EP1335001A1 - Solid whitener preparations - Google Patents

Abstract

Particulate solid optical brightener composition comprises 81-99.45 wt.% of an optical brightener; 0.05-9 wt.% of a (poly)glycol with a b. pt. above 150 degrees C, a surfactant with a hydrophilic-lipophilic balance (HLB) below 12 and/or a 13-15C alkane sulfonate; and 0.5-18.95 wt.% moisture, the sum of these ingredients being more than 85 wt.% of the composition. Particulate solid optical brightener composition comprises: (a) 81-99.45 wt.% of an optical brightener; (b) 0.05-9 (0.1-5) wt.% of (i) a (poly)glycol with a b. pt. above 150 degrees C, especially di- or tripropyleneglycol, 4-8C alkane diol, or a polyglycol or diol with the a terminal group different from H, e.g. methoxy (ii) a surfactant with a hydrophilic-lipophilic balance (HLB) below 12 (below 10) and/or (iii) a 13-15C alkanesulfonate (especially as a sodium salt); and (c) 0.5-18.95 wt.% moisture. The sum of ingredients (a)-(c) is more than 85 wt.% (more than 95 wt.%) of the composition.

Description

The invention relates to solid preparations of optical brighteners, a method for their Manufacture and its use for the optical brightening of synthetic and natural materials.

Optical brighteners are today preferably in the form of aqueous liquid Formulations marketed, be it in the form of solutions or of Suspensions, also called slurries or slurries, which are usually from water-moist Press cake of the brightener by slurrying and if necessary loosening getting produced.

DE-A-27 15 864, for example, means "slurries" Suspensions of optical brighteners described by mixing the water-moist brightener press cake with dispersant and optionally Addition of electrolyte, organic extenders such as e.g. Urea as well Gelling agents are produced. However, these slurries are as in EP-A-385 374 is not stable over a long period of time. In EP-A-385 374 are therefore aqueous suspensions of the optical brighteners in the form their free acid or salts for use in liquid detergents, against by adding an anionic polysaccharide (thickener) Sedimentation can be stabilized. Similar, anionic polyhydroxy compounds Formulations containing the free acids of the optical brighteners are described in EP-A-835 906 described for use in paper. Have these suspensions however in view of their universal applicability in aqueous Brightening systems and their economic use in general and in particular Disadvantages for lightening paper pulp. So they have to Brightener crystals of a wet grinding to a particle size of <20 µm, undergo in particular <10 microns and the solubility in water is only achieved by adding alkali.

DE-A-27 15 864, on the other hand, describes the advantages with regard to dust behavior of slurries versus dry powder by drying and grinding of the wet presscakes are produced.

DE-A-35 23 207 describes low-dust solid brightener preparations for use described in textile dye baths, which are mixed by spray-dried optical brightener formulation with an aromatic carboxylic acid ester or fatty acid polyol esters and are characterized by good hot water solubility Mark (80 ° C). Such solid brightener preparations are however achievable in terms of their cold water solubility, dissolution rate Dissolution concentration and stability of concentrated stock solutions (e.g.> 4% by weight Brightener active) against crystalline precipitations still unsatisfactory, which is why e.g. for use as paper lightening preparations or in cold Textile dye baths are only suitable to a limited extent. In addition, the known solid Brightener preparations another i.A. insufficient storage stability. In particular they tend to clump after a few days, even in closed containers or are difficult to pour or meter.

DE-A-40 15 183 describes solid dye preparations, in particular reactive dyes, described with low dust behavior, which as a dedusting agent contain an alkanediol with 4 to 8 carbon atoms. These solid preparations contain in order to establish sufficient solubility up to 20% by weight on easily water-soluble agents and aids such as inorganic salts (e.g. Sodium sulfate), lignosulfonates or alkyl-substituted naphthalenesulfonic acid condensation products. As a result of the contents of the aids mentioned, the Dye content of the preparations at max. 80% by weight limited.

Such high amounts of, in particular, organic auxiliaries are in various areas of application for optical brighteners, such as in the Mass coloring of paper, in the sense of avoiding organic waste water loads and also undesirable for economic interests. In many applications optical brightener is also a very high solubility in water of the brightener active required, therefore the content of inorganic salts such as Sodium sulfate based on less than 2 wt .-%, in particular less than 0.5 wt .-% on the brightener ingredient.

a) 81 bis 99,45 Gew.-% wenigstens eines Aufhellerwirkstoffes,

b) 0,05 bis 9 Gew.-%, insbesondere 0,1 bis 5 Gew.-% bezogen auf die feste Präparation, wenigstens einer Verbindung aus der Gruppe

b1) der Glykole und/oder Polyglykole mit einem Siedepunkt oberhalb von 150°C, insbesondere Di- u/o Tripropylenglykol, Alkandiole mit 4 bis 8 C-Atomen und/oder Polyglykole oder Diole mit endständigen von Wasserstoff verschiedenen Gruppen, vorzugsweise Methoxygruppen,

b2) der oberflächenaktiven Verbindungen mit einem HLB-Wert von weniger als 12, insbesondere weniger als 10, und/oder

b3) der Alkylsulfonate mit einer mittleren Kohlenwasserstoffkettenlänge von C₁₃ bis C₁₅, vorzugsweise deren Natriumsalze und

c) 0,5 bis 18,95 Gew.-%, insbesondere 1 bis 16 Gew.-% Restfeuchte,
dadurch gekennzeichnet, dass die Summe der Komponenten a), b) und c) >85 Gew.-%, bevorzugt >90 Gew.-% und insbesondere >95 Gew.-% bezogen auf die feste Präparation beträgt, hervorragend lagerstabil sind.

