US3646015A - Optical brightener compounds and detergent and bleach compositions containing same - Google Patents

Optical brightener compounds and detergent and bleach compositions containing same Download PDF

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US3646015A
US3646015A US3646015DA US3646015A US 3646015 A US3646015 A US 3646015A US 3646015D A US3646015D A US 3646015DA US 3646015 A US3646015 A US 3646015A
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isoindolinyl
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Lewis R Hamilton
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Procter and Gamble Co
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    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07DHETEROCYCLIC COMPOUNDS
    • C07D209/00Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D209/02Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom condensed with one carbocyclic ring
    • C07D209/44Iso-indoles; Hydrogenated iso-indoles
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07HSUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
    • C07H5/00Compounds containing saccharide radicals in which the hetero bonds to oxygen have been replaced by the same number of hetero bonds to halogen, nitrogen, sulfur, selenium, or tellurium
    • C07H5/04Compounds containing saccharide radicals in which the hetero bonds to oxygen have been replaced by the same number of hetero bonds to halogen, nitrogen, sulfur, selenium, or tellurium to nitrogen

Abstract

OPTICAL BRIGHTNER COMPOUNDS DEFINED AS ISOINDOLINYL COMPOUNDS. THE OPTICAL ACTIVITY OF THESE COMPOUNDS CAN BE EMPLOYED TO ADVANTAGE IN THE OPTICAL BRIGHTENING OF A WIDE VARIETY OF NATURAL AND SYNTHETIC MATERIALS. THEY ARE USEFUL IN THE BRIGHTENING OF FABRICS AND FIND APPLICATION IN THE PREPARATION OF LAUNDRY DETERGENT COMPOSITIONS AND HYPOCHLORITE BELACH-CONTAINING COMPOSITIONS.

Description

AU 165 Ex United States Patent O ABSTRACT OF THE DISCLOSURE Optical brightener compounds defined as isoindolinyl compounds. The optical activity of these compounds can be employed to advantage in the optical brightening of a wide variety of natural and synthetic materials. They are useful in the brightening of fabrics and find application in the preparation of laundry detergent compositions and hypochlorite bleach-containing compositions.

Hamilton & Gamble BACKGROUND OF THE INVENTION This invention relates to optical brightening agents. More particularly, it relates to optical brightening agents useful in the optical brightening of a wide variety of materials and to detergent and hypochlorite bleach-containmg compositions containing them.

In recent years, the use of optical brightening agents, oftentimes termed optical bleaches or fluorescers, has grown enormously. These compositions which are colorless dyestutis function by absorbing light in the ultraviolet invisible range (300-400 nm.) such as is contained in natural daylight and remitting this as visible, blue-white light (400-500 nm.). This fluorescence masks natural yellowing of textile fibers and results in a highly desirable blue-white glow on white goods and a fresher, cleaner appearance of colored goods. The fluorescence of optical brightening agents, while in the blue range, varies somewhat in dominant wavelength. Where the dominant wavelength is longer, the blue fluorescence is considered to have a slightly greenish tinge. A shorter dominant wavelength near the violet end of the spectrum results in blue fluorescence which is slightly reddish. For practical purposes, particularly for use in laundry detergent formulations, a neutral blue fiuoroescence is generally preferable.

Optical brighteners suitable for textile applications must exhibit a high degree of fluorescence. Frequently, the fluorescence of conventional optical brighteners is destroyed or quenched by contact with hypochlorite and similar oxidizing bleaches. Since many of the deeply embedded soils and stains encountered in the laundering of textile fabrics are conventionally removed by the action of chemical bleaching, great effort has been expended in the search for optical brighteners which resist the destructive efiects of hypochlorite bleaches.

Accordingly, it is an object of this invention to provide optical prighteners having 'a hi'glii'degree' of fluorescence and resistance to thehestructive efiectsuofshypochlorite bleacli'sf Another object of this invention is to provide detergent compositions containing an organic detergent, an alkaline builder salt and an optical brightener.

A further object of this invention is to provide laundry detergent compositions containing an organic detergent, an alkaline builder salt, a hypochlorite bleach and an optical brightener.

Still another object of this invention is to provide aqueous and granular hypochlorite bleach compositions containing an optical brightener.

3 46,015 Patented Feb. 29, 1 972 "ice Other objects of this invention will become apparent from consideration of the detailed description of the invention which appears hereinafter.

SUMMARY OF THE INVENTION The above and other objects of this invention are achieved by the present invention which comprises the provision of optical brightener compounds of the formula:

wherein each a is an integer from 1 to 4; x is 0 or 1; each A is selected from hydrogen; alkyl of l to 10 carbon atoms (e.g., methyl, ethyl, propyl, butyl, octyl, decyl), preferably of 1 to 4 carbon atoms; halogen (e.g., chlorine, bromine); alkoxy of 1 to 10 carbon atoms (e.g., methoxy butoxy, hexoxy, decoxy); aryl of from 6 to 12 carbon atoms (e.g., phenyl, biphenyl, naphthyl); alkylsulfonyl of from about 1 to 10 carbon atoms (e.g., methylsulfonyl, octylsulfonyl, decylsulfonyl); alkoxyalkyl of from 2 to 10 carbon atoms (e.g., methoxymethyl, butoxymethyl, ethylhexyloxymethyl); polyethylenoxy of the formula H(CI-l CH O) where n is an integer from 1 to 10 -gs s( 2 2 )'a-) haloalkyl of from 1 to 10 carbon atoms (e.g., trifiuoromethyl, perfluoroethyl, dichloroethyl); alkanoyl of from 2 to 10 carbon atoms (e.g., acetyl, propionyl, hexanoyl, octanoyl, decanoyl); cyano; polyhydroxyalkyl of from 1 to 10 carbon atoms (e.g., 1,2,3-trihydroxypropyl, sorbitol); when x is 0, Z is a monovalent radical selected from ture; and

wherein each A is as hereinbefore defined and each p is l or 2;

and when x is one, Z is a bivalent radical of the formula El) Bl) wherein each B and eachb are as defined hereinbefore.

