DE1806256A1 - Use of phthalimidinyl derivatives as optical brighteners - Google Patents

Description

Dk. ju. ». .

DR. JUR. HANS CHK. _Bui .

ι
FRANKFURTAM MAIN-HOCHSf

ADEIONSIRASSEM

Our Mr. 15138

The Procter & Gamble Company |

Cincinnati (Ohio, U.S.A.)

Use of phthalimidinyl derivatives as optical

Brightener.

BLe present invention relates to the use of mono- and diphthalimidinyl derivatives of fluorescent aromatic Amines (1) in detergent and cleaning agent compositions for washing laundry that contains an organic detergent and a salt of an alkaline G-builder, and (2) in aqueous and granular hypochlorite bleach mixtures.

In recent years, the use of optical brighteners, and occasionally optical bleaching agents or fluorescent substances, has increased called, increased extraordinarily. Such opti see bleaching agents are "colorless dyes" with fabric substantivity, the effect of which is that they emit light in the invisible ultraviolet range (300-400 mm) like it is contained in natural daylight, and emit it as visible, blue-white light (400-500 nm). This fluorescent scene masks the natural yellowing of textile fibers and results in a highly desirable blue -

& Q9834 / 1S21 originally inspected

white "sheen" on white products and for a fresher, cleaner look on colored products. DLe fluorescence the optical brightener, although rich in blue, varies somewhat in relation to the predominant one Wavelength. If the predominant wavelength is longer, the blue fluorescence gives a weak green tint. One shorter predominant wavelength near the purple end

of the spectrum leads to a blue fluorescence that is faint appears reddish. For practical purposes, especially for Use in batches for detergents and cleaning agents

in general, a neutral blue fluorescence becomes preferred.

Optical brighteners, aie are suitable for use in washing processes, must be substantive to fabrics, Have alkali stability, water solubility and a high degree of fluorescence. In addition, it is particularly advantageous when an optical brightener is resistant to the damaging effects of hypochlorite bleaches. Hypochlorite and similar oxidizing bleaches are generally known to have the fluorescent properties of conventional ones optical brighteners, such as those in detergent and cleaning agent mixtures used, eliminated or destroyed. Since much of the deeply embedded dirt and stains, as they occur when washing textile fabrics, only effectively eliminated by the action of chemical bleaching agents the use of chemical bleaching agents cannot be eliminated for practical reasons. Accordingly Much effort has been expended in researching such brighteners that are compatible with hypochlorite bleach and are suitable for use in washing processes in which they come into contact with them.

Accordingly, it is an object of the present invention to find optical brighteners with fabric substantivity, alkali stability, water solubility and high degree of fluorescence, which are compatible with hypochlorite bleaching agents and which are resistant to the destructive effects of hypochlorite bleaching ^;

9 09 8 3 47 15 21 _ßAD

have, so that they are sctiungen for detergent and cleaning agents can be used which an organic detergent, a salt of an alkaline builder and optionally additionally contain a hypochlorite lead agent.

The present invention relates to the use of mono- and BLphthalimidinyl derivatives of the general formula:

Z-N

in which a is in each case an integer from 1 to 4; x zero or 1; A each represents a hydrogen atom, an alkyl group having 1 to about 10, preferably 1 to 4 carbon atoms, a halogen atom; a C ₁ - to about C ₁ Q -alkoxy group, an aryl group with 6 to about 12 carbon atoms, a C ₁ - to about C-, Q-alkylsulfonyl, Cp- to about C ₁ Q-alkoxyalkyl or a polyethyleneoxy radical of the formula H (CH ₂ CHpO) _n , where η is an integer from 1 to 10, or a haloalkyl group with 1 to about 10 carbon atoms, an alkanoyl group with 2 to about: 10 carbon atoms, a cyano or polyhydric oxyalkyl group with 1 to about 10 carbon atoms and wherein Z, if χ = zero, represents a monovalent radical, is obtained by elimination of a primary amino group from a fluorescent aromatic mono- or BLamine, which is obtained by ultraviolet absorption in the range from 325 to 400 nanometers (nm) and fluorescence is characterized in the range from 400 to 475 nm, or, if χ = 1, a divalent radical obtained by eliminating two primary amino groups from a fluorescent aromatic biamine with the absorption and fluence mentioned above orescence-spectral characteristics, as optical brighteners in detergents and cleaning agents.

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The said compounds are excellent optical Brighteners for use in detergents and cleaning agents for washing laundry, the alkaline builder materials and they are particularly characterized by their resistance to the destructive effects of chlorine-containing, bleaching acting compounds characterized. Accordingly, they can • be used in detergent and cleaning agent mixtures, which contain alkaline builder compounds and active chlorine-containing compounds with a bleaching effect.

DLe mono- and diphthalimidinyl derivatives proposed according to the invention of the general formula given above are phthalimidinyl derivatives as mono- and di-phthalimidinyl, depending on the value of the symbol characterized. If χ in the general formula is JJuIl, it is a monophthalimidinyl compound, whereas x = 1 in the case of diphthalimidinyl compounds.

The monophthalimidinyl optical brighteners are conductive of fluorescent aromatic primary mono- or diamines, which by UV absorption in the range from 325 to 400 mn and Fluorescence in the range from 400 to 475 nm are characterized. These fluorescent amines can be through the formula (HpN) -Z, where Z is the remainder of the fluorescent amine, i.e. the entire molecule, except from the amino group, and η = 1 in the case of a monoamine and 2 in the case of a diamine. The equimolar implementation of a monoamine with an aromatic o-dialdehyde under BiI-. Formation of a monophthalimidinyl compound can be illustrated as follows will:

CHO

+ H ₂ NZ - } A _a OHO

In a similar reaction, an amino group of a DLamina of the type defined above can be combined with an aromatic ortho

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dialdehyde to form a monophthalimidinyl compound to be brought to implementation, in which a non-implemented Amino group is present on the Z radical.

In the same way, fluorescent aromatic are subject to üLamines with the same spectral characteristics, which are symbolized by the formula HpN-Z-NHp, the reaction with aromatic o-uialdehydes according to the following Reaction chema:

-4 A -f- ¹ I NZN CHO

The remainder Z is used in the context of the invention to symbolize that remainder which after elimination "an or two primary amino groups from a fluorescent aromatic Amin of the type described above arises. !! Readers rest is only defined for reasons of expediency as a residue formed by elimination, but this characterization continues of the amine residue is not an actual elimination in a chemical sense in the formation of the brightener compounds of the type proposed according to the invention.

Lie aldehydes, as used in the preparation of the invention applicable optical brighteners can be used and represented by the general formula

CHO
CHO

are symbolized, where A and a have the meanings given above are aromatic o-maldehydes and include, for example, phthaldehyde, 4-tert.-butyl-1,2-phthalaldehyde,

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3-chloro-1,2-phthalaldehyde, 4,5-dimethoxy-1,2-phthalaldehyde, 4-naphthyl-1,2-phthalaldehyde, 3-methylsulfonyl-1,2-phthalaldehyde, 4-ethoxyethyl-1,2-phthalaldehyde, 3-trifluoromethyl-1,2-phthalaldehyde, 3-phenyl-1,2-phthalaldehyde, 4-chloro methyl-1,2-phthalaldehyde, 3-cyano-1,2-phthalaldehyde and 4- (1,2-LtLhydroxyäthyl) -l, 2-phthalaldehyde. A preferred o-DLaldehyde is phthalaldehyde, which is easy to react and convenient is available.