Surprisingly, it has now been found to contain solid, particular brightener preparations

a) 81 to 99.45% by weight of at least one brightening agent,

b) 0.05 to 9% by weight, in particular 0.1 to 5% by weight, based on the solid preparation, of at least one compound from the group

b1) the glycols and / or polyglycols with a boiling point above 150 ° C., in particular di- and / or tripropylene glycol, alkanediols with 4 to 8 carbon atoms and / or polyglycols or diols with terminal groups other than hydrogen, preferably methoxy groups,

b2) the surface-active compounds with an HLB value of less than 12, in particular less than 10, and / or

b3) the alkyl sulfonates with an average hydrocarbon chain length of C ₁₃ to C ₁₅ , preferably their sodium salts and

c) 0.5 to 18.95% by weight, in particular 1 to 16% by weight, of residual moisture,
characterized in that the sum of components a), b) and c) is> 85% by weight, preferably> 90% by weight and in particular> 95% by weight, based on the solid preparation, is outstandingly stable in storage.

The groups b1), b2) and b3) are of course different from one another.

The brightener preparations according to the invention have a very high solubility and Dissolving speed in cold and hot water and also excel Concentrations above 5 wt .-% by a very good stability against crystalline precipitates.

Even with significant residual moisture, the solid brightener preparations also have with longer storage a low tendency to clump and good flowability, so that they are easy to dose as solids.

The dust filter value is determined using a method such as that described in "Berger-Schunn et al, determination of the dust behavior of dyes, textile finishing 24 (1989), 7/8, pp. 277-280 ". Here, the occurring Dust is sucked off through a filter and the amount of the filter covering is determined visually. A filter value of 1 means high dust generation, a filter value of 5 means that a dust deposit is not visible on the filter and that it is a very dust-free product.

The solid brightener preparations according to the invention preferably have one high content of optical brightening agent and are preferably largely free of unwanted inorganic or organic components such as Setting and blending agents. They are preferably X-ray amorphous solids. she are preferably free from crystalline brightener particles, in particular hydrate crystals. They are therefore for continuous and discontinuous brightening of synthetic or natural materials such as Fiber materials, detergents and especially of paper in the mass and in the surface very well suitable.

The invention further relates to the use of the solid according to the invention Brightener preparations for whitening natural and synthetic Materials, especially textiles, paper and detergents, especially from aqueous pulp mixtures (paper in bulk), paper coating slips or Papierleimpressenflotten. The use is preferably characterized in that that the solid brightener preparation either yourself or if necessary after mixing with water in an aqueous cellulose mixture, paper coating slip or size press liquor is introduced.

The invention therefore also relates to a method for optically brightening Paper in bulk and / or surface in which the solid brightener preparation continuously or discontinuously, preferably continuously, with a Concentration of 0.01 to 40 wt .-% based. to component a), in particular 1 up to 25% by weight at a temperature of 10 to 75 ° C, in particular 15 to 55 ° C, and a pH of 6.0 to 12, in particular 6.5 to 11, very particularly 6.5 to 9.5, is preferably completely dissolved, and so or undiluted in the form of the solid Preparation itself in the aqueous cellulose mixture, dilution water, size press or film press fleet and / or paper coating slip is introduced.

worin

R¹, R² und R³

unabhängig voneinander Phenoxy; mono- oder disulfoniertes Phenoxy; Phenylamino; mono- oder disulfoniertes Phenylamino; Phenylamino substituiert durch C₁-C₃-Alkyl, Cyano, Halogen, COOR, CONH-R, NH-COR, SO₂NH-R, O-R; Morpholino; Piperidino; Pyrrolidino; -OC₁-C₄-Alkyl; -NH(C₁-C₄-Alkyl); -N(C₁-C₄-Alkyl)₂; -NHC₂-C₄-Alkylen-OR; -N(C₂-C₄-Hydroxyalkyl)₂; -NHC₂-C₄-Alkylen-O-C₂-C₄-Alkylen-OR; eine Aminosäure oder ein Aminosäureamid, von deren Aminogruppe ein Wasserstoffatom entfernt wurde; -NHCH₂CH₂OH; -N(CH₂CH₂OH)₂; -N(CH₃)(CH₂CH₂OH); -NH₂; -OCH₃; -S-C₁-C₄-Alkyl; -S-Aryl; -Cl; -NH-CH₂CH₂SO₃H; -N(CH₂CH₂SO₃H)₂ oder -N(CH₂CH₂OH)CH₂CH₂CONH₂ bedeuten, und

R

H oder C₁-C₃-Alkyl und M den Rest eines Alkali-, Erdalkali, Ammoniumoder Aminsalzes bedeutet. Unter Aminsalzionen sind solche der Formel H⊕NR⁴R⁵R⁶ bevorzugt, in denen R⁴, R⁵ und R⁶ unabhängig von einander Wasserstoff, Alkyl, Alkenyl, Hydroxyalkyl, Cyanoalkyl, Halogenalkyl oder Phenylalkyl bedeuten oder worin R⁴ und R⁵ zusammen die Ergänzung zu einem 5 bis 7-gliedrigen gesättigten Stickstoffheterozyklus darstellen, der noch zusätzlich ein Stickstoff- oder Sauerstoffatom als Ringglied enthalten kann, beispielsweise einen Piperidin, Piperazin, Pyrrolidin-, Imidazolin- oder Morpholinring, während R⁶ für Wasserstoff steht.

