as bright yellow crystals with a melting point of 208-210°C. 8.05 g of this compound was dissolved in 30 ml of dimethylformamide with stirring at a temperature of 115 °C and added to this solution a 33% alcoholic solution of dimethylamine.
Add 30ml. At this time, lower the temperature to 80℃.
After stirring for another 2 hours at 80°C, cool and add water.
Add 60ml. The precipitated product is filtered off with suction, washed repeatedly with water and dried under vacuum at 100°C. Thus, 9.3 g of the compound of the following formula (302) is obtained as pale yellow crystals with a melting point of 140 to 140°C (after recrystallization from nonane). Example 4 Compound of formula (101) in 50 ml of methyl ethyl ketone
2.5 ml of dimethyl sulfate is added dropwise to the solution containing 5.9 g while stirring at about 70°C. After heating under reflux for a further 1 hour, it is cooled and the precipitated product is filtered off with suction and washed repeatedly with methyl ethyl ketone. 100℃
The mixture was dried under vacuum to obtain 8.2 g of a compound of the following formula (600). This compound still contains about 1/2 mole of water of crystallization and takes the form of pale yellow crystals, whose melting point is
The temperature is 235-238°C. Chlorobenzene can also be used instead of methyl ethyl ketone as a solvent. In the same manner, the compounds listed in the table of the following formula (601) were obtained from the compounds listed in the table and the compounds of formulas (302) and (401), respectively.

【table】

Table: To prepare the compound of formula (613), chloroform or dioxane is used instead of methyl ethyl ketone to dissolve the starting materials and the operation is carried out at reflux temperature. Example 5 By quaternizing the isomer mixture of formula (200) according to Example 4, the following two symmetrical compounds (700a) and (700b) and one asymmetrical compound (700c) are obtained. An isomer mixture of formula (700) is obtained. This product contains approximately 1 mole of water of crystallization and has a melting point of 272-285°C. Example 6 Compound of formula (103) in 50 ml of methyl ethyl ketone
1.0 ml of dimethyl sulfate is added dropwise to the solution containing 5.6 g while stirring at 70°C. Heat under reflux for an additional hour, filter while hot, and wash three times with warm methyl ethyl ketone. Thus, a mixture of the symmetrical compound of the above formula (602) and the asymmetrical compound of the following formula (800) is obtained. Its melting point is 233-240°C. Similarly, starting from (114), the above formula (614)
A mixture of the compound represented by the formula (801) and the compound represented by the following formula (801) is obtained. Melting point is 249-252°C. Example 7 11.2 g of the compound of formula (103) are stirred in 25 g of dimethylmethanephosphonate at a temperature of 120° C. for 2 hours. At this time, the desired product crystallizes out.
Dilute with 25 ml of methyl ethyl ketone, cool, filter with suction and wash the residue repeatedly with methyl ethyl ketone. Vacuum dry at 100℃ and use the following formula (900)
13.1 g of the compound is obtained. This compound contains 1/2 mole of water of crystallization and its melting point is 243°C (decomposed). Similarly, starting from (104) and (101), compounds of the following formulas (901) and (902) were obtained, respectively. Crystals containing approximately 2 moles of water of crystallization, melting point 222-235°C Crystals containing about 11/2 moles of water of crystallization, melting point 165~
178°C Example 8 Dissolve 5.4 g of the compound of the following formula (1000) in 100 ml of chlorobenzene. Trimethylamine is introduced into this solution at 120° C. until saturation (approximately 10 minutes). After being allowed to cool to room temperature, the precipitated product is filtered off with suction, washed repeatedly with chlorobenzene and methyl ethyl ketone and dried under vacuum at 100°C. However, the melting point is 175℃
(Decomposition) to obtain 6.5 g of a compound of the following formula (1001). The starting material of formula (1000) is obtained as follows. Biphenyl-4 in 600ml of dimethylformamide,
42.0 g of 4'-dialdehyde and 197.7 g of the compound of the following formula (1002) are dissolved. To this solution, 159.3 g of a 30.5% methanol solution of sodium methylate was added dropwise while stirring under a nitrogen atmosphere. At this time, make sure the temperature does not exceed 40℃. After maintaining the temperature at 40-45 DEG C. for 2 hours, it is cooled and the reaction mixture is poured into 3000 ml of water with stirring. Neutralize to pH 8 by introducing carbon dioxide until saturation or by adding dry ice. This causes the reaction product to become resinous and precipitate. The aqueous phase is decanted, the reaction product is diluted with 3000 ml of water, filtered off with suction and washed repeatedly with water. The wet residue is dissolved in 1000 ml of boiling methyl ethyl ketone, the solution is clarified hot with 0.4 g of bleaching earth and concentrated to half its volume. After cooling to 0°C, the crystallized product is filtered off with suction, washed twice with 50 ml each of cold methyl ethyl ketone and dried under vacuum at 100°C. Thus, 34.7 g of a compound of the following formula (1003) was obtained. Melting point, 280-287°C (after recrystallization from methyl ethyl ketone). 15.6 g of the compound of formula (1003) was added to 40 ml of chloroacetyl chloride, and the mixture was stirred under reflux overnight. This gives a complete solution at the end. 40ml of this solution