ItLe amines that can be used to make the present optical brighteners are any of the fluorescent aromatic primary mono- and ULamines characterized by UV absorption in the range of 325 to 400 nm and fluorescence in the range of 400 to 475 nm. These compounds are customary, per se known brightener chromophores. Examples of fluorescent amines with the prescribed spectral features and their monovalent or divalent radicals (Z), which are derived therefrom by eliminating one or more amino groups, include the following preferred structures:

(1) 7-aminocoumarins of the formula:

wherein each symbol ρ denotes 1 or 2 and each radical A has the meaning given above;

(2) 5-Amino-1,8-naphthalenecarboximide of the formula:

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C C

C C

"where ρ and A are as defined above and R = hydrogen, a C ₁ - to C ^ -alkyl or aryl group having 6 to about 12 carbon atoms;

(3) 4-aminostilbenes of the formula

<J

CMH

CH = CH

B,

'a

wherein each symbol a has the meaning given above and each symbol b has the meaning of A or -SO ₂ (M or

-SO ₀ N - ** ^R symbolizes, where M = hydrogen or an Al-

potassium metal (eg sodium, potassium or lithium) and R and R ¹ each represent hydrogen or alkyl radicals having 1 to about 4 carbon atoms or are part of a ring structure (eg morpholine);

(A) 4,4'-Iä.aminostilbene of the formula:

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CH = GH

wherein each symbol a has the meaning given above and each symbol B has the meaning given above for A.

or so

or S

symbolizes, where M = tfasser-

substance or an alkali metal (for example sodium, potassium, lithium) and R and R ^{1 have} the meaning given above;

(5) 2-aminonaphthalenes of the formula:

where each symbol ρ has the meaning given above and each B has the meaning given for A or

-SO ₀ OM or -SO ₀ N * ^ symbolizes, where M is a hydrogen

R '

atom or an alkali metal (for example sodium, potassium, lithium) and R and R ^{f have} the meaning given above;

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(6) 3-Ajnino-2,5-diarylheterocycles of the formula:

GH

ar ar ar ar

where X for oxygen or J> iCB, stent, ar is a phenyl, iMaphthalBulfonat- or a phenyl group with a substituent in the m-, p- or both in the m- and p-position, where all the substituents are chlorine, a Wethoxy, dulfonate or J-dialkylamino _c .: Group and each alkyl group can have 1 to about 4 cone atoms.

.Particularly preferred amines for reasons of ease, with aer you the desired reaction with aromatic o-oil aldehydes are also 3-atnino-2,5-diarylfurans

ar ar

vjorin ar has the meaning given above (eg 3-amino-2,5-diphenylfuran), the 7-iüninocoumarins (eg 4-1 ^v iethyl-6-methoxyoumarin), the aminostilbenes ( eg 4-amino-4'-methoxystilbene -

BAD ORlQtNAL 909834/1521

2,2'-disulfonic acid

SO ₂ OH

SO ₂ OH

the BL sodium salt thereof, 4-Arüino-4'-methoxystilbene-2.2 ^t -disulfonamide

OCH,

SO ₂ HH ₂

^{4.4 l} -diaminostilbene-2.2 ^l -di.sulfonic acid

H ₂ N

fs \

CH = CH

SO ₂ OH

the BLsodium salt thereof and 4.4 ^l --ÜLaminostilbene-2.2 ^l -disulfon amide).

£ ü.e above indicated special Aminohromophore merely serve only for exemplary explanation "It is believed that the particular type of fluorescent imine ₅ which is used during the reaction of secondary Bede '. with regard to the presence of the essential phthalate

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BATH ORIGINAL

imidinyl radicals

which at least partly for the remarkable bleach tolerance and durability of the optical brighteners proposed according to the invention is responsible, so that the selection of suitable fluorescent aromatic amines, which by a UV absorption in the range of 325 to 400 nm and fluorescence in the range from 40Ü to 475 nm is not a critical aspect of the present invention.

Optical brighteners derived from the preferred amines have the following structures:

A "-

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CH »CH _x , \ = fc /

and

CH

ar X ar

where a, pt A »B» ar · X and R ignore the meanings given above.

Optical, brighteners · the preferred from the particular Amines are produced "have the following structures"

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CK = CH

SO ₂ OM

SO ₂ OM

OCH

CH = CH

SO ₂ OM SO ₂ OM

CH = CH -

The mono- and BLphthalimidinyl compounds to be used according to the invention can be produced by methods known per se. For example, they can be used in the Yakugal u Zasshi, 8Jj (12), 3. 1042-1049 (1965)

. ' 4 Λ t.

will hold. A convenient method involves the reaction of a dialdehyde with a suitable amine of the above "type described. The reaction may be at a temperature ranging from about -2O ⁰ G to about 150 ⁰ C by reacting an aromatic o-Haldehyds with a fluorescent aromatic primary amine having the spectral characteristics set forth above, DLe ratios of o-DLaldehyde to fluorescent primary amine that can be employed are generally in the range of about 0.8: 1 to 3: 1 on a molar basis Case of making Yer bonds of the type

Z-N

_Jx

where χ = zero, a range of about 0.8: 1 to 1.5: 1 is used. Since the o-DLaldehyde used in the course of the reaction can be removed from the reaction vessel more conveniently than the fluorescent primary amine, it is preferred to use a slight excess of the o-DLaldehyde over a molar proportion of the fluorescent primary amine. Accordingly, a molar ratio of about 1.1: 1 of o-aldehyde to fluorescent primary amine is particularly preferred. In the case of the preparation of compounds which have a bie structure, ds those in which χ in the formula given above is 1, the molar ratio of o-DLaldehyde used is to. fluorescent primary amine about 1.8 s 1 to about 3: Ii, the ratio of 2.2: 1 being particularly preferred. If asymmetric uphthalimidine yl derivatives are desired, any mixture of two or more o-maldehydes can be used, the only limitation being that. that the molar ratio of mixed o-DLaldelmi to. fluores - excreniem primary Araia in the range of. - ^ ml _s ci? 1 el ^ * t ^ a

DLe reaction of the above-mentioned o-DLaldehyde with the The above fluorescent amine chromophores can be added by adding a solution of the amine to a solution of the aromatic o-DL-aldehyde be effected. Conversely, an amine solution can be added to a solution of the o-aldehyde, the the latter sequence is preferred. Although the reaction was through

ο ο

Reaction may be effected at a temperature of -20 C to 150 C, a preferable Temperatürint ervall between about -10 to about 100 ⁰ C. reactions which are carried out at the low temperature of the preferred range, ie at about ü C, generally a period of about 24 hours before walking. Conversely, reactions take less time at around 100 C and can, in good yields, be carried out in around 30 minutes. It is particularly preferred to carry out the reaction at about 0.degree. C. to about 60.degree.

In general, the process is carried out in a polar organic solvent which is essentially non-reactive with either the o-dialdehyde or the fluorescent amine used in the reaction. The amount of solvent employed is not critical so long as there is sufficient amount to conveniently dissolve the fluorescent amine employed. In general, a minimum amount of about five times the weight of the amine used is sufficient, especially in the batch of non-ionic, fluorescent amines. The maximum amount of solvent used is not subject to any limitation, with 30 times the weight of the fluorescent Amine is economically satisfactory Examples of suitable substantially non-reactive solvents which may be used are low molecular weight N, N-DLalkylamides such as dimethylformamide, cyclic ethers such as tetrahydrofuran and BLoxane, aromatic hydrocarbons such as benzene and certain organic solvent-water mixtures, such as DLmethylformamide-water, dimethylformamide, "which, calculated on a volume basis, contains about 1 to about 60 % water.