Insbesondere bedeuten R¹, R² und R³ unabhängig voneinander -NH₂, -NH-CH₃, -NH-C₂H₅, -N(CH₃)₂, -N(C₂H₅)₂, -NH-CH₂CH₂OH, -NH-C₂-C₄-Hydroxyalkyl, -N(C₂-C₄-Hydroxyalkyl)₂-NH-CH₂CH₂SO₃H; -NH-CH₂-CH₂-O-CH₂-CH₂-OH, -OCH₃, -OCH(CH₃)₂, -O-CH₂-CH₂-O-CH₃, -N(CH₂-CH₂-OH)₂, -N(CH₂-CHOH-CH₃)₂, Morpholino, -SCH₃, -N(CH₂-CH₂-OH)CH₂-CH₂-CONH₂ sowie einen der nachstehenden Reste

The optical brighteners of component a) are preferably compounds from the group of 4,4'-bis (triazinylamino) -stilbene-2,2'-disulfonic acids, 4,4'-bis (triazol-2-yl) -stilbene -2,2'-disulfonic acids, 4,4'-dibenzofuranyl biphenyls, 4,4 '- (diphenyl) -stilbenes, bis- (benzoxazol-2-yl) derivatives, bis- (benzimidazol-2-yl) - derivatives, coumarins, pyrazolines, naphthalimides, triazinyl-pyrenes, 2-styryl-benzoxazoles or -naphthoxazoles, benzimidazole-benzofurans or -oxanilides. These are preferably brighteners from the group of the compounds containing sulfo and / or carboxyl groups, in particular from the group of stilbene compounds, very particularly distilbenes and triazinylflavonates of the general formula (I)

wherein

R ¹ , R ² and R ³

independently phenoxy; mono- or disulfonated phenoxy; phenylamino; mono- or disulfonated phenylamino; Phenylamino substituted by C ₁ -C ₃ alkyl, cyano, halogen, COOR, CONH-R, NH-COR, SO ₂ NH-R, OR; morpholino; piperidino; pyrrolidino; -OC ₁ -C ₄ alkyl; -NH (C ₁ -C ₄ alkyl); -N (C ₁ -C ₄ alkyl) ₂ ; -NHC ₂ -C ₄ alkylene-OR; -N (C ₂ -C ₄ hydroxyalkyl) ₂ ; -NHC ₂ -C ₄ alkylene-OC ₂ -C ₄ alkylene-OR; an amino acid or an amino acid amide from whose amino group a hydrogen atom has been removed; -NHCH ₂ CH ₂ OH; -N (CH ₂ CH ₂ OH) ₂ ; -N (CH ₃ ) (CH ₂ CH ₂ OH); -NH ₂ ; -OCH ₃ ; -SC ₁ -C ₄ alkyl; -S-aryl; -Cl; -NH-CH ₂ CH ₂ SO ₃ H; -N (CH ₂ CH ₂ SO ₃ H) ₂ or -N (CH ₂ CH ₂ OH) CH ₂ CH ₂ CONH ₂ , and

R

H or C ₁ -C ₃ alkyl and M represents the remainder of an alkali, alkaline earth, ammonium or amine salt. Preferred amine salt ions are those of the formula H⊕NR ⁴ R ⁵ R ⁶ in which R ⁴ , R ⁵ and R ⁶ independently of one another are hydrogen, alkyl, alkenyl, hydroxyalkyl, cyanoalkyl, haloalkyl or phenylalkyl or in which R ⁴ and R ⁵ together represent the addition to a 5 to 7-membered saturated nitrogen heterocycle which may additionally contain a nitrogen or oxygen atom as a ring member, for example a piperidine, piperazine, pyrrolidine, imidazoline or morpholine ring, while R ^{6 is} hydrogen.

In particular, R ¹ , R ² and R ³ independently of one another denote -NH ₂ , -NH-CH ₃ , -NH-C ₂ H ₅ , -N (CH ₃ ) ₂ , -N (C ₂ H ₅ ) ₂ , -NH -CH ₂ CH ₂ OH, -NH-C ₂ -C ₄ -hydroxyalkyl, -N (C ₂ -C ₄ -hydroxyalkyl) ₂ -NH-CH ₂ CH ₂ SO ₃ H; -NH-CH ₂ -CH ₂ -O-CH ₂ -CH ₂ -OH, -OCH ₃ , -OCH (CH ₃ ) ₂ , -O-CH ₂ -CH ₂ -O-CH ₃ , -N (CH ₂ -CH ₂ -OH) ₂ , -N (CH ₂ -CHOH-CH ₃ ) ₂ , morpholino, -SCH ₃ , -N (CH ₂ -CH ₂ -OH) CH ₂ -CH ₂ -CONH ₂ and one of the following leftovers

Preferred amino acid residues derive e.g. from glycine, sarcosine, β-alanine, Aspartic acid or iminodiacetic acid.

M is preferably H, Na, Li, K, Ca, Mg, ammonium or ammonium, which is mono-, di-, tri- or terasubstituted by C ₁ -C ₄ alkyl, C ₂ -C ₄ hydroxyalkyl or a mixture it.

R¹ und R²

für -N(CH₂-CH₂-OH)₂ und

R³

für

stehen und

M

die obige Bedeutung hat, insbesondere für Na⁺ oder K⁺ steht.

Optical brighteners of the formula (I) in which

R ¹ and R ²

for -N (CH ₂ -CH ₂ -OH) ₂ and

R ³

For

stand and

M

has the above meaning, in particular stands for Na ⁺ or K ⁺ .

Optical brighteners from the distilbene series, such as them, can also be used are described for example in EP-A-0 385 374, and cationic brighteners. Brighteners may also be used, which are obtained by cationizing anionic ones, in particular brighteners containing sulfo and / or carboxyl groups, for example by means of polymeric quaternary ammonium compounds. Such Brighteners are e.g. in WO-A-9967317.