of cyclohexane is added, cooled, and the precipitated product is filtered off with suction and washed repeatedly with cyclohexane. Vacuum drying at 100° C. and recrystallization from perchlorethylene give 13.4 g of the compound of formula (1000) in the form of pale yellow crystals. The melting point of the crystals is 182-185°C (after recrystallization from xylene). Example 9 Using the isomer of the following formula (1100) in place of the compound of formula (1000) in Example 8, A compound of the following formula (1101) was obtained. In this example, pyridine (3.2 ml) was used in place of trimethyleneamine. After a reaction time of one and a half hours, 4.5 g of a compound of the following formula (1102) was obtained. The starting compound of formula (1100) is obtained as follows. 4,4'-bis- in 1000ml of dimethylformamide
Dissolve 418 g of (dimethoxyphosphonomethyl)-biphenyl (purity 96.9%) and 256.2 g of 3-hydroxybenzaldehyde. 797 g of 30.5% sodium methylate methanol solution while stirring under nitrogen atmosphere and making sure the temperature does not rise above 40℃.
Add. After maintaining the temperature at 40-45°C for 4 hours, cool and add 2000 ml of water. Neutralize to approximately pH 8 by introducing carbon dioxide until saturation or by adding dry ice. The precipitated product is filtered off with suction, washed repeatedly with water and isopropanol, and dried under vacuum at 100°C.
317.9g). Recrystallization from dioxane gives a compound of formula (1103) in the form of pale yellow crystals. This compound is converted to formula (1100) according to Example 10, formula (1000). Example 10 102 g of the compound of the following formula (1400) is suspended in a mixture of 1000 ml of chlorobenzene and 2 ml of dimethylformamide at room temperature with stirring. 125 ml of thionyl chloride are added dropwise over 10 minutes, heated to 80°C and the reaction mixture is stirred at 80-85°C for 3 hours. After cooling to room temperature, the crystallized product was filtered off with suction, washed with hexane and 80-85
Vacuum dry at °C. Thus, 105.7 g of a compound represented by the following formula (1401) was obtained. 24.2 g of the compound of formula (1401) are suspended in 250 ml of 1,2-dimethoxyethane at 20° C. with stirring.
Then 2-dimethylamino-ethanol for 15 minutes.
Add 35.7 g dropwise and stir at 2-5° C. for 23 hours. The temperature of the suspension is then raised to 20° C. in 45 minutes and stirred for a further 4 hours at a temperature of 20-25° C. Pour this reaction mixture into 25000ml of water,
The product is filtered and dried under vacuum at 50-60°C. The product thus obtained was heated using activated carbon.
Recrystallize twice from a mixture of ml ethanol and 75 ml water. Therefore, the compound of the following formula (1402)
19.1g is obtained. Example 11 5.9 g of the compound of formula (1402) are dissolved in 250 ml of methyl ethyl ketone at 45° C. with stirring. After adding 2.5 ml of dimethyl sulfate, heat to boiling point and boil under reflux for 3.5 hours. After cooling to room temperature, the product is filtered off with suction, washed with methyl ethyl ketone and dried under vacuum at 60-70°C. Thus, 7.6 g of a compound of the following formula (1500) was obtained. Example 12 A bleached cotton fabric was treated in a dyeing device using an aqueous bath at a bath ratio of 1:20. The aqueous baths used are formulas (600), (602) to (606), (608), (617), (700
a
-c), (800), (900) or (901) in an amount of 0.1% based on the weight of the cotton fabric and 5 g of 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 13 A bleached cotton fabric was brightened using an aqueous bath at room temperature. The aqueous bath used is the formula (600), (602) -
(606), (608), (617), (700a-c), (800),
It contained 1 g/brightener of (900) or (901). The squeeze rate was 75%. The film was then dried using a heat fixing device at a temperature of 70° C. for 30 seconds. The cotton fabric treated as described above showed an excellent gloss effect. Example 14 A polyacrylonitrile fabric (trade name "Orlon 75") was treated in a dyeing apparatus with an aqueous bath in a bath ratio of 1:20: the aqueous bath used contained the following components: Equations (101), (103) ~ (107), (600), (602) ~
(606), (610), (700a-c), (800) or (901) brightener...0.1% (based on the weight of the fabric), 35% of ethylene per mol of stearyl alcohol
Mol adduct...1 g/, 85% formic acid...1.5 ml, the temperature program of the treatment was as follows: 40-97°C/30 minutes 90°C/30 minutes 97-40°C/15 minutes The polyacrylonitrile fabric was then rinsed in running softened water for 20 seconds and dried in a drying chamber at a temperature of 70°C. Fabrics treated in this way showed excellent gloss effects. Example 15 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 liquid.