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Specific examples of brightener compounds which, according to the invention, are used in detergent and cleaning agent mixtures Applied for laundry are the following:

(1) 3-phenyl-7-phthalimidinyl coumarin;

(2) 2- (p-chlorophenyl) -7-phthalimidinyl coumarin;

(3) 3-phenyl-7- (2-methylphthalimidinyl) coumarin;

(4) 3-Ehenyl-5-Hiethoxy-7-phthalimidinyl coumarin;

(5) 3- (p-henylsulfonic acid) -7-phthalimidinyl coumarin;

(6) N-methyl-5-phthalimidinyl-1,8-naphthalenecarboxamide;

(7) 4-phthalimidinyl-4'-methylstilbene;

(8) 4 ~ phthalimidinyl-4'-methoxystilbene;

(9) sodium 4-phthalimidin.yl-4'-stilbene sulfonate;

(10) 4-phthalimidinyl-4'-phenylstilbene;

(11) 4-phthalimidinyl-3-methoxy-4'-methylstilbene;

(12) 4- (2-chlorophthalimidinyl) -4 '- (2-methylphthalimidinyl) -stlbenedisulfonic acid;

(13) Sodium 4,4 · -diphthalimidinyl-2,2 · -stilbene disulfonate;

(14) 4,4-BLphthalimidinyl-2,2'-stilbene disulfonamide;

(15) 4-phthalimidinyl-4 '- (2-chlorophthalimidinyl) -2,2'-stilbene disulfonamide;

(16) DLsodium 4,4'-dlphthalimidinyl-6,6 »-dichloro-2,2 · -stilbene disulf onat;

Sodium e-phthalimidinyl - ^ - naphthalene sulfonate;

(18) 6-phthalimidinyl-2-naphthalenesulfonamide;

(19) sodium 4-chloro-6-phthalimidinyl-2-naphthalenesulfonate;

(20) 2,5-phenyl-3-phthalimidinyl furan;

(21) DLsodium 2,5- (p-phenylsulfonate) -3-phthalimidinyl furan;

(22) 2,5-3) L- (p -chlorophenyl) -3-phthaliiaidinylfuraii;

(23) 2- (p-methoxyphenyl) -3-phthalimidinyl-5- (p-chlorophenyl) furan;

(24) N-methyl-2,5-diphenyl-3-phthalimidinyl pyrfol;

(25) 2,5-IV- (ni-methoxyphenyl) -3-phthalimidinyl furan.

DLe proposed according to the invention to erverbindüngen on bright are alkali-stable and have a high degree of fluorescence as well as noun! tat compared to cellulose, super polyamide -

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(Nylon) and acetate fabrics, especially with regard to cotton fabrics. The water solubility of these brightener compounds is also satisfactory.

These brightener compounds are employed in amounts ranging from about 0.01 to about 3% Laundry detergent and cleaning agent compositions lie. A preferred amount of brightener is about 0.5 # to about 1.5 #. They are used as additives for washing and Detergent compositions used that at least about 10 #> a mixture of an organic Detergent and an alkaline builder in a ratio of about 5: 1 to about 1:20, preferably about 2: 1 to about 1:10. This mixture " may be present in proportions so high that it corresponds to the remainder of the composition. He organic detergents and salts of alkaline builders are discussed in more detail below.

Organic detergents:

The organic detergent compounds found in the detergent compositions to which the optical brighteners can be added, based are as follows:

a) Water soluble soaps.

Examples of suitable soaps for use in the context of the invention are the sodium, potassium, ammonium and alkanolammonium (e.g. mono-, di- and triethanol ammonium) salts of higher fatty acids ( ^G in ~ ^G 22 ^ * Particularly useful the sodium and potassium salts of mixtures of fatty acids derived from coconut oil and tallow, e.g. sodium and potassium tallow and coconut soaps.

b) Anionic, synthetic non-soap detergents.

A preferred class can generally be water-soluble salts, in particular alkali metal salts, organic

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Sulfuric acid reaction products are addressed which in their molecular structure have an alkyl radical with about 8 Ms about 22 carbon atoms and a radical which is derived from the group comprising sulfonic acid and sulfuric acid ester radicals. (The term "alkyl" also includes the alkyl portion of higher acyl radicals). Important examples of these anionic synthetic detergents are the sodium and potassium alkyl sulfates, especially those obtained by sulfating higher (Gg- to C ₁₈ -) alcohols (which can be prepared by reducing the glycerides of tallow or coconut oil), sodium or potassium alkylbenzenesulfonates, in which the alkyl radical can be straight-chain or branched and contains from about 9 to about 15 carbon atoms, preferably from about 12 to 14 carbon atoms; 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 acid alcohol (e.g. tallow or coconut oil alcohol) and about 1 to 6 moles of ethylene oxide; Sodium or potassium alkylphenolethylene oxide ether sulfates with 1 to 10 units of ethylene oxide per molecule, in which the alkyl radical has 8 to 12 carbon atoms; the reaction product of fatty acids esterified with isethionic acid and neutralized with sodium hydroxide, for example the fatty acids being derived from coconut oil; Sodium and potassium salts of the fatty acid amide of a methyl tauride, in which the fatty acids are derived, for example, from coconut oil; Sodium and potassium salts of SO ^ -sulfonated C- ^ Q-Cg ^ -a-olefins

c) Nonionic synthetic detergents.

One class of nonionic detergents can generally be defined as compounds formed by the condensation of alkylene oxide groups (hydrophilic type) with organic hydrophobic compounds, which can be of the aliphatic or alkyl aromatic type, are obtained »Me

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I «ff I« "IIKIIHIliHpNllll IFf Il IfI:., - _?. !! ι ;;,;. · -Yqmqgn ;,. ,,,;," .. ,,. ",,,,.,., ,, ^,

Length of the hydrophilic or polyoxyalkylene radical associated with Any particular hydrophobic group is condensed, can be conveniently adjusted to be a water-soluble Compound with the desired ratio between hydrophilic and hydrophobic elements is obtained. One the second class of nonionic detergents includes the higher ones Fatty acid amides. Its third class of non-ionic detergents has semi-polar o characteristics. These three classes can be illustrated in more detail as follows:

(1) A class of nonionic synthetic detergents is commercially available under the name "Pluronic" expelled. These compounds are obtained by the condensation of ethylene oxide with a hydrophobic base made by Condensation of propylene oxide with propylene glycol occurs. The hydrophobic part of the molecule, which is insoluble in water, has a molecular weight of about 1500 to 1800. By adding polyoxyethylene ethylene to this hydrophobic part is considered to be an increase in the water solubility of the molecule Whole achieved and the fluid characteristics of the product are retained until the polyoxyethylene content is about 50 # of the total weight of the condensation product.

(2) Alkylphenol-polyethylene oxide condensates are condensation products of alkyl phenols having an alkyl group containing about 6 to 12 carbon atoms in either straight or branched lines Contains chain arrangement, with ethylene oxide, wherein the ethylene oxide is present in amounts that 5 to 25 moles of ethylene oxide correspond to per mole of alkylphenol. The alkyl substituent in such Compounds can, for example, from polymerized propylene, Dlisobutylene, octane or honing can be derived.

(3) Nonionic synthetic detergents can be derived from the condensation of ethylene oxide with the product be that in the reaction of propylene oxide and ethylenediamine arises and comprises compounds which contain about 40 to about 80 W-Ew .- # Polyoxyäthylen and a molecular weight from about 5000 to about 11,000. Such compounds disfigure the reaction of ethylene oxide with a

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hydrophobic base obtained from the reaction product of ethylenediamine and excess propylene oxide is built up, the base having a molecular weight on the order of 2500 to 3000.

(4) Other nonionic detergents include condensation products aliphatic alcohols with 8 to 22 carbon atoms either in a straight-chain or branched arrangement, with ethylene oxide, e.g. a coconut alcohol ethylene oxide condensate, 'the 5 to 30 moles of ethylene oxide per mole of coconut alcohol having.

(5) ItLe ammonia, monoethanol and diethanoi ami de of fatty acids with an acyl radical of about 8 to about 18 Carbon atoms are useful nonionic detergents. These acyl residues are usually from naturally occurring Q-lycerides, e.g. coconut oil, palm oil, soybean oil and tallow, derived, but can also have been obtained synthetically, e.g. by the oxidation of petroleum or by Hydrogenation of carbon monoxide using the Fischer! Dropach process.