The compounds of component b) are preferably water-miscible or water-soluble compounds with a boiling point above 150 ° C, in particular above 250 ° C. Water-soluble is understood to mean that the compounds a solubility in water at room temperature of> 1 g / 1, in particular > 5 g / l. Water-miscible is understood to mean that the compounds in a concentration of> 5 g / l, in particular> 10 g / l at room temperature Do not separate water.

Glycols of comp. B1) are preferably understood to be vic. Diols and / or 1,2-diols, such as, for example, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, and in particular tripropylene glycol. Alkanediols with 4-8 C atoms, such as 1,3-butylene glycol, 1,4-butanediol, hexylene glycol, 2-methyl-1,3-propanediol and neopentyl glycol, are particularly preferred. Possible components b1) are furthermore optionally substituted diols, for example diols substituted by C ₁ -C ₄ -alkyl, aryl, halogen or SO ₃ .

Polyglycols of component b1) are preferably polyethylene or polypropylene glycols and their copolymers and block copolymers understood with a molecular weight of less than 1000 g / mol, in particular less than 800 g / mol.

Particularly preferred polyglycols and diols of component b1) are those Compounds with terminal groups other than hydrogen, in particular Methoxy groups, e.g. Polyethylene glycol methyl ether and dimethyl ether with a molecular weight of <1000 g / mol, preferably <500 g / mol.

i) gesättigten und/oder ungesättigten Fettalkoholen mit 6 bis 25 C-Atomen oder

j) Alkylphenolen mit 4 bis 12 C-Atomen im Alkylrest oder

k) gesättigten und/oder ungesättigten Fettaminen mit 14 bis 20 C-Atomen oder

l) gesättigten und/oder ungesättigten Fettsäuren mit 14 bis 22 C-Atomen oder

m) hydrierten und/oder unhydrierten Harzsäuren,

n) aus natürliche oder modifizierte, gegebenenfalls hydrierte Rizinusölfettkörper hergestellte Veresterungs- und/oder Arylierungsprodukte, die gegebenenfalls durch Veresterung mit Dicarbonsäuren zu wiederkehrenden Struktureinheiten verknüpft sind.

The surface-active agents of comp. B2) are preferably so-called wetting agents, as described for example in Stache, " Tensid Handbuch", 2nd edition, Carl Hanser Verlag Munich Vienna 1981, p.205, in the form of non-ionic or aniogenic compounds with an HLB Value (hydrophilic-lipophilic balance) of less than 12, in particular less than 10. The surface-active agents of component b2) are selected in particular from the group of the reaction products of alkylene oxides with alkylatable compounds, such as, for example, fatty alcohols, fatty amines, fatty acids, phenols, Alkylphenols, carboxamides and resin acids. These are, for example, alkylene oxide adducts from the class of the reaction products of ethylene oxide and / or propylene oxide with:

i) saturated and / or unsaturated fatty alcohols with 6 to 25 carbon atoms or

j) alkylphenols with 4 to 12 carbon atoms in the alkyl radical or

k) saturated and / or unsaturated fatty amines with 14 to 20 carbon atoms or

l) saturated and / or unsaturated fatty acids with 14 to 22 carbon atoms or

m) hydrogenated and / or unhydrogenated resin acids,

n) esterification and / or arylation products which are produced from natural or modified, optionally hydrogenated castor oil fatty substances and which are optionally linked to recurring structural units by esterification with dicarboxylic acids.

Surface-active agents of component b2) with a medium agent are preferred Molecular weight of 500 to 3000 g / mol, in particular 500 to 1500 g / mol Basis of the compounds i) to l) by mixed and / or blockwise Reaction with ethylene and propylene oxide can be obtained; particularly preferred they contain a final (poly) propylene oxide block with 1 to 10, preferably 2 to 8 mole units of propylene oxide.

Further preferred compounds of component b3) are those from the group of the alkyl sulfonates of the general formula Z- SO ₂ -OH with Z = alkane, cycloalkane, alkene, especially paraffin,
as well as their salts in question.

These are preferably technical mixtures of the sodium salts of various alkanesulfonates with an average hydrocarbon chain length of C ₁₃ to C ₁₅ . These compounds can also contain up to 1% by weight of organically bound chlorine.

Components b1) to b3) can be used alone or in combination with one another be used.

Furthermore, in combination with the compounds b1) to b3) mentioned Dicarboxylic acid esters and their mixtures are used. Are preferred Dimethyl ester of glutaric, adipic and / or succinic acid.

The solid brightener preparations according to the invention contain as component c) Water in the form of residual moisture. Under residual moisture, the amount of water is as Moisture, based on the solid preparation, understood, including free Water, trapped water and adsorbed water, not crystal water (i.e. water stoichiometrically integrated in a crystal structure) or constitutional water [see Widmann, Riesen: "Thermoanalyse", Hüthigverlag, Heidelberg 1984]. The solid brightener preparations according to the invention are preferably X-ray amorphous.

If necessary, the solid brightener preparations can contain other auxiliaries, preferably in an amount of less than 10% by weight, based on the preparation, contain; as such e.g. to name formulation aids such as adjusting agents, Blending agents, other surface-active agents, and / or defoamers, and organic thickeners (protective colloids), preservatives, and electrolytes. However, the solid brightener solutions preferably contain from ecological Only very small proportions of other organic additives (auxiliaries, Impurities), in particular less than 5% by weight, based on brightener a), very particularly less than 2 wt .-%.