0.2g and formulas (600), (602) to (608), (700a-
c), (900) or (901) brightener. 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 16 A bleached cotton fabric was 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 mole added...0.5g, formula (600),
(602) ~ (609), (617), (700a-c), (800),
(900) or (901) brightener...0.01g. The cotton fabric was then rinsed for 20 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 17 Modified polyacrylonitrile fabric (Courtelle)
was processed in a dyeing apparatus using an aqueous bath with a bath ratio of 1:20. The aqueous bath used contained the following ingredients: Equations (101), (103) ~ (107), (600), (602) ~
(606), (610), (700a-c), (800) or (901) brightener...0.1% (based on fabric weight), oxalic acid...1g/, polyphosphate as complex builder...0.25 g/
, Sodium metabisulfite...0.25g/. The temperature program after treatment was as follows: 40-97°C/30 minutes 97°C/30 minutes 97-40°C/15 minutes The polyacrylonitrile fabric was then rinsed with softened running water for 30 seconds. And then 70℃
It was dried in a drying room at a temperature of . Fabrics treated in this way showed excellent gloss effects. Example 18 A polyamide-6-fiber fabric 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: Compound of formula (101), (103)-(107), (109), (200) or (302)...0.3% (based on the weight of the fabric) Stearyl alcohol 35 ethylene oxide per mole
Adduct with 8 moles of ethylene oxide added to 1 mole of p-tert-octylphenol...1g/ Sodium phosphate buffer...0.5g/. The temperature program for treatment was as follows: 50-100°C/10 minutes 100°C/20 minutes 100-50°C/5 minutes The fabric was then rinsed in softened cold water and dried at 60°C. . Fabrics treated in this way showed excellent gloss effects. Example 19 A polyamide-6-fiber fabric 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 (600), (602)-(607), (700a-c),
(800), (900) or (901) compound...0.3%
(based on fabric weight) 35 ethylene oxide per mole of stearyl alcohol
Adduct with added moles...1g/Adduct with 8 moles of ethylene oxide added to 1 mole of p-tert-octylphenol...1g/Sodium phosphate buffer...0.5g/The treatment temperature program is as follows: Temperature: 30-60℃ reached in 10 minutes, kept at 60℃ for 20 minutes. The fabric was then rinsed in cold softened water and dried at 60°C. Fabrics treated in this way showed excellent gloss effects. Example 20 5 g of fibrous material (consisting of 1:1 bleached sulfite pulp and bleached beech pulp) is placed in 50 ml of water and prepared according to formula (600), (602) to (606), (900) or (901). It was mixed in a mixer for 15 minutes with 150 ml of a brightener solution containing 2.5 mg of brightener (corresponding to a concentration of 0.05%). Then 1.5% by weight of lime (eg Bewoidleim) and 2.5% by weight of aluminum sulfate (both based on pulp dry weight) were added and diluted to 1000ml with approximately 10° dH water. Paper was made using this pulp suspension. The paper obtained showed an excellent gloss effect. Example 21 5 g of pulp (consisting of 1:1 bleached sulphite pulp and bleached beech pulp) was placed in 150 ml of water containing 5 mg of cationically active polyetheramine. This liquid was mixed in a mixer with 50 ml of a brightener solution containing 2.5 mg (corresponding to a concentration of 0.05%) of brightener of formula (600), (602)-(606), (900) or (901). then lime (e.g. Bewoidleim) 1.5% by weight,
Add 2.5% by weight of aluminum sulfate and 0.1% of cationically active polyetheramine (both based on pulp dry weight) and add 1000 ml of water at approximately 10° dH.