(6) Semipolar nonionic detergents include long chain tertiary amine oxides, those of the following general formula

H ²

- (OR ⁴ ) _n -N

correspond, where R is an alkyl radical with about 8 to about 18

■? 3

Carbon atoms, R and R ^ each methyl, ethyl or Hydroxyethyl radicals, R ethylene and η = zero to about 10 mean. The arrow in the formula is a common representation of a semi-polar bond. Specific examples of amine oxide detergents include DLmethyldodecylamine oxide and bis ~ (2-

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hydroxyethyl) dodecylamine oxide.

(7) Other semipolar nonionic detergents include long chain tertiary phosphine oxides corresponding to the following general formula RR'R "P -> 0, where E is an alkyl, alkenyl, or monohydroxyalkyl radical of 10 to 20 carbon atoms and R ¹ and R", respectively Denote alkyl or monohydroxyalkyl groups having 1 to 3 carbon atoms. The arrow in the formula is a common representation of a semipolar bond, examples of suitable phosphine oxides are given in U.S. Patent No. 3,304,263 and include: BLmethyldodecylphosphine oxide and dimethyl (2-hydroxydodecyl) phosphine oxide.

(8) Other semi-polar nonionic synthetic detergents and cleaning agents include long-chain sulfoxides the general formula

r ⁵ -Lr ⁶

wherein R is an alkyl radical having about 10 to about 28 carbon atoms, Hull to about 5 ether bonds and zero to about 2 hydroxyl substituents, with at least a portion of the radical R _e j. _n comprises an alkyl radical having zero ether bonds and having from about 10 to about 18 carbon atoms, and wherein R is an alkyl radical having 1 to 3 carbon atoms and 1 to 2 hydroxyl groups. Specific examples of these sulfoxides are: dodecyl methyl sulfoxide and 3-hydroxytrideeyl methyl sulfoxide.

d) Ampholytic synthetic detergents can generally be used as derivatives of aliphatic secondary and tertiary Amines are designated in which the aliphatic radical is straight-chain or can be branched chain alkyl groups and wherein one of the aliphatic substituents is from about 8 to 18 carbon contains atoms and an anionic, water-soluble

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Has group, e.g. carboxy, sulfo, sulfato, phosphato or phosphorus residues. Examples of compounds falling under this definition are sodium 3-dodecylaminopropionate and sodium 3-dodecylaminopropanesulfonate.

e). Zwitterionic synthetic detergents can generally referred to as derivatives of aliphatic quaternary ammonium, phosphonium and sulfonium compounds, in which the aliphatic radical can be a straight or branched chain alkyl group and in which one of the aliphatic substituents about 8 to 24 carbon atoms ■ k and another an anionic water-solubilizing group,

e.g. a carboxy, sulfo, sulfato, phosphato or phosphono radical, contains. Examples of compounds falling under this definition are ^ - (w.N-dimethyl-il-hexadecvlammonio) -propane-l-sulionate and 3- (N, N-dimethyl-ü-hexadecylammonio) -2-hydroxypropane-l-sulfonate, which are preferred for their cold water washing and cleaning characteristics (see e.g. Canadian patent Wr. 708.148).

These soap and non-soap type detergent compounds having anionic, nonionic, ampholytic and zwitterionic character can be used alone or in combination. DLe above examples are merely illustrative of the many ψ suitable detergents.

Other organic detergent compounds can also be used will.

Builder salts .

The detergent and cleaning agent mixtures for which the present phthalimidiny compounds according to the invention Can be used as optical brighteners, also contain water-soluble builder salts of organic or inorganic Type.

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Examples of water-soluble, inorganic salts of alkaline Builders on which detergents and cleaning agents are based are alkali metal carbonates and borates, phosphates, polyphosphates, bicarbonates, silicates and sulfates. Particular examples of such salts are sodium and Potassium tetraborates, perborates, bicarbonates, carbonates, tripolyphosphates, pyrophosphates, orthophosphates and hexametaphosphates.

Examples of salts of organic alkaline builders, on which detergents and cleaning agents may be based are: (l) Water-soluble aminopolyacetate, e.g. sodium and potassium ethylenediamine tetraacetate, nitrilotriacetate and -N- (2-hydroxyethyl) nitrilodiacetate; (2) water soluble I

lent salts of phytic acid, e.g. sodium and potassium phytate (see U.S. Patent No. 2,739,942; (3) water-soluble polyphosphonates, including in particular sodium, potassium and lithium salts of ethane-1-hydroxy-1-diphosphonic acid, sodium -, potassium and lithium salts of methylenediphosphonic acid, sodium, potassium and lithium salts of ethylene diphosphonic acid, and sodium, potassium and lithium salts of ethane-1,1,2-triphosphonic acid.Other examples include these alkali metal salts of ethane-2-carboxy-1 , l-diphosphonic acid, hydroxymethanediphosphonic acid, carbonyldiphosphonic acid, ethane-hydroxy-1,1,2-triphosphonic acid, ethane-2-hydroxy-l, l, 2-triphosphonic acid, propane-l, l, 3 »3-tetraphosphonic acid, propane ' { 1,1,2,3-tetraphosphonic acid and propane-1,2,2,3-tetraphosphonic acid;

(4) water-soluble salts of polycarboxylate polymers and copolymers as described in U.S. Patent No. 3-308,067 are described. In particular contains a builder material for detergents and cleaning agents, a water-soluble salt of a polymeric aliphatic polycarboxylic acid, which has the following has structural relationships with regard to the position of the carboxylate groups and the following prescribed has physical characteristics: (a) a minimum molecular weight of about 350, calculated on the basis of the acid form; (b) an equivalent weight of about 50 to about 80 calculated as

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Acid form; (c) at least 45 moles of the monomer types with at least 2 carboxyl radicals, which are mutually by nioht more than 2 carbon atoms are separated; (d) the point of attachment of the polymer chain of any carboxyl-containing one Remainder is by no more than 3 carbon atoms along the line Polymer chain removed from the junction of the next carboxyl-containing residue. Polymers are particular examples of itaconic acid, aconitic acid, maleic acid, kessconic acid, Fumaric acid, methylenemalonic acid and Gitraconic acid as well as copolymers of these compounds with one another and with other compatible monomers, such as ethylene.

Mixtures of organic and / or inorganic builders can also be used as a basis for the detergents and cleaning agents lie. Such a mixture of builders is in the Canadian patent Ur. 755.038 described, e.g. ternary mixtures of sodium tripolyphosphate, trisodium nitrilotriacetate and trisodium ethane 1-hydroxy-1,1-diphosphonate. The builders described above can

also available individually.

The preferred builders are sodium tripolyphosphate and sodium nitrilotriacetate, alone or in admixture. The preferred organic detergents and cleaning agents are the anionic sulfates and sulfonates. The detergent and cleaning agent mixtures result preferably pH values in the range from about 8.5 to about 11.5

According to the invention, the phthalimidinyl derivatives can be used to form detergent compositions for washing are added by laundry as a brightener, which if necessary. in addition to organic detergent and glycerin, any contain the following common additives for such mixtures, which the product even more attractive or effective do. For example, perfumes, dyes, proteolytic enzymes, corrosion inhibitors, oxygen and oxygen bleaches, Agents preventing dirt redeposition or other brighteners are also present. Thinners, such as water, moisture, and sodium sulfate, can also

9C9834 / 1521

be used, mn a, brightener, organic washing and containing detergents and alkaline builder salt To add to the mixture as required.