The electrolyte is sodium chloride, sodium sulfate, sodium carbonate, or one of the corresponding potassium salts or mixtures of the substances mentioned. The Amount of electrolyte can be 0.001 to 2 wt .-% based on the total weight of the solid preparation, in particular 0.001 to 0.5 wt .-%.

A) sulfonierten Aromaten

B) Aldehyden und/oder Ketonen und gegebenenfalls

C) einer oder mehrerer Verbindungen aus der Gruppe der nicht sulfonierten Aromaten, Harnstoff und Harnstoffderivaten enthalten.

In particular, the solid brightener preparations according to the invention can contain formulation auxiliaries of component d), preferably 0.1 to 5% by weight, based on the solid preparation of at least one condensation product based on

A) sulfonated aromatics

B) aldehydes and / or ketones and optionally

C) one or more compounds from the group of unsulfonated aromatics, urea and urea derivatives.

As sulfonated aromatics of Comp. A) are also in the context of this application understood sulfomethylated aromatics. Preferred sulfonated aromatics are: Naphthalenesulfonic acids, phenolsulfonic acids, dihydroxybenzenesulfonic acids, sulfonated Ditolyl ether, sulfomethylated 4,4'-dihydroxydiphenyl sulfone, sulfonated diphenylmethane, sulfonated biphenyl, sulfonated hydroxybiphenyl, especially 2-hydroxybiphenyl, sulfonated terphenyl or benzenesulfonic acids.

Aldehydes and / or ketones of component B) include, in particular, aliphatic, cycloaliphatic as well as aromatic in question. Aliphatic are preferred Aldehydes, with particular preference formaldehyde and other aliphatic aldehydes with 3 to 5 carbon atoms.

Examples of unsulfonated aromatics of component C) are phenol, Cresol, 4,4'-dihydroxydiphenylsulfone or dihydroxydiphenylmethane in question.

As urea derivatives, for example, dimethylol urea, melamine or Guanidine can be called.

A) wenigstens einem sulfonierten Aromaten, ausgewählt aus der Gruppe von Phenolsulfonsäuren, Dihydroxybenzolsulfonsäuren, sulfomethyliertes 4,4'-Dihydroxydiphenylsulfon, sulfoniertes Diphenylmethan, sulfoniertes Biphenyl, sulfoniertes Hydroxybiphenyl, insbesondere 2-Hydroxybiphenyl, sulfoniertes Terphenyl und Benzolsulfonsäuren, insbesondere Naphthalinsulfonsäuren und sulfonierte Ditolylether,

B) Formaldehyd und gegebenenfalls

C) einer oder mehreren Verbindungen, ausgewählt aus der Gruppe von Phenol, Kresol, 4,4'-Dihydroxydiphenylsulfon, Dihydroxydiphenylmethan, Harnstoff, Dimethylolharnstoff, Melamin und Guanidin

eingesetzt.The preferred condensation product of component d) is one based on

A) at least one sulfonated aromatic, selected from the group of phenolsulfonic acids, dihydroxybenzenesulfonic acids, sulfomethylated 4,4'-dihydroxydiphenyl sulfone, sulfonated diphenylmethane, sulfonated biphenyl, sulfonated hydroxybiphenyl, especially 2-hydroxybiphenyl, sulfonated terphenyl acids and benzenesulfonyl sulfonic acids, especially benzenesulfonyl sulfonic acids,

B) formaldehyde and optionally

C) one or more compounds selected from the group of phenol, cresol, 4,4'-dihydroxydiphenylsulfone, dihydroxydiphenylmethane, urea, dimethylolurea, melamine and guanidine

used.

The condensation product preferably obtained in the condensation preferably has an average degree of condensation of 1 to 150, particularly preferred from 1 to 20, in particular from 1 to 5.

The condensation products of component d) can be in the form of an aqueous solution or Suspension or as a solid, for example as a powder or granules, preferably as spray-dried powder or granules.

Preferred condensation products of component d) have an inorganic one Salinity below 10% by weight, preferably below 5% by weight, in particular below 1 wt .-%, based on the aqueous solution or suspension used Component or based on the solid of component d) used.

It is also preferred to have residual monomer-low to residual monomer-free condensation products to use component d).

"Low monomer" means a residual monomer content of less than 30% by weight, preferably less than 20 wt .-%, based on the condensation product, in particular <10% by weight, preferably <5% by weight. Among residual monomers in this context are used to produce the condensation product understood reactants used.

Such low salt and low residual monomer condensation products are for example known from EP-A 816 406.

The condensation products of component d) can be produced in this way, for example that the sulfonated aromatics of component A) optionally in a mixture with unsulfonated aromatics of component C) by reacting the underlying aromatics with a sulfonating agent preferably sulfuric acid, especially concentrated sulfuric acid, chlorosulfonic acid, Amidosulfonic acid or oleum.

1 mol of the aromatics on which component A) is based are preferred 0.4 to 3.2 mol, in particular 0.8 to 1.6 mol, of sulfonating agent are used.

The condensation then takes place with aldehydes and / or ketones of the components B), preferably formaldehyde, optionally together with others Compounds of component C). The condensation is preferably carried out in aqueous Solution at a pH of 0 to 9. Here, preferably per mol of sulfonated aromatics A) or per mole of a mixture of sulfonated aromatics of component A) and unsulfonated aromatics of component C) 0.4 to 1.5 mol, in particular 0.4 to 1.0 mol of component B) are used.

This may be followed by the neutralization of the sulfonic acid condensation product component d) with a base.

The separation of the inorganic acid or its salts and the reduction the residual monomer content can, for example, by means of membrane separation processes be performed. The preferred membrane separation processes are Ultrafiltration, diffusion dialysis or electrodialysis in question.