The compounds prepared according to the present invention are excellent optical brighteners for use in a variety of natural and synthetic materials and are especial- 1y characterized by their resistance to the destructive action of chlorine-containing bleaching compounds. Accordingly, they can be employed in detergent compositions containing alkaline builder compounds and active chloline-containing bleaching compounds and in aqueous and granular bleach compositions.

DETAILED DESCRIPTION OF THE INVENTION The optical brightener derivatives of the present in- 'vention having the hereinbefore defined formula are termed herein as isoindolinyl compounds and are characterized by the presence of the group wherein A and a are as defined hereinbefore. As will be apparent from the hereinbefore described formulae and definitions, the compounds of the invention are characterized by the presence of at least one of such groups.

The optical brighteners of the present invention are derived from fluorescent aromatic primary monoor diamines characterized by ultraviolet absorption in the 310 to 400 nanometer range and fluorescence in the 400 to 475 range. These fluorescent amines can be represented by the formula (H N) Z, wherein Z represents the residue of the fluorescent amine, i.e., the entire molecule exclusive of the amino group and q is one in the case of a monoamine and two in the case of a diamine. The equimolar condensation reaction of a monoamine with a reactive aromatic halide to form a mono-isoindolinyl compound is illustrated by the following reaction scheme:

wherein X is halogen (e.g., chlorine, bromine) and Z is the residue of a fluorescent aromatic amine as hereinbefore defined.

Similarly, fluorescent aromatic diamines having the same spectral characteristics and represented as undergo reaction with a reactive aromatic halide according to the following scheme:

Hr-X

Aa N-Z-N An The radical, 2, where employed herein is used to represent the radical derived by abstraction of one or two primary amino groups from a fluorescent aromatic amine described hereinbefore. It will be understood that this radical is considered as being derived by abstraction for convenience only and that the characterization of the amine residue in such terms is not intended to imply that abstraction in a chemical sense is actually involved in the formation of the brightener compounds of the present invention.

The amines which can be employed to prepare the optical brighteners of the present invention are fluorescent aromatic primary monoand diamines characterized by ultraviolet absorption in the range of 310 to 400 nm. and fluorescence in the 400-475 nm. range. These compounds are conventional brightener chromophores known to those skilled in the art. Examples of fluorescent amines having the prescribed spectral characteristics and their monovalent or bivalent radicals (Z) include the following:

(l) 4-aminostilbenes of the formula:

where each b is as defined above and each B is defined as A above or 40 0M or where each b is as defined above and each B is defined the same as A above or SO OM or R -SO2N/ where M is hydrogen or an alkali metal; and R and R are each hydrogen; alkyl of 1 to 4 carbon atoms; aryl; glucosyl; hydroxyalkyl of 1 to 4 carbon atoms or together comprise part of a ring structure; and

(3) 7-aminocoumarins of the formula;

wherein each p is 1 or 2 and each A is as helcinbefore defined.

Preferred amines for reasons of facility in undergoing the desired reaction with a reactive halide and excellent bleach stability of the brightener compounds obtained, are the 4-aminostilbenes (e.g., 4-amino-4-methoxy-2,2' stilbenedisulfonic acid,

0 0a so on the disodium salt thereof; 4 amino 4 methoxy-2,2- stilbenedisulfonamide,

4amino-2-stilbenesulfonic acid,

and the sodium salt thereof) and the 4,4'-diaminostilbenes (e.g., 4,4-diamino-2,2'-stilbenedisulfonic acid,

50 B SO OH the disodium salt thereof; and 4,4 diamino-2,2'-stilbenedisulfonamide).

Optical brighteners derived from amines of the present invention have the following structures:

Ap Ap la @11 o 7 and AB @311 Ql-FCEPQ" win wherein a, b, p, A and B have the meanings defined above. Optical brighteners prepared from preferred amines have the structures:

it =cn QC i p N CH=C g: /2 H g 3' a n o n so it 2 2 of the preparation of compounds of the formula C j z n l those wherein x in the molar proportion of l,2-di(halomethyl)benzene to wherein M, R and R fluorescent primary amine employed is from 1.811 to 3:1, the ratio of 2:1 being preferred. When asymmetrical isoindolinyl derivatives are desired, two or more dissimilar l,2-di(halomethyl)benzenes can be employed. Preferably, the l,2-di(halomethyl)benzenes are sequentially reacted with the fluorescent amine.

While the reaction can be effected by reacting at a temperature of from 0 C. to 150 C., a preferred tempera ture range is about 50 C. to about C. Reactions conducted at the lower temperature of the suitable range, i.e., at about 0 C. normally are efiected in a period of time of about 24 hours. Conversely, reactions at about 100 C. require less time and may be eflected in good yield in about 30 minutes.

The isoindolinyl compounds of the invention can be prepared in a polar organic solvent which is essentially non-reactive to either the 1,2-di(halomethyl)benzene or fluorescent amine employed in the reaction. The amount of solvent employed is an arrount at least suflicient to dissolve the fluorescent amine, an amount of about three times the weight of amine employed being sufficient. Examples of suitable essentially non-reactive solvents which can be employed are water, alcohols, N,N-dialkyl low molecular weight amides such as dimethylformamide, cyclic ethers such as tetrahydrofuran and dioxane, aromatic hydrocarbons such as benzene and certain organic solvent-water mixtures such as dimethylformamide-water, e.g., dimethylformamide containing from about 1 to about 60% water on a volume/volume basis. A preferred solvent is water.

The preparation of the optical brighteners of the invention is accompanied by formation of hydrochloric acid by-product. This acid can be neutralized in a conventional manner by addition of a suitable base, e.g., sodium carbonate, sodium bicarbonate, sodium hydroxide, triethylamine, or pyridine to the reaction product. Preferred herein is sodium bicarbonate.