EtLe mono- and diphthalimidinyl derivatives which can be used according to the invention as optical brighteners are stable against attack by hypochlorite compounds. Thus, these stable class of brighteners is advantageously in washing and cleaning compositions for the washing of laundry comprising from about 0.5 7 ", more usually 3 to $ 17, an active chlorine-containing bleaching acting compound to about 25 $>. Examples of such compounds are: dichlorocyanuric acid; 1,5-ItLchlor-5,5-dimethyl- A hydantoin; Ν, Ν'-diehlobenzoylene urea; p-toluenesulfone dichloramide; Trichloromelamine; N-chlorammelin; N-chlorosuccinimide; NjN'-DLchlorazodicarboxamide;N-chloroacetylurea; Ν, Ν'-mohlorbiuret; chlorinated dicyandiamide; Sodium hypochalorite; Calcium hypochlorite; Lithium hypochlorite; chlorinated trisodium phosphate. Preferred compounds are DLchlorocyanurates, ie dichlorocyanuric acid and the sodium and potassium salts thereof.

The optical mono- and DLphthalimidinyl brighteners can also be used in aqueous and granular bleach mixtures. In general, aqueous bleach mixtures are prepared by adding an optical brightener | dissolves or disperses in an aqueous solution of alkali metal hypochlorite bleach. The optical brighteners proposed according to the invention are readily soluble in aqueous hypochlorite solution and remain stable over a considerable period of time, so that they can be conveniently packaged, shipped and stored without the whiteness-increasing effect of the optical brightener or the oxidizing effect of the bleaching agent being lost. Liquid bleach mixtures are characterized by a pH in the range of about 10.5 to about 13.0 and consist essentially of about 1.0 to about 10 percent alkali metal hypochlorite bleach and about 0.002 to about 2 percent of the optical brightener.

909834/1521

Preferred mixtures containing hypochlorite bleach have an alkali metal hypochlorite bleach component content of about 1 to 10 % , preferably about 3 to 7 %, with about 5> 2 ^a / ° being particularly preferred.

The permanent component can be any of the alkali metal hypochlorites. Examples of such useful bleaching agents are sodium hypochlorite, potassium hypochlorite, Lithium hypochlorite and the like,. However, sodium hypochlorite is particularly preferred because of its superior properties and ready availability.

The optical brightener is, after addition in the mixtures in an amount that 0.002 to about 2.0%, preferably about 0.01 fö to about 0.1%, with $ 0.05 are particularly preferred.

The bleach-stable brighteners used according to the invention are capable of maintaining their bleaching degree-increasing and lightening effects even after treatment with aqueous 1 to 10 -fold hypochlorite-containing bleach solutions for extended periods of time, for example several weeks of storage. The bleach stability, which is usually attributed to the common optical brighteners, is usually to be understood in such a way that these optical brighteners do not become ineffective if they are exposed to dilute solutions of the bleaching agent for limited periods of time, e.g. under the conditions prevailing in the washing machine, if that Hypochlorite bleach is present in aqueous solutions at a hypochlorite level of about 0.02 % for up to 20 to 30 minutes. In contrast to the compatibility with bleaching agents, as it is usually defined, the compatibility of the present optical brighteners is such that they retain their desired effect after treatment with hypochlorite bleach concentrations * which do not normally occur in the course of the laundry process.

309834/1521

■ ··. ■ ", ■■" ■ '■!

- 27 -

The desired bleach compatibility of the present optical brighteners is used to advantage when these brighteners are used in solid mixtures containing hypochlorite bleach. These mixtures usually contain about 1 to about 99 # active chlorine-containing bleaching compound, which is capable of developing hypochlorite in contact with water, and 0.005 to 10 % optical brighteners of the type proposed according to the invention. Granular bleach mixtures preferably contain about 1 to 80 % the active chlorine-containing bleach compound, about 2 to 25 # of an organic detergent active ingredient and about 5 to 60 $> a Öalzes an alkaline builder substance j, the bleaching compounds, the detergent active compounds and ™

G-scaffold salts are of the type described above.

DLe granular bleach mixtures can be used if desired contain any of the usual additives for such mixtures in addition to the bleaching compound, which makes them more attractive or effective, for example perfumes, dyes, proteolytic enzymes, corrosion inhibitors, other chlorine bleaches, anti-redeposition agents, and other brighteners.

These granular bleach mixtures have a pH in the range of about 8 to 12 and develop after up ^: | dissolve active hypochlorite chlorine in water for the effective bleaching of cellulose fabrics.

Preparations for illustrating, by way of example, the use according to the invention of the phthalimidinyl derivatives as optical brighteners are described below, with Roman numerals in brackets denoting the compounds referred to in Table I below.

909834/1521

Example I :

Preparation of Disodium 4,4'-diphthalimidinyl-2,2'-stilbene disulfonate (1):

SO ₂ ONa

BO ₂ ONa

DLe solution, which is obtained by dissolving 4.14 g (0.01 mol) of disodium 4, 4'-diamino-2,2'-stilbene disulfonate in 1 1 of jümethylformamide, is converted into a solution of 2 within one hour while stirring Give 94 g (0.022 mol) of phthaldehyde puffs dissolved in 200 ml of dimethyl formamide; the temperature is kept at 60 G. The reaction is carried out in a 2 liter flask equipped with a magnetic stir bar and a dropping funnel. After stirring for a further hour at 60 ° C., the dimethylformamide is removed using a rotary evaporator. The disodium 4,4'-diphthalimidinyl-2,2'-stilbene disulfonate is then recrystallized from water with a yield of 5.78 g. The UV absorption A ₁₁₁ Q was 349 nm and the fluorescence
the following result:

Max

429 nm. Elemental analysis gave

Calc .: G = 52.9 #; H = 3.52 9b; N = £ 4.11; found i C = 53.3%; H = 4.23 #; N = $ 4.05.

BLe infrared spectra (IR) showed carbonyl absorption at 5 * 97 / U; aromatic absorption at 6.25 At and 6.67 / U. and sulfonate absorption at 8.35 / U, and 9.70 / li. The nuclear magnetic resonance spectra gave a methyl singlet at 4.9 T " and an aromatic multiplet from 1.6 T to 2.9 T

Substantially similar results are obtained when the following compounds are used in place of phthalaldehyde

909834/1521

above example can be used, with the corresponding substituted phthalimidinyl compounds are formed: 4,5-dichloro-1,2-phthalaldehyde; 4-chloro-1,2-phthalaldehyde; 3-isopropoxy-1,2-phthalaldehyde; 4,5-diisopropyl-1,2-phthalaldehyde; 5-batoxy-1,2-phthalaldehyde; 3-trifluoromethyl-1,2-phthalaldehyde; 3- (l, 4,7-trioxanoyl) -1, 2-phthalaldehyde; 4-methoxymethyl-1,2-phthalaldehyde; 3-ihenyl-1,2-phthalaldehyde; 3-waphthyl-1,2-phthalaldehyde; 3-metholsulfonyl-1,2-phthalaldehyde; 4-cyano-1,2-phthalaldehyde and 4- (1,2,3-'i! Rihydroxypropyl ) t1, 2-phthalalaehycl.

Example 11; Preparation of 4,4'-diphthalimidinyl-2,2 ^I -

stilbene disulfonainide (H):

CyIt = GH

The solution, which is obtained by adding 3.68 g (0.01 mol) of 4,4'-diamino-2.2 ^l -stilbene disulTOnamide to 200 ml of dimethylformamide, is stirred within one hour to a solution of 2.94 g ( 0.022 mol) phthalaldehyde, which is dissolved in 200 ml of dimethyl formamide, was added; the temperature is kept at 60 G. The reaction is carried out in a 1 l flask equipped with a magnetic stirrer and dropping funnel. After stirring for a further hour, the dimethylformamide is removed on a rotary evaporator and the 4,4'-diphthalimidinyl-2,2'-stilbene disulfonamide is then recrystallized from ethanol (yield: 4.01 g). The UV absorption A _n ^ _x was 357 nm; the fluorescence A _max was 438 mm; Infrared and nuclear magnetic resonance spectra are consistent with the above structure.