diluted to. Paper was made using this pulp suspension. The paper obtained showed an excellent gloss effect. Example 22 5 g of pulp (consisting of 1:1 of bleached sulfite pulp and bleached beech pulp) was mixed with 5 mg of polyethyleneimine.
into 150 ml of water containing, and the formula (600),
Brighteners from (602) to (606), (900) or (901)
It was mixed in a mixer for 15 minutes with 50 ml of a brightener solution containing 2.5 mg (corresponding to a concentration of 0.05%). Then 1.5% by weight of lime (e.g. Bewoidleim), 2.5% by weight of aluminum sulfate and 0.1% by weight of polyethyleneimine.
% (based on pulp dry weight) and approx.
Diluted to 1000ml with 10°dH water. When paper was made using this pulp suspension, paper was obtained that exhibited an excellent gloss effect. Example 23 100 parts polyvinyl chloride, stabilizer (Advastat
BD100; Ba/Cd complex) 3 parts, titanium dioxide 2 parts, dioctyl phthalate 59 parts and a compound of formula (101), (103) to (107) or (201)
150 to 155 of an intimate mixture consisting of 0.01 to 0.2 parts
It was rolled into a foil by calendering at °C. The resulting opaque polyvinyl chloride foil exhibited a substantially higher degree of whiteness than the foil containing no brightener. Example 24 A concentrated liquid detergent was prepared by mixing the following ingredients. Weight% Ethoxylated alcohol (addition of 6.5 moles of ethylene oxide to _C12 - _C13 alcohol) 60.0 1-Methyl-1-oleylamide-ethyl-2-
Oleylimidazolium methosulfate 26.7 Formula (600), (602)-(609), (700), (800),
(900) or (901) 0.3 Water 12.0 Applicable additives 1.0 Hard content 100ppm containing 50 to 60g of the above detergent
2 kg of bleached cotton cloth was washed in 60°C of water at a temperature of 60°C for 10 minutes. After rinsing and drying, the washed fabric exhibited a strong shine effect and a soft feel. In addition, 0.2 g of active chlorine in the form of sodium hypochlorite was added to the above washing bath, and washing was carried out in the same manner as above. The same high effects as above were obtained. Similar results were obtained when a liquid detergent having the following composition was used instead of the above composition. Weight% Ethoxylated alcohol (6.5 moles of ethylene oxide added to _C12-13 alcohol) 55.0 1-Methyl-1-stearylamidoethyl-2-
Stearylimidazolinium methosulfate
26.0 Formula (600), (602) to (609), (700), (800),
Compounds of (900) or (901) 0.3 Water 13.0 Isopropanol 5.0 Conventional additives 0.7 Furthermore, liquid detergents containing other nonionic surfactants and cationic substances such as the commercially available “Perwoll liquid” or the Samtess Similar results were obtained when the inventive brightener was added. Example 25 A liquid detergent was prepared by mixing the following ingredients. Weight % Ethoxylated alcohol (7 moles of ethylene oxide added to C _14-15 alcohol) 12.0 Ethoxylated alcohol (6.5 moles of ethylene oxide added to C _12-13 alcohol) 12.0 Non-rigid di-stearyl-dimethyl ammonium chloride 6.4 Ethanol 15.0 Bicarbonate Sodium 0.25 Formula (600), (602) ~ (609), (700), (800),
Compound (900) or (901) 0.41 Common additives 0.41 Water 53.53 When a cotton cloth was washed using the above detergent in the same manner as in Example 24, a strong gloss effect and a soft feel were obtained. Dyeing Comparative Example Polyamide-6-fiber fabrics were treated in a dyeing apparatus using an aqueous bath with a bath ratio of 1:20. The aqueous bath used contained the following components: Compound of formula (614) or Comparative Compound A
…0.05%, 0.1%, 0.2% (based on fabric weight) Sodium tripolyphosphate …0.5 g/ The temperature program for the treatment was as follows: 40-103°C reached in 10 minutes, 103°C for 20 minutes Hold and cool to 40°C for 10 minutes. Fabrics were rinsed with water and dried. Structural formula of comparative compound A: Whiteness was measured with a Zeiss FRC3 spectrophotometer. The results are shown in the table.