The optical brighteners of the present invention exhibit remarkable stability in the presence of hypochlorite bleach. While applicants do not wish to be bound by any theory as to the nature of such stability, it is believed that the stability is due at least in part to the presence of essential moieties of the formula and to the absence of a free hydrogen attached to a nitrogen atom. These moieties, named herein as substituents on a fluorescent stilbene or coumarin nucleus, i.e., isoinolinyl, provide resistance to the harmful effects of hypochlorite bleaches and resulting loss of fluorescence. Other fluorescent aromatic amines can likewise be rendered resistant to degradative attack by hypochlorite bleaching compounds. Examples of such chromophoric amines are S-amino-1,8-naphthalenecarboximides, 2-aminonaphii 113161365, 3-arnino-2,S-diaryl-pyrroles and -furans and the Specific examples of optical brightener compounds of the invention include the following:

(1) 3-phenyl-7- (isoindolinyl coumarin (2) 3-methyl-7-(isoindolinyl coumarin (3) 3-chloro-7-(isoindolinyl)coumarin (4) 4- (isoindolinyl -4'-methylstilbene (5) 4-(isoindolinyl -4-methoxystilbene (6) sodium 4-(isoindolinyl)-4'-stilbenesulfonate (7) 4-(isoindolinyl) -4-phenylstilbene (8) 4- isoindolinyl -3-methoxy -4'-methylstilbene (9) 4-(2-chloroisoindolinyl)-4-(Z-methylisoindolinyl 2,2'-stilbenedis-ulfonic acid (10) disodium 4,4'-diisoindolinyl-2,2'-stilbene disulfonate (1 l 4,4'-diisoindolinyl-2,2'-stilbenedisulfonamide The optical brightener compounds of the present invention can be employed for the optical brightening of a wide 'variety of natural and synthetic materials. Natural materials include organic fibrous materials such as silk and wool. Synthetic fibers include such materials as polyester, polyacrylonitrile, polyamide, acetylized polyvinyl alcohol and polyolefin and cellulose acetate fibers. The brightener compounds of the invention provide excellent brightening and light fastness and can be employed in aqueous or solvent-containing brightening compositions. These compositions can contain bleaching components such as hypochlorites without substantial loss of fluorescence.

The optical brighteners of the present invention can be incorporated into polymeric melts and processed to a variety of products including synthetic fibers. Alternatively, they can be applied to a substrate by application of a solution to the surface of a polymeric substrate.

The treatment of fibrous materials can be carried out by immersion of the fibrous materials in an aqueous dispersion of the optical brightening compound of the invention and a surface-active agent. Suitable surface-active agents include anionic or nonionic compounds such as alkylbenzenesulfonic acid, the condensation product of naphthalenesulfonic acid and formaldehyde or polyoxyethylenealkylether and the like. The fibrous material is immersed in the aqueous dispersion of brightener at a temperature of from 50 C. to 130 C. depending on the kind of fibrous material treated. The fibrous material is normally dried by heating at a temperature of from 160 C. to 220 C. for a time of from 0.5 to 2 minutes.

The brightener compounds of the invention can also be employed in laundry detergent compositions to provide an improved appearance to laundered goods. When so employed they range from 0.01% to 3% of the detergent composition. A preferred amount of brightener is from 0.5% to 1.5%. In addition to these brightener compounds, the laundry detergent compositions of the invention comprise at least of a mixture of an organic detergent and an alkaline builder salt in a ratio in the range of from 5:1 to 1:20, preferably from 2:1 to 1:10. This mixture can be as much as the balance of the composition. The organic detergent compounds and alkaline builder salts are more fully described below.

ORGANIC DETERGENTS The organic detergent compounds which can be utilized in the detergent compositions of this invention are the following:

(a) Water-soluble soaps.--Examples of suitable soaps for use in this invention are the sodium, potassium, ammonium and alkanolarnmonium (e.g., mono-, di-, and triethanolammonium salts of higher fatty acids (C -C Particularly useful are the sodium and potassium salts of the mixture of fatty acids derived from coconut oil and tallow, i.e., sodium and potassium tallow and coconut soaps.

(b) Anionic synthetic non-soap detergents.--A preferred class can be broadly described as the water-soluble salts, particularly the alkali metal salts, of organic, sulfuric acid reaction products having in their molecular structure an alkyl radical containing from about 8 to about 22 carbon atoms and a radical selected from the group consisting of sulfonic acid and sulfuric acid ester radicals. (Included in the term alkyl is the alkyl portion of higher acyl radicals.) Important examples of these anionic synthetic detergents are the sodium or potassium alkyl sulfates, especially those obtained by sulfating the higher alcohols (C -C carbon atoms) produced by reducing the glycerides of tallow or coconut oil; sodium or potassium alkylbenzenesulfonates, in which the alkyl group can be a straight or branched chain and contains from about 9 to about carbon atoms, preferably about 12- 14 carbons; sodium alkyl glyceryl ether sulfonates, especially those ethers of the higher alcohols derived from tallow and coconut oil; sodium coconut oil fatty acid monoglyceride sulfates and sulfonates; sodium or potassium salts of sulfuric acid esters of the reaction product of one mole of a higher fatty alcohol (cg, tallow or coco-- nut oil alcohols) and about 1 to 6 moles of ethylene oxide; sodium or potassium alkyl phenol ethylene oxide ether sulfates, with 1 to 10 units of ethylene oxide per molecule and wherein the alkyl radicals contain from 8 to 12 carbon atoms; the reaction product of fatty acids esterified with isethionic acid and neutralized with sodium hydroxide where, for example, the fatty acids are derived from coconut oil; sodium or potassium salts of fatty acid amide of a methyl tauride in which the fatty acids, for example, are derived from coconut oii; sodium and potas sium salts of SO sulfonated C -C a-olerirzs (c) Nonionic synthetic detergents.---One class of nonionic detergents can be broadly defined as compounds produced by the condensation of alkylene oxide groups (hydrophilic in nature) with an organic hydrophobic compound, which may be aliphatic or alkyl aromatic in nature. The length of the hydrophilic or polyoxyalkylene radical which is condensed with any particular hydrophobic group can be readily adjusted to yield a water-- soluble compound having the desired degree of balance between hydrophilic and hydrophobic elements. A second class of nonionic detergents comprises higher fairy amides. A third class of nonionic detergents has semi-polar characteristics. These three classes can be dehned in further detail as follows:

(1) One class of nonionic synthetic detergents is marketed under the trademark of Pluronic." 'lhese detergent compounds are formed by condensing eth lene ox ide with a hydrophobic base formed by the condensation of propylene oxide with propylene glycol. The hydrophobic portion of the molecule which, of course, exhibits water insolubility, has a molecular weight of from about 1500 to 1800. The addition of polyoxyethylene radicals to this hydrophobic portion tends to increase the water solubility of the molecule as a whole and the liquid character of the product is retained up to the point where the polyoxyethylene content is about of the total weight of the condensation product.