909834/1521

Analysis:

calc .: G = 62.6%; H = 3.47 °; IM = 9.72 f »; Found: G = 62.0 7 °; H = 3.37 Jb \ N = 9.90 Jo.

In essence, results are obtained when Place the above reaction in the following solvents of dimethyl formamide is performed? Dimethylacetainide; IlLmethylisopropamide; Tetrahydrofuran; DLoxane; Morpholine; Benzene; Toluene; Xylene and petroleum ether.

Example III: Preparation of 2,5-M- (p-chlorophenvl) -

3-phthalimiainylfuran.

(PG ₆ H ₄ Gl) 0 (PG ₆ Ii ₄ Cl)

DLe solution, which is obtained by adding 4.52 g (0.01 hol) 2,5-DL- (p-chlorophenyl) -3-aminofuran to 300 ml JJimetnylformamid, is over a period of 2 hours with stirring to a solution of 1.47 g (0.011 mol) of phthalaldehyde which is dissolved in 100 ml of dimethylformamide, and kept at 60 ⁰ C. The reaction is carried out in a 500 ml flask equipped with a magnetic stirrer and a dropping funnel. After stirring for a further 3 hours at 60 G, the dimethylformamide is removed by evaporation under reduced pressure. The 2,5-DL- (p-chlorophenyl) -3-phthalimidinylfuran is recrystallized from ethanol, about 4.8 g of the product being obtained.

4/1521

Essentially the same results of the Phthaiimidinylverbindungen be obtained when the following compounds in place of the 2,5-di- (p-chlorophenyl) ~ dung 1-3-aminofurans in the above reaction for tii be used are: 2,5-diphenyl-3-aJaino furan; 2,5-diphenyl -3-amino-i> l-methyl pyrrole; 2-phenyl-5- (mm <ithoxy phenyl) -3-atui no furan; 2-phenyl-5- (p-diethylamino) -3-amino furan; Diethyl-2-pheny] -b- (p-niethoxy) -3-aminopyrrole; 2- (p-Chlorophenyl) -S- (m-sodium phenyl sulfonnt) -3-aminofuran and 2- (p-sodium ^{naphthyl sulfonate) - t} j- (p-chlorophen.yH) -3-aminofuran.

Example IV: Preparation of 4-wethyl-4 '-phthalaemidinyl-

stilbene: J

The solution, which is obtained by adding 2.09 g (0.01 iHol) of 4-amino-4'-methylst practice (I) to 1U ml of dimethyl formamide, is obtained for a period of time; From minutes with stirring to a solution of 1.4 7 g (u.Oll ihoJ.) of phthalaldehyde, which is dissolved in 100 ml of dimethylformamide and kept at 85 ° C. The reaction is carried out in a 250 ml actinic round bottom flask equipped with a magnetic stirrer and a dropping funnel. After stirring for a further 15 minutes at 8 ° C., the dimethylformamide is removed by distillation under reduced pressure. The 4-methyl-4'-phthalimidinyl stilbene is obtained in a yield of about 3 g after recrystallization from benzene.

Example V: Preparation of Sodium-6-phthalimidinyl -

2-naphthalene sulfonate.

909834/1521

A solution of 2.45 g (0.01 mole) sodium tri-6-amino-2-naphthalenesulfonate in 100 ml of a mixture of water and ümethylformamide in a ratio of 1: 1 is used within an otund to a solution of 1.47 g (0.011 mol) of phthalaldehyde in 100 ml .Dimethylformamide are dissolved, added and adjusted to 4 5 ° O held. The reaction is carried out in a 250 ml round bottom flask, which is equipped with a magnetic stir bar and dropping funnel is. After stirring for a further 5 hours at 45 ° C., the solvents are reduced by evaporation with ver Pressure removed. The sodium 6-phthalimidinyl-2-naphthalenesulfonate is recrystallized from water and obtained in a yield of about 2.87 g.

Example VI;

Production of 5-phthalimidinyl naphthalimide,

909834/152 i

The addition of 2.02 g of 5-aminonaphthalimia to 100 ml of dimethylformamide solution obtained is within one hour with stirring to a solution; from 1.4-7 g (O, Ü11. WoI) Phthalaldehyde, in 100 ml of dimethylformamide is dissolved, added and kept at a temperature of HO C. IUe reaction is carried out in a 500 ml dog flask, which is equipped with a wagon stirrer and a dropping funnel is. After stirring for a further 40 minutes at 95 ° C weu the dimethylformamide by distillation under reduced Pressure removed. The 5-phthalimidinylnaphthalimide wi-'d obtained after recrystallization from benzene in a yield of about 2.8 g.

Example VII: Preparation of 3-phenyl-V-phthalimidinyl

coumarin.

The solution obtained by adding 2.22 g (0.01 mol) of 7-amino - ^ - phenylcoumarin to 75 ml of dimethylformamide is obtained within one hour with Kuhren to a solution of 1.47 g (0.011 mol) of phthalaldehyde dissolved in 100 ml of dimethylformamide and in a 250 ml round-bottomed flask, which is equipped with a magnetic stir bar, kept at 50 ° C. After stirring for two hours, the dimethylformamide is through Distillation removed. The 3-phenyl-7-phthalimidinyl coumarin is obtained in good yield after recrystallization from ethanol (about 3 g) obtained.

Substantially the same results are obtained when the following compounds are used in place of the 7-amino-3-phenylcoumarin for the formation of phthaliraidinyl compounds

909834/1521 ^BA0

the following are used: 7-amino-4-phenylcoumarin; '/ (sodium p-phenylsulfonate) coumarin; 7-amino-3- (m-mot, hoxyphen.yl) -coumarin; 7-amino-5-chloro-coumarin; 7-amino-3-phenyl-8-methoxy'coumarin;7-amirio-3-diethylcoumarin; 7 -. '3, ¹ S, 8-trimetboxycoumarin; 7-amino-3, 5-diphenyl coumarin; 7-amino - ') - phenyl-5-chloromethylcoumarin and 7-amino-5- (3', 5 ', 7'-trioxanonyl) -3-phenylcoumarin.

Brightener tests.

Table I contains Juten, the polluted during the washing of straight, i'luoreszenzstof f-free cloth from the indicated tissues in 200 ml, 0.47 Vaseinlesung in a 1-pot in a Waschmeßgerät (laundrometer) during 50 i ^v iinuten at 54 0 were obtained. IiLe washing solutions were made up of 0.15 ^: / ° of the tfasch and detergent mixture given below, water with a hardness of 0.1197 g / liter [7 grains / oallone) and the special brightener compound (I ocier II ) in the specified concentrations. We 'leieh .-' tability of brighteners in Table I was tested ate conditions as they occur tfiwaschprozetf usually at Haushai. Heser's test sees the incorporation of 0.5 ml of an aqueous solution containing 5% sodium hypochlorite into the 2 ^ 0 ml solution in the vaschmeter (laundrometer) container and 0.15 % of the washing and Detergent mixture and brightener in the quantities given in Table I below. The aqueous hycochlorite solution was added to the washer-meter container, which was kept at a temperature of 54 ° C., 6 minutes before the addition of the fluorescence-free fabric to be washed. IiLe brighteners subjected to the bleaching test in this way are indicated by a (+), which is indicated next to the GM assessment. The trials were run with 2 parts / million of the creamer; however, Table I also contains data for 4, 5 and 6 parts per million. Me numbers under each tissue type represent GM (Galvanek worrison fluorimeter) units, where

BAO 9Q9834 / 1521

the gröi3eren numbers the better to light ere r _c '; ebnisse lift.