Those used in membrane separation processes, preferably in ultrafiltration In a preferred embodiment, membranes have a molecular weightcut-off (MWCO) from 1,000 to 10,000 daltons.

The separation of the inorganic acid using a membrane separation process is preferably carried out by diafiltration with acid-stable ultra or Cross-flow filtration nanofiltration membranes. As suitable membranes Examples include polyhydantoin membranes such as those found in EP-A 65 20 44 are known.

Preferred membranes for this purpose have a MWCO level of 2,000 to 10,000 daltons. If necessary, concentration is carried out simultaneously in this process step.

In a particular embodiment, the solid brightener preparations according to the invention also contain inorganic solids, such as, for example, layered silicates, optionally hydrophobized highly dispersed, amorphous pyrogenic silicas, highly dispersed silica sols such as bentonite or montmorillonite, very finely divided, optionally hydrophobicized kaolin or highly dispersed aluminum oxide; In particular, component d) has a specific surface area [BET method] of 2 to 1,500, preferably 10 to 800 m ² / g.

The solid brightener preparations can also contain organic protective colloids contain.

Suitable protective colloids are those from the group of anionic or nonionic organic water-soluble polymers. Particularly preferred are organic thickeners that have a solubility in water of> 100 g / l have.

A compound is preferably used as the organic thickener, whose 4% aqueous solution has a viscosity of ≥2 mPa.s at 20 ° C.

• Dextrine oder Cyclodextrine,
• Stärke und Stärkederivate, insbesondere abgebaute oder teilabgebaute Stärke,
• anionische Polyhydroxyverbindungen, insbesondere Xanthan oder Carboxymethylcellulose
• Cellulosederivate wie z.B. Methylcellulose, insbesondere Hydroxymethyl-, Hydroxyethyl- oder Hydroxypropylcellulose,
• partiell hydrolysierte Polymerisate von Vinylacetat, vorzugsweise Polyvinylalkohol, die zu mehr als 70 % hydrolysiert sind und/oder Vinylalkohol-Copolymerisate, vorzugsweise Copolymere aus Vinylacetat und Alkylvinylester, die partiell oder vollständig verseift sind, sowie Polyinylalkohol selbst,
• Polymerisate von N-Vinylpyrrolidon, oder Copolymerisate mit Vinylestern,
• Polyacrylamide (vorzugsweise nicht ionisch oder anionisch).

Preferred organic thickeners are compounds selected from the following groups:

• Dextrins or cyclodextrins,
• Starch and starch derivatives, especially degraded or partially degraded starch,
• anionic polyhydroxy compounds, especially xanthan or carboxymethyl cellulose
• Cellulose derivatives such as methyl cellulose, especially hydroxymethyl, hydroxyethyl or hydroxypropyl cellulose,
• partially hydrolyzed polymers of vinyl acetate, preferably polyvinyl alcohol, which are more than 70% hydrolyzed and / or vinyl alcohol copolymers, preferably copolymers of vinyl acetate and alkyl vinyl ester, which are partially or completely saponified, and also polyvinyl alcohol itself,
• Polymers of N-vinylpyrrolidone, or copolymers with vinyl esters,
• Polyacrylamides (preferably non-ionic or anionic).

Starch, derivatized starch and in particular are preferred as thickeners degraded starch in question.

Polysaccharides, in particular, come as preferred anionic polyhydroxy compounds Xanthan and carboxymethyl cellulose in question.

As cellulose derivatives, methyl cellulose, Hydroxymethyl cellulose, hydroxyethyl and propyl cellulose can be used.

Manufacture of solid brightener preparations:

The brighteners of component a), in particular of the general formula (I), are either known or can be prepared by methods known per se and are usually as free acid or as its salts, preferably alkali metal salts used.

The solid brightener preparations are preferably produced by Drying a concentrated solution of the brightener described for the component a) optionally together with the auxiliary substances mentioned. In particular can at least part of component b) and / or d) of the concentrated solution of the brightener (Comp. a)) are added before drying, which is the Advantage of an improved dissolving stability at higher brightener concentrations Possesses drying; at least a part of Comp. b) can, however, also after the Drying can be added as a dedusting agent.

The invention also includes a method of making the solid Brightener preparations, in which the optical brighteners of Comp. A) are preferred in solid form as finished or unfinished powder, granules or especially as a water-moist press cake in an aqueous medium optionally together with at least part of comp. b) and / or d) as well as any other additives completely dissolves and then dries.

An aqueous medium is preferably used which has a pH of 6.5 to 12, in particular from 7.5 to 12. Generally a temperature from 15 to 98 ° C, preferably from 40 to 98 ° C, in particular from 60 to 95 ° C for Achieved a complete solution. If necessary, clarification filtration the solution to separate unwanted by-products (e.g. triazines) to be required.

Following this, the aqueous solution is preferably adjusted to a pH of 6.5 to 10, in particular 7.5 to 9.5, and by drying in the invention solid brightener preparation transferred. As a suitable process for the Drying is in particular spray drying, preferably single-component spray drying using high pressure or swirl chamber nozzles or spray drying using atomizing disks, Freeze drying with upstream or downstream granulation or dry processing, build-up granulation for example after the plate or Drum granulation process, optionally with partially pre-dried product, Fluid bed drying and granulation, mixer agglomeration and drying optionally in combination with fluidized bed or fluid bed drying call. Methods such as mixed agglomeration in suspension may also be used downstream fluidized bed or fluid bed drying, granulation by means of paste deformation and subsequent post-drying and crushing or pelleting and steam jet agglomeration in question. Combinations of the above Procedures are also possible.