(2) Alkylphenol-polyethylene oxide condensates are condensation products of alkyl phenols having an alkyl group containing from about 6 to 12 carbon atoms in either a straight chain or branched chain configuration with ethylene oxide, the said ethylene oxide being present in amounts equal to 5 to 25 moles of ethylene oxide per mole of alkyl phenol. The alkyl substituent in such compounds may be derived from polymerized propylene, diisobutylene, octene, or nonene, for example.

(3) Nonionic synthetic detergents can be derived from the condensation of ethylene oxide with the product re sulting from the reaction of propylene oxide and ethylene diamine and include compounds containing from about 40% to about polyoxyethylene by weight and having a molecular weight of from about 5,000 to about 11,000. Such cempounds result from the reaction of ethylene oxide with a hydrophobic base constituted of the reaction product of ethylene diamine and excess propylene oxide, said base having a molecular weight of the order of 2,500 to 3,000.

(4) Other nonionic detergents include condensation products of aliphatic alcohols having from is to 22 carbon atoms, in either straight chain or branched chain configuration, with ethylene oxide, eg. a coconut alcoholethylene oxide condensate having from 5 to 30 moles of ethylene oxide per mole of coconut alcohol.

(5) The ammonia, monoethanol and diethanol amides of fatty acids having an acyl moiety of from about 8 to about 18 carbon atoms are useful nonionic detergents. These acyl moieties are normally derived from naturally occurring glycerides, e.g., coconut oil, palm soybean oil and tallow, but can be derived synthetically, eg, by the oxidation of petroleum, or by hydrogenation of carbon monoxide by the Fischer-Tropsch process.

(6) Semi-polar nonionic detergents include long chain tertiary amine oxides corresponding to the following general formula t. wherein R is an alkyl radical of from about 8 to about 18 carbon atosm, R and R are each methyl, ethyl or bydroxyethyl radicals, R is ethylene, and n ranges from to about 10. The arrow in the formula is a conventional representation of a semi-polar bond. Specific examples of amine oxide detergents include dimethylodecylamine oxide and bis-(2-hydroxyethyl) dodecylamine oxide.

(7) Other semi-polar nonionic detergents include long chain tertiary phosphine oxides corresponding to the following general formula RRR"P-O wherein R is an alkyl, alkenyl or monohydroxyalkyl radical containing from 10 to carbon atoms and R and R" are each alkyl or monohydroxyalkyl groups containing from 1 to 3 carbon atoms. The arrow in the formula is a conventional representation of a semi-polar bond. Examples of suitable phosphine oxides are found in US. Pat. 3,304,263 which issued Feb. 14, 1967, and include: dimethyldodecylphos phine oxide and dimethyl-(2-hydroxydodecyl) phoshine oxide.

(d) Ampholytic synthetic detergents can be broadly described as derivatives of aliphatic secondary and tertiary amines, in which the aliphatic radical can be straight chain or branched alkyls and wherein one of the aliphatic sub stituents contains from about 8 to 18 carbon atoms and one contains an anionic water solubilizing group, e.g., carboxy, sulfo, sulfato, phosphato, or phosphono. Examples of compounds falling within this definition are sodium-3- dodecylaminopropionate and sodium-3-dodeeyclaminopropane sulfonate.

(e) Zwitterionic synthetic detergents can be broadly described as derivatives of aliphatic quaternary ammonium, phosphonium and sulfonium compounds, in which the aliphatic radical can be straight chain or branched alkyl, and wherein one of the aliphatic substituents contains from about 8 to 24 carbon atoms and one contains an anionic water solubilizing group, e.g., carboxy, sulfo, sulfato, phosphate or phosphono, Examples of compounds falling within this definition are 3-(N,N- dimethyl-N-hexadecylammonio) propane-l-sulfonate and 3-(N,N-dimethyl-N-hexadecylammonio)-2 hydroxy propane-l-sulfonate which are preferred for their cool water detergency characteristics. See, for example, Snoddy et a1., Canadian Pat. 708,148.

These soap and non-soap anionic, nonionic, ampholytic and zwitterionic detergent compounds can be used singly or in combination. The above examples are merely illustrations of the numerous suitable detergents. Other organic detergent compounds can also be used.

BUILDER SALTS tates; (2) water-soluble salts of phytic acid, e.g., sodium and potassium phytates-see U.S. Pat. 2,739,942; (3) water-soluble polyphosphonates, including specifically, sodium, potassium and lithium salts of ethane-l-hydroxyl,1-diphosphonic acid, sodium, potasium and lithium salts of methylene diphosphonic acid, sodium. potassium and lithium salts of ethylene diphosphonic acid, and sodium, potassium and lithium salts of ethane-l,l,2-triphosphonic acid. Other examples include the alkali metal salts of ethane-2-carboxy-l,l-diphosphonic acid, hydroxymethane phosphonic acid, carbonyldiphosphonic acid, hydroxymethane diphosphonic acid, carbonyldiphosphonic acid, ethane-l-hydroxy-l,1Z-triphosphonic acid, ethane-Z-hydroxy-l l ,2-triphosphonic acid, propane-l ,1 ,3,3-tetraphosphonic acid, propane-1,1,2,2-tetraphosphonic acid, and propane-1,2,2,3-tetraphosphonic acid; (4) water-soluble salts of polycarboxylate polymers and copolymers as described in the patent of Francis 1.. Diehl, U.S. Pat. 3,308,067 issued Mar. 7, 1967. Specifically, a detergent builder material comprising a water-soluble salt of a polymeric aliphatic polycarboxylic acid having the following structural relations as to the position of the carboxylate groups and possessing the following prescribed physical characteristics: (a) a minimum molecular weight of about 30 calculated as to the acid form; (b) an equivalent weight of about 50 to about calculated as to acid form; (c) at least 45 mole percent of the monomeric species having at least two carboxyl radicals separated from each other by not more than two carbon atoms; (d) the site of attachment to the polymer chain of any carboxy-containing radical being separated by not more than three carbon atoms along the polymer chain from the site of attachment of the next carboxyl-containing radical. Specific examples are polymers of itaconic acid, aconitic acid, maleic acid, mesaconic acid, fumaric acid, methylene malonic acid, and citraconic acid and copolymers with themselves and other compatible monomers such as ethylene.