Detergent and cleaning agent mixture:

7.8 ° / o sodium linear dodecylbenzenesulfonate; 9.5% sodium tallow alkene sulfate;

49.4% sodium tripolyphosphate;

5.9 ° h sodium silicate;

13.7 <& ^Na 2 ^S0 4 »

0.2 % sodium carboxymethyl cellulose; 2.2 % non-toxic foam regulating agents; Residual moisture.

Parts / ^v iillion brighteners in an aqueous solution with 0.15% of this mixture are another way of stopping the use of 0.133 * of the brightener in the complete batch given above.

T a b e 1 1 e

I:

Brightener , I. I. Brightener GM units: uuper- Ace link: concentra poly- did: 1 tion in ΐei amide ■ len / million: tree (Nylon): II wool 24 16 - - - - 2 87 - - 4th 137 30th 24 6th 175 - - 6th 17I ⁺ - - 2 60 5 95 5
ι 95 ⁺

= Lead tested.

909834/152 1

These data in G-M units show favorable results compared with other available brightener compounds of different chemical types, which are generally difficult and are expensive to synthesize.

Further tests were carried out in order to evaluate the bleaching agent compatibility of the brighteners of the type proposed according to the invention in concentrated aqueous, hypochlorite-containing solution. An aqueous, sodium hypochlorite-containing "solution which contained about 5» 25 i ° sodium hypochlorite and 0.1 io of the compound (I), ie disodium 4,4'-diphthalimidinyl-2,2'-stilbene disulfonate, was prepared by the Optical brightener was dissolved in the aqueous solution containing hypochlorite, the resulting solution was periodically checked for fluorescence under ultraviolet light.

Detergent and cleaning agent mixtures (detergents and brighteners) are illustrated by the following examples, indicating various builder compositions in which the mono- and diphthalimidinyl optical brighteners are applied can be. These mixtures give pH values in the range from 8.5 to 11.5.

Example 1:

35 % sodium soap made from 20:80 coconut: tallow fatty acids;

10 i » sodium silicate;
40 io tetrasodium pyrophosphate; 6 io sodium chloride;

$ 0.05 disodium ^ .A '

stilbene disulfonate;

Residual moisture.

909834/1521

This mixture is good for washing clothes and shows good lightening properties in cotton fabrics.

Example 2:

A granular (rerüststoff- synthetic detergent and cleaning agent mixture with the following composition thereof can be prepared with the inventively proposed brighteners under incorporation. The mixture giving the cleaned in the solution · tissues effective fluorescence, apart from their good performance in terms of detergency. 'A

17.5 ^J / o sodium linear dodecylbenzenesulfonate;

$ 50> sodium tripolyphosphate;

14 ° i ° sodium sulfate;

0.5 "/>' sodium carboxymethyl cellulose;

7 # sodium trium silicate;

0.10 # 4.4 ^l -l? Phthalimidinyl-2,2'-disulfonamide;

Residual moisture.

Example 3:

An excellent granular wash and lightening mix for laundry has the following composition:

5 "/> DLmethyldodecylphosphine oxide;

10 "fa condensation product of 11 weeks of ethylene oxide with 1 mol of coconut fatty alcohol;

10 <$> tetrasodium methylenediphosphonate; 60 % sodium tripolyphosphate;

0.5 ° fo sodium carboxymethyl cellulose; 10 i> sodium silicate;

$ 0.20>3-phthalimidinyl-2,5-diphenyl-2,5-diphenylfuran; Residual moisture.

An aqueous solution which has the concentrations of the above approaches corresponding to 0.15 #, 0.3 96 or 0.45 ^,

909834/1521

gives very good results when cleaning and lightening cotton fabrics when washing laundry in the household.

Example 4:

Hey next grainy mix that is an effective When it comes to cleaning, it is found to contain chlorine bleach the increase in the degree of whiteness and in the case of lightening as very good;

7 io sodium tallow alkyl sulfate;

7 ⁰ Jo ijsodium linear dodecylbenzenesulfonate; "/ Ό sodium tripolyphosphate;
io sodium carbonate;
io sodium sulfate;
io potassium dichlorocyanurate;
0.5 io 7-phthalimiciinyl-3,6-dimethylcoumarin; 0.05 ° / o 7-Ph thai imidiny 1-4, b-dichiorcumarin; Rest. Moisture.

Example 5?

A liquid, builder-containing mixture for washing laundry that both brightens and cleanses, and which is suitable for washing fabrics commercially, can have the following composition:

6 io sodium 3-dodecylaminopropionate; 6 % sodium linear dodecylbenzenesulfonate; 20 ia potassium pyrophosphate;
8 ^c / o potassium toluenesulfonate;
3.8 io sodium silicate;

0.3 Ί » Garboxymethyl hydroxyethyl cellulose; 0.05 # 4,4'-lä-phthalimi-ainyl-2,2'-di stilbene sulfonic acid;

Rest water.

Example 6:

Another liquid builder washing and cleaning 909834/1521

Medium mixture, the phthalimidinyl derivatives according to the invention contains as optical brighteners, has the following composition:

6 % sodium linear dodecylbenzenesulfonate;

6 % ULmethyldoaecylamine oxide;

10 % trisodium ethane-l-hydroxy-ljl-diphosphonate;

10 % tripotassium nitrilotriacetate;

8 ^c yes potassium toluenesulfonate;

5.8 μb sodium silicate (ratio SiO ₂ : Na ₂ = 2: 1);

0.3 ^ sodium carboxymethyl cellulose; 0.20 # 2,5-DLphenyl-3-phthalimidinyl-N-methylpyrrole;

Rest water. M.

This detergent and cleaning agent mixture is at the Washing and lightening of iuinstharz-treated "wash and wear "cotton fabrics effectively.

Example 7:

A mixture for washing clothes in the household can contain the following ingredients:

10 % sodium salt of bO ^ -sulfonated tetradecene;

10 io mmethylkokosnuflalkylammonioacetat} · |

60 i » Trinat riumethhan-hydroiy tripho sp honat;

10% sodium carbonate;

0.10 f> 2.5-lÄ- (p-phenylsulfonamide) -3-phthalimidinyl furan;

Residual moisture.

This mixture both brightens and cleans and can be beneficial for washing super polyamide (nylon) fabrics are used.

Example 8:

An effective granular detergent and cleaning agent

909834/1521

mixture has the following composition

7.5 # sodium linear dodecylbenzenesulfonate;

2 i • sodium tallow alkyl sulfate;

2.2 i » hydrogenated marine oil fatty acid foam suppressor;

40 io ■ sodium tripolyphosphate;

20 # irisodium nitrilotriacetate;

10 # sodium silicate (ratio SiO ₂ : Na ₃ O β'2: 1)

13 <j6 sodium sulfate;

0.5.9t 4-phthalimidinyl-4'-methoxy-2,2'-distilbene sulfonic acid j

Rest water.
Example 9t

Another effective granular laundry detergent and cleaning agent has the following composition:

10 # sodium linear dodecylbenzenesulfonate;

10 io condensation product of 1 mole of nonylphenol and 12 moles of ethylene oxide;

10 io sodium tripolyphosphate j

30% trisodium ethane-l-hydroxy-ljl-diphosphonate;

10 io trisodium nitrilotriacetate;

. 6% sodium silicate (ratio SiO ₂ : Na ₃ O ■ 2 ί l);

"10 io trisodium phosphate;

0.5 io sodium carboxymethyl cellulose;

0.1 io sodium 4.4 ^l -diphthalimidinyl-2-isopropyl-2 ^l -. stilbene sulfonate;

0.2 io sodium 6-phthalimidinyl-2-naphthalenesulfonate; Residual moisture.