Table: The compounds of the invention show a whiteness that is 7-8% higher than the comparative compounds. Dyeing Comparative Example A concentrated liquid detergent was prepared by mixing the following components. Weight% Ethoxylated alcohol (addition of 6.5 moles of ethylene oxide to _C12 - _C13 alcohol)...60.0 1-Methyl-1-oleylamidoethyl-2-oleylimidazolium methosulfate...26.7 Compound of formula (614) Or Comparative Compound A...0.3 Water...12.0 Common additives...1.0 Add 4 g of the above detergent/4 g of the above detergent/and 250 ppm active chlorine 4 to cotton fiber in a bath ratio of 1:20.
The mixture was treated in an aqueous bath containing 40°C for 15 minutes. The fabric was rinsed with water and dried. Whiteness was measured with a Zeiss FRC3 spectrophotometer. The results are shown in Table V.

Table: The compounds of the invention exhibit higher bleach fastness than the comparative compounds.

Claims (1)

[Claims] 1 formula (In the above formula, X ₁ means a direct bond, oxygen, sulfur, -OCO- or -COO-, Y ₁ and Y′ ₁ independently of each other mean C _1-4 -alkylene or hydroxypropylene. , R″ ₁ and R″ ₂ independently represent C _1-4 -alkyl, or together they form a pyrrolidine ring, piperidine ring or morpholine ring, or
together with R′ ₃ forms a pyridine ring, R′ ₃ is hydrogen, C _1-4 -alkyl or together with R″ ₁ and R″ ₂ forms a pyridine ring, R ₅ is hydrogen, Chlorine, C _1-4 -alkyl, C _1-3 -alkoxy, R ₆ means hydrogen, chlorine, C _1-4 -alkyl, C _1-3 -alkoxy, n and n' are each other. distyryl biphenyl independently of the number 0 or 1 and A meaning a colorless anion). 2 formulas (In the above formula, X ₂ means oxygen, sulfur, -OCO- or -COO-, Y ₂ means C _1-4 -alkylene, R ₁ means C _1-4 -alkyl or _R2
together with 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 C _1-4 -alkyl or R ₁
together with form a pyrrolidine ring, piperidine ring or morpholine ring, or together with R ₁ and R ₃ form a pyridine ring, R ₃ means hydrogen, C _1-4 -alkyl, or R ₁ and R together with ₂ to form a pyridine ring, n is a number of 0 or 1, and A means a colorless anion; benzene nuclei B and C can be further replaced by non-chromophores). Distyryl biphenyl according to claim 1. 3 formulas (In the formula, X ₁ means a direct bond, oxygen, sulfur, -OCO- or -COO-, Y ₁ means C _1-4 -alkylene or hydroxypropylene, R″ ₁ and R″ ₂ are mutually C _1-4 - independently represents alkyl, or both together represent a pyrrolidine ring,
forming a piperidine ring or a 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 pyridine forming a 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 -alkoxy Distyrylbiphenyl according to claim 1, with the meaning: n is the number 0 or 1 and A means a colorless anion. 4 formula (In the formula, X ₁ means a direct bond, oxygen, sulfur, -OCO- or -COO-, Y ₁ means C _1-4 -alkylene or hydroxypropylene, and R ₁ and R ₂ are independent of each other. C _1-4 -alkyl, or together they form a pyrrolidine ring, piperidine ring or morpholine ring, or together with R′ ₃ they form a pyridine ring, R′ ₃ is hydrogen, C _{1- 4} - means alkyl or together with R ₁ and R ₂ form a pyridine ring, R' ₅ is hydrogen, chlorine, C _1-4 -alkyl or C _1-3
-alkoxy, n is the number 0 or 1 and A means a colorless anion) distyrylbiphenyl according to claim 3. 5 formula (In the formula, Y ₃ means C _2-4 -alkylene, R ^IV ₁ means C _1-3 -alkyl or
R ^IV ₂ together with R IV 2 forms a pyrrolidine ring, piperidine ring or morpholine ring, R ^IV ₂ means C _1-3 -alkyl or
together with R ^IV ₁ to form a pyrrolidine 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 means a colorless anion distyryl biphenyl according to claim 3 of the formula 6. (where A′ is CH ₃ OSO ₃ or C ₂ H ₅ OSO ₃
and R ₃ means methyl or ethyl)
Distyryl biphenyl according to claim 5. 7 formula (In the formula, A′ is CH ₃ OSO ₃ or C ₂ H ₅ OSO ₃ ,
and R ₃ means methyl or ethyl)
Distyryl biphenyl according to claim 5. 8 formula (where A′ is CH ₃ OSO ₃ or C ₂ H ₅ OSO ₃
and R ₃ means methyl or ethyl)