Mixtures of organic and/or inorganic builders can be used and are generally desirable. One such mixture of builders is disclosed in Canadian Pat. 755,038 of Burton H. Gedge, e.g., ternary mixtures of sodium tripolyphosphatc, trisodium nitrilotriacetate and trisodium ethane-lhydroxy-l,l-diphosphonate. The above described builders can also be utilized singly in this invention.

The preferred builders are sodium tripolyphosphate and sodium nitrilotriacetate, alone or in admixture. The preferred organic detergents are the anionic sulfates and sulfonates. The detergent compositions preferably provide pHs in the range of about 8.5 to 11.5.

The laundry detergent compositions of this invention can contain, if desired, in addition to the brightener, organic detergent and builder, any of the usual additives for such compositions which make them more attractive or effective. For example, perfumes, dyes, proteolytic enzymes, corrosion inhibitors, oxygen and chlorine bleaches, soil redeposition agents and other brighteners can be used. Diluents such'as water, moisture and sodium sulfate can also be used to make up any balance of a composition comprising brightener, organic detergent and alkaline builder salt.

The optical brighteners of the invention are stable to attack by hypochlorite compounds. Accordingly, they are advantageously employed in laundry compositions which contain from 0.5% to 25%, usually 3-17%, of an activechlorine containing bleach compound. Examples of such compounds are: dichlorocyanuric acid; 1,3-dichloro-S,5- dimethyl hydantoin; N,N'-dichlorobenzoylene urea; paratoluene sulfondichloramide; trichloromelamine; N-chloroammeline; N-chlorosuccinimide; N,N'-dichloroaz0dicarbonamide; N-chloroacetyl urea; N,N'-dichiorobiuret; chlorinated dicyanidiamide; sodium hypochlorite; calcium hypochlorite; lithium hypochlorite; chlorinated trisodium phosphate. Preferred compounds are dichlorocyanurates, i.e., dichlorocyanuric acid and the sodium and potassium salts thereof.

In other embodiments of the present invention the optical brighteners are employed in aqueous and granular bleach compositions. In general, aqueous bleach compositions are prepared by dissolving or dispersing an optical brightener in an aqueous solution of alkali metal hypochlorite bleach. The optical brighteners of the present invention are readily soluble in aqueous hypochlorite solution and remain stable over an extended period of time so that they can be successfully packaged, shipped and stored without rendering ineffective the whitening action of the optical brightener or the oxidizing action of the bleach. Liquid bleach compositions prepared in accordance with the present invention are characterized by a pH ranging from 10.5 to 13.0 and consist essentially of from 1.0% to alkali metal hypochlorite bleach, from 0.002% to 2% of the optical brightener and the balance water.

Preferred hypochlorite bleach-containin compositions contain the alkali metal hypochlorite bleach component in an amount of from 1% to 10%, preferably from 3% to 7%, with about 5.2% being especially preferred.

The bleach component can be any one of the alkali metal hypochlorites. Examples of such useful blcaches are sodium hypochlorite, potassium hypochlorite, lithium hypochlorite, and the like. However, sodium hypochlorite is highly preferred because of its superior properties and its ready availability.

The optical brightener is present in the liquid bleach compositions of this invention in an amount ranging from 0.002% to 2.0%, preferably from 0.01% to 0.1% with about 0.05% being especially preferred.

The bleach stable brighteners of the present invention are capable of retaining their whitening and brightening effects even after exposure to aqueous 1-l0% hypochlorite-containing bleach solutions for extended periods of time, e.g., several weeks of storage. The bleach stability which is normally ascribed to conventional optical brighteners is commonly understood to mean that these optical brighteners are not ineffective when exposed to dilute solutions of bleach for limited periods of time, e.g., at washing machine conditions where the hypochlorite bleach is present in aqueous solutions at about 0.02% hypochlorite level for up to to 30 minutes. In contradistinction to the bleach compatibility commonly understood in the art, the presently claimed optical brighteners retain their desirable effects after exposure to hypochlorite bleach concentrations much higher than normally found in the course of the laundering process.

The desirable bleach compatibility of the optical brighteners of the present invention is employed to advantage in the use of these brighteners in liquid hypochlorite or granular bleach-containing compositions. The latter compositions normally comprise from 1% to 99% of an active chlorine-containing bleaching compound which is capable of evolving hypochlorite upon contact with water and from 0.005% to 10% of the optical brightener of the present invention. Dispersible polymeric stabilizing or suspending agents can also be employed. Suitable examples are described in US. Pat. 3,393,153 to Zimmer et al. issued July 16, 1968. Preferably the granular bleaching compositions of the invention contain from 1% to 80% of the active chlorine-containing bleaching compound, from 2% to of an organic detergent and from 5% to 60% of an alkaline builder salt, said bleaching compounds and builder salts being of the type hereinbefore described.

The granular-bleach compositions of this invention can contain, if desired in addition to the bleaching compound, any of the usual additives for such compositions which make them more attractive or effective, for example, perfumes, dyes, proteolytic enzymes, corrosion inhibitors, other chlorine bleaches, soil redeposition agents and other brighteners may be used.

These granular bleach compositions having a pH ranging from about 8 to 12 and upon dissolution in water evolve active hypochlorite chlorine for the effective bleaching of cellulosic fabrics.