Example 10;

A lightening mixture for washing laundry, which is particularly effective on cotton fabrics and cold water temperatures is, has the following composition:

909834/1521

5 i » sodium tallow alkyl sulfate;

12 i » 3- (HfN-BLmethyl-N-dodecylammonio) -2-hydroxypropane-1-sulfonate;

5 $> sodium salt of bO, -sulfonated oc-tridecenj 3C ^ sodium tripolyphosphate;

20 i » irisodium nitrilotriacetate; IO96 sodium silicate (SiO ₂ : Na ₃ O = 1.6: 1) j

$ 10> sodium sulfate;

$ 0.3> sodium carboxymethylhydroxyethyloellulose}

0.1 # Sodium 4.4 ^L -di (3-chlorophthalimidinyl) -2-stilgendieulfonate; '

0.1 i » sodium 4-meth.yl-4 '- (3-chlorophthalimidinyl) -2-stilbene sulfonate}

Residual moisture.

Example 11:

Another cold water-effective, granular Gherliststoff mixture, di-e especially for plastic-treated cotton fabrics is effective has the following composition

5,96 sodium tallow alkyl sulfate;

5 i » 3- (N, N'-ItLmethyl-li-hexadeoylammonio) propane isulphonate;

10 $> DLmethyldodeoylphosphine oxide; 5 i » trisodium ethane-1-hydroxy-ll-diphoephonatj 10 i» trisodium nitrilotriacetatej 40 i> sodium tripolyphosphate;

10 9έ sodium silicate (Na ₃ O t SiO ₂ »1 t 2.5) J

0.3 ^ sodium carboxymethyl cellulose; 10 i> sodium sulfate;

0.3 i » 3-phthalimidinyl-2,5-di-m-chlorophenylfuran;

Residual moisture.

Aqueous and granular · bleaching mixtures are used illustrated by the following examples showing various approaches in which the mono- and DLphthalimidinyl-

909834/1521

derivatives can be used as optical brighteners according to the invention. However, BLe invention is not based on this Examples are limited for illustrative purposes only.

Example 12:

An excellent aqueous lead mixture that increases the whiteness of bleached textiles, can have the following composition:

5.2 fi sodium hypochlorite;

0.2 # sodium 4,4'-diphthalimidinyl-2,2-stilbene disulfonate;

Rest water.

Example 13:

An aqueous, bleaching mixture that works in improving the appearance of white and colored Tissues is effective, can have the following composition:

3.5 io potassium hypochlorite;

0.05 » 4,4'-lä.phthalimidinyl-2.2 ^l -stilbene disulfonamide;

Rest water.

Example 14:

An aqueous bleaching agent which gives an advantageous bleaching effect and whiteness improvement can have the following composition to have:

5.2 # sodium hypochlorite;

$ 0.05> 3-i ⁾ henyl-7-phthalimidinyl-coumarin;

Rest water.

909834/1521

Example 15t

A grainy, bleaching mixture that dissolves easily in an automatic household wax machine, can have the following composition

65 ^ Kali umdi chloro cyanurate;

6 ft sodium linear dodecylbenzenesulfonate} 25 i » potassium pyrophoaphatj

3 l. Sodium 4-phthalimidinyl ~ 4 ^l -methyl-2-stilbene sulfonate;

0.3 9 &moisture; {

Remainder sodium sulfate.

Example 16 »

A grainy, bleaching mixture that improves the appearance of bleached fabrics can be the following Composition have:

40 % sodium dichlorocyanurate;
10 # sodium tallow alkyl sulfate;
25 i » potassium tripolyphosphate;

1 i » N, N ^l -sodium 4-phthalimidinyl-4'-methoxy-2-stilbene sulfonate;

Remainder sodium sulfate.

909834/1521

Claims (5)

Patent claims? 1. Use of phthalimidinyl derivatives of the following general formula as optical brighteners in detergent compositions, which essentially from a mixture of an organic detergent and a salt of an alkaline builder in the ratio of about 5: 1 to about It20 and optionally about 0.5 to about 25 # of a bleach compound containing active chlorine contain: where in this formula a is in each case an integer from 1 to 4; χ zero or 1; A each represents a hydrogen atom, an alkyl group having 1 to about 10 carbon atoms, a halogen atom, a C 1-4 alkoxy group, an aryl group having 6 to about 12 carbon atoms, a C ₁ to about C 1 -C alkylsulfonyl, Co - Up to about C- · Q-alkoxyalkyl or a polyethyleneoxy radical of the formula H (CHpCHpO) _n -, where η is an integer from 1 to about 10, or a haloalkyl group with 1 to about 10 carbon atoms, an alkanoyl group with 2 to about 10 carbon atoms, a cyano or polyhydroxyalkyl group having 1 to about 10 carbon atoms, and Z, if χ = zero, is a monovalent radical which is obtained by eliminating a primary amino group from a fluorescent aromatic mono- or DLamine obtained by UV absorption in the range from 325 to 400 nm and fluorescence in the range from 90983Λ / 152 1 is characterized up to 475 nm; or, if = 1, is a divalent radical derived from a fluorescent aromatic BL-amine with the above-mentioned absorption and fluorescence spectral characteristics. 2. Use according to claim 1, characterized in that the optical brightener is a phthalimide derivative that in the general formula χ = zero and Z one of the following represents monovalent residues: (a) a 7-gumarin residue of the general formula: where A in each case has the meaning given above and ρ Is 1 or 2; (b) an S-naphthalene-ljB-carboximide radical of the general Formula: where A has the meaning given above, ρ is in each case 1 or 2 and R is a hydrogen atom, O ₁ - to C ^ - alkyl or Og - to 0 -, ^ - ArylTeBii } (o) a 4-stilbene radical of the general formula: 909834/1521 where a is in each case an integer from 1 to 4 and B has the same meaning as A or a radical -SOpOM or ^ -SO ₀ N represents, where M = a water atom or an alkali metal and R and R ^{1 are} each hydrogen atoms, C- to about C-alkyl radicals or part of a ring structure; (d) 4-stilbene radical of the general formula GH = CH B. wherein a, B and thus also M, furthermore R and R ^{1 have} the meaning given under (c); (e) a 3- (2,5-JÄaryl) -heterocyclua radical of the general Formula: ar ar wherein X is an oxygen atom or an FCH-z group, ar each a phenyl, naphthylsulfonate or phenyl group with 909834/1521 a substituent in the m-, p- or both in the m- as is also p-position, the substituents being chlorine atoms, Methoxy, sulfonate or DLalkylamino groups can be and the alkyl radicals of which each have 1 to about 4 carbon atoms sen; or (f) a 2-naphthyl radical of the general formula where ρ = 1 or 2 and each radical B has the meaning given for A or a radical -SOpOM or is », where M is a hydrogen atom or an alkali metal and R and R 'are hydrogen, C -, - to about C, -alkyl group or part of a ring structure. 3. Use according to claim 1, characterized in that that the optical brightener is a phthalimide derivative, in its general formula χ «1 and Z a bivalent Remainder of the general formula CH = CH represents, in which a is in each case an integer from 1 to 4 and B has the meaning given above for A or a radical _ _{s0 0M or} _ ₀ 0 _ο Ν ^ ^Ε atom or alkali metal and R and R ^{1 are} each hydrogen is where M «is a water 909834/1521 atoms »C - to C, -alkyl groups or part of a ring structure are. ' 4. Use according to one of claims 1 Ms 3t thereby characterized in that the composition is organic Detergent an anionic sulfate or sulfonate detergent • and ala alkaline G-builder Katriuintripolyphosphat or Contains sodium nitrilotriacetate. 5. Use according to claim 1, characterized in that the optical brightener 4 »4'-IUphthalimidinyl-stilbene-2,2'-disulfonamide, sodium-4-phthalimidinyl-4'-methoxy-ethylbene-2,2'-disulfonic acid or Disodium 4,4'-diphthalimidinyl stilbene-2,2 ^L -sulfonate is. For The Procter & Gamble Company 909834/1521