Distyryl biphenyl according to claim 5. 9 formula (wherein, X ₂ means oxygen, sulfur, or -COO-, Y ₂ means alkylene having 2 to 4 carbon atoms, R ^v ₁ means alkyl having 1 to 4 carbon atoms or together with R ^v ₂ to form a pyrrolidine ring, piperidine ring or morpholine ring, R ^v ₂ means an alkyl having 1 to 4 carbon atoms, or together with R ^v ₁ to form a pyrrolidine ring, piperidine ring forming a ring or morpholine ring, R ^IV ₃ means hydrogen or alkyl having 1 to 4 carbon atoms, A is the equivalent of a colorless anion, and n is a number of 0 or 1, and the benzene nucleus B and C
may be further substituted by a non-chromophore). 10 formula (wherein X ₂ , Y ₂ , R ^v ₁ , R ^v ₂ , R ^IV ₃ , A and n have the meaning defined in claim 9 and benzene nuclei B and C are further Distyrylbiphenyl according to claim 9, which may be substituted by a chromophore. 11 formula (In the formula, Y ₂ means alkylene having 2 to 4 carbon atoms, R ^v ₁ means alkyl having 1 to 4 carbon atoms, or together with R ^v ₂ , pyrrolidine ring, piperidine R ^v ₂ means alkyl having 1 to 4 carbon atoms or together with R ^v ₁ forms a pyrrolidine, piperidine or morpholine ring, R ^IV ₃ is hydrogen or alkyl having 1 to 4 carbon atoms, A is the equivalent of a colorless anion, and n is a number of 0 or 1, and the benzene nucleus B and C
may be further substituted by a non-chromophore). 12 formula (In the above formula, X ₁ means a direct bond, oxygen, sulfur, -OCO- or -COO-, Y ₁ and Y′ ₁ independently mean C _1-4 -alkylene, R″ ₁ and R″ ₂ independently represent C _1-4 -alkyl, or together they represent a pyrrolidine ring,
forming a piperidine ring or a 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 pyridine forming a ring, A means a colorless anion, and n and n' independently of each other are numbers of 0 or 1; benzene nuclei B and C are further substituted by a non-chromophore; In the method for producing distyryl biphenyl of (In the formula, benzene nuclei B and C and X ₁ , Y ₁ , Y′ ₁ ,
1 molar equivalent of distyrylbiphenyl of the formula _R ' _{3 -A} (wherein
R' ₃ and A have the meanings given above) are quaternized or protonated with 1 or 2 molar equivalents of an alkylating agent or acid. 13 formula (In the formula, Y ₃ means C _2-4 -alkylene, R ^IV ₁ means C _1-3 -alkyl or
R ^IV ₂ together with R IV 2 forms a pyrrolidine ring, piperidine ring or morpholine ring, R ^IV ₂ means C _1-3 -alkyl or
together with R ^IV ₁ forms a pyrrolidine 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 means a colorless anion ), in the presence of a strong base, the formula A compound with the formula [In both formulas above, Y ₃ , R ^IV ₁ and R ^IV ₂ have the above meanings, one of Z ₁ and Z ₂ represents an OCH- group, and the other represents the following formula [Formula] [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 (wherein Y ₃ , R ^IV ₁ and R ^IV ₂ have the meanings given above) by alkylation of the compound of the formula R″ ₃ —A, where R″ ₃ and A have the meanings given above. A production process characterized by quaternization or protonation with 2 moles of agent or acid. 14 formula (In the above formula, X ₁ means a direct bond, oxygen, sulfur, -OCO- or -COO-, Y ₁ and Y′ ₁ independently of each other mean C _1-4 -alkylene or hydroxypropylene. , R″ ₁ and R″ ₂ independently represent C _1-4 -alkyl, or together they form a pyrrolidine ring, piperidine ring or morpholine ring, or
together with R′ ₃ forms a pyridine ring, R′ ₃ is hydrogen, C _1-4 -alkyl or together with R″ ₁ and R″ ₂ forms a pyridine ring, R ₅ is hydrogen, Chlorine, C _1-4 -alkyl, C _1-3 -alkoxy, R ₆ means hydrogen, chlorine, C _1-4 -alkyl, C _1-3 -alkoxy, n and n' are each other. A method for fluorescently brightening an organic material, characterized in that distyrylbiphenyl (independently a number of 0 or 1 and A means a colorless anion) is blended into the organic material or applied to the surface thereof. . 15. A method according to claim 14 for fluorescently brightening polyacrylonitrile or cellulose as organic material.