Preparations of exemplary optical brighteners of this invention are described as follows:

Example l Preparation of disodium 4,4-(isoindolinyl CH=CH- O ONa t O ONa A solution of 5.28 parts (0.02 mole) of 1,2-di- (bromomethyhbenzene, 4.6 parts -(0.01 mole) of di sodium 4,4 diamino 2,2'-Stilbenedisulfonate, 4.2 parts sodium bicarbonate and ml. of water was heated on a steam bath for 22 hours. The reaction was conducted in a 250-ml. one-necked, round-bottomed flask equipped with a reflux condenser. The reaction mixture, light-brown in color, was removed from the steam bath, cooled, to 0 (7., filtered through a sintered glass funnel and washed with acetone to yield 1.95 parts of a light-tan product. An additional 6.54 parts of light-brown product was iso lated from the filtrate upon concentration. The combined portions were washed with acetone, dried and identified as disodium 4,4'-(isoindolinyll-2,2-stilbenedisulfonate.

Calc. (percent): C, 56.7; H, 4.08; N, 4.40. Found (percent): C, 56.3; H, 4.6; N, 3.2.

NMR analysis showed a singlet at 4.5-r and a complex aromatic multiplet centered at 1.81. The ultraviolet absorption A was 342; the fluorescence a was 457 Similar results are obtained when equimolar proportions of 4,5-dichlorol ,2-di( chloromethyl benzene; 4-chloro-l ,2-di (chloromethyl) benzene; 3-isopropoxy-1,2-di (chloromethyl benzene; 4'di-diisopropyll,2-di(chloromethyl benzene; 4-butoxyl ,2-di (chloromethyl benzene; 3-trifiuoromethyl-1,2-di(chloromethyl)benzene; 3-(1,4,7-trioxanonyl)-l,2-di(chloromethyl)benzene; 4-methoxymethyli ,2-di( chloromethyl benzene; 3-phenyll ,2-di(chloromethyl benzene; 3-naphthyl-1 ,2-di (chloromethyl benzene 3-methylsulfonyl-l,2-di (chloromethyl )-benzene; 4-cyano-1,2-di(chloromethyl )benzene; and 4-( 1,2,3-trihydroxypropyl)-1 ,2-di chloron'iethyl) benzene are employed in place of 1,2-dilbromomethyl)benzene in that the following fluorescent optical brighteners are obtained:

disodium 4,4-(7,8-dichloro-l-isoindolmyl 'l,2'-

stilbenedisulfonate;

disodium 4,4'-(7-chloro-l-isoindolinyl )-2,2'-stilb:nedisulfonate;

disodium 4,4-(6-isopropoxy-l-isoindolinyl )2,2'-

stilbenedisulfonate;

disodium 4,4-(7,8-dii;opropyl-l-isoindoli iyl )-'.1,2'-

stilbenedisulfonate;

disodium 4,4'-(7-butoxy-l-isoindolinyl)-2,2-stilbenedisulfonate;

disodium 4,4'-(6-trifluoromethyl-l-isoinclolinyl)-2,2-

stilbenedisulfonate;

disodium 4,4'-[6-(1,4,7-trioxanony1)-l isoindolinyl|-2,2'-

stilbenedisulfonate;

disodium 4,4'-(7-methoxymethyl-l-isoindolinyl )-2,2-

stilbenedisulfonate;

disodium 4,4-(6-phenyl-1-isoindolinyl)-2,2'-

stilbenedisulfonate;

disodium 4,4'-(6-naphthyl-l-isoindolinyl -2,2-

stilbenedisulfonate;

disodium 4,4'-(6-methylsulfonyll-isoindolinyl )-2,2-

stilbenedisulfonate;

I disodium 4-amino-4-ethoxy-2,2'-stilbencdisuldisodium (7-cyano-l-isoindoliny1)-2,2'-stilbenedisulfonate; and

disodium 4,4'-[7-(1,2,3-trihydroxypropyl)-l-isoindolinyl]-2,2'-stilbenedisulfonate. Similar results are obtained when equimolar proportions of disodium 4-amino-4'-ethoxy-2,2'-stilbenedisulfonate;

disodium 4-amino-4-methoxy-2,2'-stilbenedisulfonate;

fonamide; and

disodium 4-amino-4-methyl-2,2'-stilbenedisulfonamide are employed in place of disodium 4,4 diamino 2,2- stilbenedisulfonate in that the following optical brightener compounds are obtained:

Example 11 (a) Preparation of 4,4-(isoindolinyl)-2,2-stilbenedisulfonyl chloride |l N@CH=CH- A suspension of 6.18 parts of (0.01 mole) of disodium OzCl 4,4-(isoindolinyl) 2,2 stilbeneclisulfonate, parts thionyl chloride and 300 parts of dimethyl formamide is stirred at C. temperature for 15 minutes. The resulting solid product is filtered, washed with water, acetone and dried to give the desired product, 4,4 (isoindolinyl)-2,2-stilbenedisulfonyl chloride.

(b) Preparation of 4,4'-(isoindolinyl-2,2-

O Cl

stilbenedisulfonamide W0 \V S OzNHz S OZNHZ and wherein R and R are described, respectively, in

Table 1 as follows:

Example 111 Preparation of sodium 4-(isoindolinyl -2- stilbenesulfonate -cn=on yr! i l t SOQONQ The suspension obtained by dissolving 1.75 parts (0.01 mole) of l,2-di(chloromethyl)benzene, 3.10 parts (0.01 mole) of sodium 4-amino-2-stilbenesulfonate and 50 parts of water is placed onto a steam bath in a 100-ml. one-necked round-bottomed flask equipped with a refiuxcondenser. The reaction vessel is heated at a temperature of -90 C. for 16 hours. The reaction mixture is concentrated under the pressure of an aspirator and at a bath temperature of 50 C. and filtered to provide a solid residue which is filtered, washed with acetone and dried to provide the desired product, sodium 4-(isoindolinyl)-2- stilbenesulfonate. The compound is a bleach-stable optical brightener.