Spray drying processes using high-pressure or swirl chamber nozzles, spray drying with integrated and / or downstream Fluid bed agglomeration and / or drying, the build-up granulation using the plate process and fluid bed granulation and drying.

In particular, the solid brightener preparations produced by these processes have a residual moisture content of 0.5 to 18.95% by weight, in particular 1 to 16% by weight, based on the solid preparation, and an average volume-based Particle size from 5 to 5000, preferably 15 to 2000 and in particular 40 to 1000 µm. The solid brightener preparations according to the invention are based preferably on a spherical or spherical shape or derived therefrom Particle structure. Agglomerates of particles also come from the mentioned forms in the range of the specified particle size in question. According to the invention can the solid brightener preparations powder, granules or so-called microgranules (e.g. from single-component nozzle spray drying).

After drying, the solid preparations can also be used known methods worked up, in particular dusted. The dedusting can be used directly in connection with drying e.g. as injection or Aerosol dedusting as well as after drying, for example in one Mixer done.

According to the invention, at least some of the compounds of the Components b1) to b3) used as the sole dedusting agent. in principle However, additional dedusting agents can also be used.

As such come both water soluble or water miscible as well water-insoluble or poorly soluble compounds. Such funds are on known; Examples of water-soluble polyethylene glycols and PEG block copolymers.

Preferred additional sparingly soluble dedusting agents are mentioned White oils and aromatic or aliphatic alkyl esters boiling above 150 ° C.

The solid brightener preparations according to the invention are optical brighteners for different substrates. Are particularly preferred on natural cellulose-based substrates such as Cotton, paper and wood pulp in fine distribution, or materials made from regenerated cellulose, from wool, or to name synthetic polyamides. The materials to be optically brightened can be in various processing conditions such as raw material, semi-finished product or finished product and in various processing forms such as Fibers, threads, fabrics, knitted fabrics, nonwovens and foils etc. are present.

With regard to the use of solid brightener preparations for optical Brighten natural and synthetic materials in aqueous liquors or Media there is no restriction according to the invention. The use concerns hence the lightening of textiles using known dyeing processes and their application for brightening detergents.

In particular, the solid brightener preparations according to the invention can solid and / or liquid detergents are added, which are the usual state of the art Technically appropriate ingredients contain.

The solid brightener preparations according to the invention can still be used during the refinement of the fiber materials in connection with synthetic resins and synthetic resin precondensates muster. The crosslinking of synthetic resins can be done in a wide range pH range, in particular from pH 1 to pH 10, carried out in a conventional manner become.

Furthermore, the compounds of the invention can be used to To increase the sun protection factor of textile materials.

To increase the sun protection factor of the textile materials, the textile Material treated directly with the solid brightener preparations according to the invention or the effect is achieved in the context of normal household laundry, if the detergent used is the solid brightener preparation according to the invention contains.

In particular, relates to the use of the solid brightener preparations according to the invention the lightening of masses of paper during paper production ("mass coloring"), e.g. Pulp, chemical and mechanical pulp, lightening of the coating slips commonly used in the paper industry, namely that Lightening of unfilled, but especially filled, paper pulp and pigmented coating slips, as well as the lightening of paper in the glue or Film press.

The use for the optical brightening of paper is preferably thereby characterized in that the solid brightener preparation according to the invention either itself or optionally after mixing and dissolving with water in an aqueous Cellulose mixture, paper coating slip or size press liquor is introduced.

When used in the pulp, the dissolving process can take place during or during the Feed into the pulp mixture and / or in the pulp mixture itself take place, whereby it should be ensured that the dissolving process before the paper sheet formation is fully completed.

Use in bulk coloring or surface coating is particularly preferred, which is preferably characterized in that the solid brightener preparation continuously or discontinuously, preferably continuously, with a concentration of 0.01 to 40 wt .-%, based. to component a), in particular 1 to 25 wt .-% at a temperature of 10 to 75 ° C, in particular 15 to 55 ° C, and a pH of 6.0 to 12, especially 6.5 to 11, very particularly 6.5 to 9.5, preferably completely dissolved and in an aqueous pulp mixture, Paper coating slip or size press fleet is introduced.

In the case of mass staining, a concentrated or dilute solution of the solid Lightening preparation of the paper pulp at every stage of the paper manufacturing process be added before leaf formation.

Continuous means that the brightener preparation in the Desired concentration, based on the mass of paper pulp, continuously the paper pulp is added; this advantageously takes place in the both the solid brightener preparation and water in a certain ratio for brightener preparation, for example in an agitator tank or in a pipeline, continuously brought together, the optical Brightener is suspended and preferably dissolved and the i.A. concentrated Solution of the material flow or the dilution water in the desired Ratio is metered.

The invention further relates to coating slips for optically brightening paper containing the brightener preparations according to the invention.

The preferred coating slips contain, for example, binders and the like. Plastic dispersions based on copolymers of butadiene-styrene, Acrylonitrile butadiene styrene, acrylic acid esters, ethylene vinyl chloride or ethylene vinyl acetate or based on homopolymers, such as polyvinyl chloride, Polyvinylidene chloride, polyethylene, polyvinyl acetate or polyurethanes. On preferred binder consists of styrene-butyl acrylate or styrene-butadiene-acrylic acid copolymers. Further polymer latices are described, for example, in US Pat. 3,265,654.

Aluminum silicates, such as, are usually used to pigment the coating slips China clay and kaolin, also barium sulfate, satin white, titanium dioxide or natural or precipitated calcium carbonate.