Similar results are obtained when 4-chloro-1 ,2-di (chloromethyl benzene; 4-propionyl-1,2-di(chloromethyl) -benzene; 3-methoxy-1,2-di(chloromethyl )benzene; 4-methyl-l ,2-di chlorometh yl benzene; 4 phenyl- 1 ,2-di(chloromethyl )-benzene; B-trifluoromethyll ,2-di (chloromethyl benzene; 4-cyano- 1 ,2-di (chloromethyl benzene; and B-methylsulforiyl-1,2-di(chloromethyl benzene are employed in place of 1,2-di(chloromethyUbenz/ene in that the correspondingly substituted optical brightener compounds are obtained, respectively, as follows:

sodium 4-(7-chloro-1-isoindolinyl )-2-stilbcnesulfonate;

sodium 4-(7-propionyl-1-isoindolinyl)-2 stilbenesulfonate;

sodium 4-(6-methoxy-1-isoindolinyl -2-stilbensulfonate;

sodium 4- (7-methyll-isoindolinyl -2-stilbenesulfonate;

sodium 4-(6-trifluoromethyl-l-isoindolinyl -2- stilbenesulfonate;

sodium 4-(7-cyano-l-isoindolinyl) -2-stilbenesulfonate;

and

sodium 4- 6-methylsulfonyll-isoindolinyl -2- stilbenesulfonate.

15 Example IV Preparation of 3-phenyl-7-(isoindolinyl coumarin The suspension obtained by adding 2.37 parts (0.01 mole) of 7-amino-3-phenylcoumarin to 2.64 parts 0.01 mole) of o-di(bromomethyl)benzene and 50 parts of water is heated on a steam bath (SO-90 C.) for a period of 16 hours. The heating is conducted in a l00-ml., onenecked, round-bottomed flask equipped with a reflux condenser. The resulting solution is cooled to 0 C. and filtered through a sintered glass funnel to provide the desired product, 3-phenyl-7-(isoindolinyl)coumarin. An additional portion of the desired product is isolated from the aqueous filtrate by concentrating the filtrate to dryness, extracting with methanol, recrystallizing with methanol and diethylether and filtering the product. The resulting compound is an optical brightener having bleachcompatibility properties.

Similar results are obtained when 7-amino-4-phenylcoumarin; 7-amino-S-chlorocoumarin; 7-amino-3-phenyl-S-methoxycoumarin;

7-amino-3 -methylcoumarin; 7-amino-3,5,8-trimethoxycoumarin; 7-amino-3,5-diphenylcoumarin; 7-amino-3-phenyl-5-chloromethylcoumarin; 7-amino-5-(3',5',7'-trioxanonyl)-3-phenylcoumarin are employed in place of 7-amino-3-phenylcoumarin in that the following bleach-stable optical brightener compounds are formed:

7-(isoindolinyl)-4-phenyl coumarin;

7- isoindolinyl -5-chlorocoumarin;

7- isoindolinyl -3-phenyl-8-methoxycoumarin;

7- (isoindolinyl -3-methylcoumarin;

7- isoindolinyl -3,5 ,S-trimethoxycoum arin;

7- isoindolinyl -3 ,5 -diphenylcoumarin;

7- isoindolinyl -3-phenyl-5 -chloromethylcoumarin;

7- isoindolinyl -5- 3 ,5 ,7-trioxanonyl -3-phenylcoumarin.

A bleach stability test was performed to evaluate the bleach compatibility of the brighteners of the present invention in concentrated aqueous hypochlorite-containing solution. Aqueous sodium hypochlorite solution containing approximately 5.25% sodium hypochlorite and 0.5% of the compound of Example I was formulated by dissolving the optical brightener in the aqueous hypochlorite-containing solution. The resulting solution was visually examined periodically under ultraviolet light for fluorescence. The solutions continued to exhibit strong fluoresence after a storage period of two hours indicating a high degree of stability under extremely adverse hypochlorite degradative conditions.

The detergent (laundering and brightening) compositions of this invention are exemplified by the following examples which describe built formulations in which the optical brighteners of the invention can be employed. These compositions provide pHs in the range of 8.511.5. The invention is not limited by these examples, however,

which are merely illustrative.

Example V Percent Sodium soap of :80 coconutztallow fatty acids 35 Sodium silicate l0 Tetrasodium pyrophosphate 40 Sodium chloride 5 Disodium 4,4 diisoindolinyl-2,2'-stilbenedisulfonate 0.05

Moisture Balance This composition launders well and exhibits good brightening properties on cotton fabrics.

Example VI A granular built synthetic detergent composition having the following formulation can be prepared with the brightening agents of this invention incorporated therein. The composition, in addition to performing well in its cleaning capacity, imparts effective fluorescence to fabrics cleaned in the solution.

The following granular composition containing an effective chlorine bleaching agent performs very well in cleaning, whitening and brightening:

Percent Sodium tallow alkyl sulfate 7 Sodium linear dodecylbenzenesulfonate 7 Sodium tripolyphosphate Sodium carbonate 10 Sodium sulfate 10 Potassium dichlorocyanurate 15 Sodium 4-(isoindolinyl)-2-stilbenesulfonate 0.5

Sodium 4 (7-chloro-l-isoindolinyl)-2-stilbenesulfonate 0.05 Moisture Balance Example V1] 1 A built liquid laundering composition which brightens as it cleans and which is suitable for laundering household fabrics can have the following composition:

Example 1X A household laundering composition can contain the following ingredients:

Percent Sodium salt of SO -sulfonate tetradecene 10 Dimethyl coconut alkyl ammonio acetate 10 Trisodium ethane-hydroxy triphosphonate Sodium carbonate l0 3-methyl-7-(isoindolinyl)coumarin 0.10 Moisture Balance 17 Example X An effective granular detergent composition has the following formulation:

Hydrogenated marine oil fatty acid suds depressant 2.2 Sodium tripolyphosphate 40 Trisodium nitrilotriacetate 20 Sodium silicate (ratio of Sio zNa O of 2:1) [10 Sodium sulfate .13

Disodium 4,4'-diisoindolinyl-2,2-stilbenedisulfonate 0.5

Water Balance 4 Example XI An effective cool water built granular composition according to this invention, particularly useful with resintreated cotton fabrics, has the following composition:

Percent Sodium tallow alkyl sulfate 5 3-(N,N dimethyl-N-hexadecylammonio)-propane-1- sulfonate The aqueous and granular bleach composition of this invention are exemplified by the following examples which are formulations in which the optical brighteners of the invention can be employed. The invention is not, however, limited by these examples which are merely illustrative.

Example XII An excellent aqueous bleach composition which improves the whitening of bleached textiles has the following composition:

Percent Sodium hypocbloride 5.2 4,4'-(isoindolinyl)-2,2-stilbenedisulfonate 0.2 Water Balance Example XIII The following granular bleach composition which dissolves readily in a household automatic washing machine has the following composition:

Percent Potassium dichlorocyanurate 65 Sodium linear dodecylbenzenesulfonate 6 Potassium pyrophosphate 25 4,4-(isoindolinyl)-2,2'-stilbenedisulfonate 3 Moisture 0.3 Sodium sulfate Balance Example XIV A granular bleach formulation which improves the appearance of bleached textiles has the following composition:

Percent Sodium dichlorocyanurate 40 Sodium tallow alkyl sulfate Potassium tripolyphosphate 3-methyl-7-(isoindolinyl)coumarin 1 Sodium sulfate Balance The foregoing description of the invention has been presented describing certain operable and preferred embodiments. It is not intended that the invention should be limited since variations and modifications thereof will 18 be obvious to those skilled in the art, all of which are within the spirit and scope of this invention.

What is claimed is: 1. A compound of the formula Aa @N z ucaa wherein each a is an integer of from 1 to 4; x is 0 or 1; each A is selected from hydrogen; alkyl of l to 10 carbon atoms; halogen; alkoxy of from 1 to 10 carbon atoms; aryl of from 6 to 12 carbon atoms; alkylsulfonyl of from 1 to 10 carbon atoms; alkoxyalkyl of from 2 to 10 carbon atoms; ethylenoxy of the formula H(Cl-l- CH O), where n is an integer from 1 to 10; haloalkyl of from 1 to 10 carbon atoms; alkanoyl of from 2 to 10 carbon atoms; cyano; and polyhydroxyalkyl of from 1 to 10 carbon atoms; when x is 0, Z is a monovalcnt radical selected from CH-CH Bb Eb wherein each b is an integer from 1 to 4 and each B is selected from groups A above; SO OM where M is hydrogen or alkali metal; and

-SO1N where R and R' are each hydrogen; alkyl of 1 to 4 car-- bon atoms, hydroxyalkyl of from 1 to 4 carbon atoms, phenyl, glucosyl or together comprise a pyridyl or morpholino group; and

wherein each A is as defined above and each p is 1 or '2; and when x is 1, Z is a bivalent radical of the formula ca=cn Bb B b wherein each b is an integer of from 1 to 4 and each B is selected from groups A above; -SL) 0M where M is hydrogen or alkali metal; and

where R and R are each hydrogen, alkyl of 1 to 4 carbon atoms, phenyl, glucosyl or together comprise a pyridyl or morpholino group.

2. A compound of claim 1 wherein at is i; and Z is a bivalent radical of the formula where R and R are each hydrogen, alkyl of l to 4 carbon atoms, hydroxyalkyl of 1 to 4 carbon atoms, phenyl, glucosyl or together comprise a pyridyl or morpholino group.

3. A compound of claim 2 wherein each B is -SO OM, where M is alkali metal; and each b is 1.

4. A compound of claim 2 wherein each B is so2N where R and R are hydrogen.

5. A compound of claim 1 wherein x is 0, and Z is a monovalent radical of the formula -Bb Eb wherein each b is an integer from 1 to 4 and each B is selected from groups A above; SO OM where M is hydrogen or alkali metal; and

/R S02N where R and R are each hydrogen, alkyl of 1 to 4 carbon atoms, hydroxyalkyl of from 1 to 4 carbon atoms, phenyl, glucosyl or together comprise a pyridyl or morpholino group.

6. A compound of claim 5 wherein each B is hydrogen /\/\O/Ro wherein each A is as defined above and each p is l or 2.

References Cited Kollner: East German Doctoral Thesis 67 HB 2042, University of Jena, East Germany, 1965, pp. 46-40, preface and subject index relied upon.

JOHN D. RANDOLPH, Primary Examiner U.S. Cl. X.R.

AQQ

"7 g? UNITED STATES PATENT OFFICE 54 CERTIFICATE OF CORRECTION 7 Patent No. 3,646,015 mad February 29, 1972 Inventofls) lgwis R. Hamilton It is certified that error appears and that said Letters Patent are hereby Column 9, line 26, "phoshine" should be phosphine in the above-identified patent corrected as shown below:

Column 14, line 53, after "sodium4-(7methyl-l-|isoindolinyl) 2-stilbenesulfonate;" insert sodium 4-(7-phanyl-l- I isoindolinyl) '-2-stilbenesulfonate Signed and sealed this 11 th day of July 1972.

(SEAL) Attest:

EDI'JARD mmmcmm, JR.

R0 BERT GOTT SCHALK Attesting Officer Commissioner of Patents 5 3 UNITED STATES PATENT OFFICE CERTIFICATE OF CQRRECTION 2-9, 1972 ?etent No. Dated February Ziawentofls) Lewis R. Hamilton It is certified that error appears in the above-identified patent mad that said Letters Patent are hereby corrected as shown below:

Column 9, line 26, "phoshine" should be phosphine Column 14, line 53, after "sodium 4-(7-methyll-\isoindolinyl) 2-stilbenesulfonate;" insert sodium 4-(7-phenyl-lisoindolinyl) --2--stilbenesulfonate Signed and sealed this 11 th day of July 1972.

(SEAL) Attest:

R0 BERT GOTT SCHALK Commissioner of Patents E WAR D M. FLETCHER JR. Attosting Officer

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