The coating slips according to the invention preferably contain 5 to 75% by weight. at least one white pigment. The binder is preferably in a Amount used that is sufficient for the dry content of polymeric compound 1 makes up to 30 wt .-%, preferably 5 to 25 wt .-% of the white pigment. The Amount of the solid brightener preparation to be used according to the invention calculated such that the brightener of component a) in amounts from 0.005 to 2% by weight, in particular 0.01 to 1.5% by weight, based on white pigment, is present.

The coating slips according to the invention can be prepared by the components in any order at temperatures from 10 to 100 ° C, preferably 20 to 80 ° C, mixes. The components here also include usual aids used to regulate the rheological properties, such as Viscosity or water retention, the coating slips are used can. Such tools are e.g. natural binders such as starch, casein, Protein or gelatin, cellulose ethers, such as carboxyalkyl cellulose or hydroxyalkyl cellulose, Alginic acid, alginates, polyethylene oxide or polyethylene oxide alkyl ether, Copolymers of ethylene oxide and propylene oxide, polyvinyl alcohol, Polyvinylpyrrolidone, water-soluble condensation products with formaldehyde Urea or melamine, polyphosphates or polyacrylic acid salts.

The solid brightener preparations according to the invention are either in the finished Spread or incorporated into one of the components of the spread. The solid preparations can be added directly or in the form of aqueous solutions are added. Aqueous solutions may be used continuously manufactured and in the process of the so-called intermediate step continuously introduced.

The coating slips containing the brightener preparations according to the invention can be used to coat cellulose-based materials, especially paper, Wood, foils, e.g. Cellulose, cellulose triacetate, cotton fabrics etc. be used. Use on paper, cardboard and is particularly preferred Cardboard as well as photo paper.

The coating slips of the invention can be applied to the substrate by any conventional methods are applied, for example with an air knife, a doctor knife, a brush, a roller, a squeegee or a stick, on which then the coating e.g. with an infrared dryer, hot air dryer and / or Contact dryer at temperatures of the substrate surface in the range of 60 to 200 ° C, preferably from 90 to 130 ° C, except for a residual moisture of 3 to 6% by weight is dried.

By using the solid brightener preparations according to the invention the coatings obtained are further characterized by an optimal Distribution of the optical brighteners over the entire surface and thereby one conditional increase in whiteness as well as high light fastness.

The solid brightener preparations according to the invention can be used for surfaces used in the usual fleets for the glue or film press in portions or continuously in the form of solid preparations themselves or solutions made from them are added.

The brightener preparations according to the invention are characterized by a number of Advantages. As solid preparations, they are very easy to store and in any Ratios dosed. Compared to the prior art (e.g. DE-A-3523207) if they are extremely free-flowing and meterable, they can be easily and lump-free Introduce water and have improved solubility and higher dissolution rate both in cold (10 ° C) and hot water (up to 80 ° C). They also form in concentrations of up to 30% by weight (at RT) or up to 75 % By weight (at 80 ° C) of crystal-free clear solutions that have one for use sufficiently long period (generally> 1 h) stable against crystalline flocculation or Sedimentation of hydrate crystals are.

example 1

700 ml of water and 10 g of sodium chloride were introduced into a reactor A and Stirred for 10min. Then 1.0 g of a polyether was exposed with stirring Isodecyl alcohol, 6 mol ethylene oxide and 8 mol propylene oxide and cooled to approx. 10 ° C.

100 g of cyanuric chloride (0.542 mol) were introduced with stirring and rinsed with 100 ml After water and stirred the suspension until the pH had dropped to 4.5. To an aqueous solution cooled to 10 ° C. was titrated in 1200 ml of 0.3 mol of 4,4'-diaminostilbene-2,2'-disulfonic acid disodium salt and contained 0.3 mol of sodium carbonate, allowing the temperature of the reaction mixture to rise to 18 ° C. For the addition you used an automatic titrator which you put on the top Set a limit of pH 4.5. Theoretically, 1084 ml could be consumed. The end point of the reaction was less than 5 within 10 minutes ml were consumed. That was after 2 to 2.5 hours with a consumption of 99% of theory is the case. A readily stirrable light yellow suspension was formed.

The titrator template was changed. The titrator template contained 250 g 10% Sodium hydroxide solution.

The pH was then adjusted to 6.8 with 7 g of 10% sodium hydroxide solution. 49.5 g of aniline (0.53 mol) were then run in within 30 minutes, allowing the temperature in the reactor to rise to 25 ° C. One stirred 1.5 Hours at 25 ° C. Up to this point, 215 g 10% sodium hydroxide solution (0.54 mol) metered in. The admission was at the end of the Stirring time less than 2 ml in 10 minutes.

In a second reactor B, 300 ml of water were introduced, 84 g of an 80% solution were added Diethanolamine solution (0.64 mol) and heated to 95 ° C. Within 1.5 The contents were transferred from reactor A to reactor B for hours. there was the temperature in reactor B to 95 ° C and the pH to 7.5 by titration with 10% sodium hydroxide solution kept constant. Then was continued under Titration heated to 98 to 100 ° C for 2.5 hours. The consumption of 10% Sodium hydroxide solution was 180 g (0.45 mol). The mixture was allowed to cool to 85 ° C. and was added this temperature by adding hydrochloric acid to a pH of 4.2. One stirred 30 minutes after and the temperature dropped to 50 to 55 ° C.

The product was filtered off and washed thoroughly with water. After this Drying at 50 ° C in a vacuum gave 245 g of product with a specific Absorbance of 600 at 350 nm.

The product corresponded to the compound of the formula

Then 430 ml of water were placed in a reactor and brought to about 90.degree heated. The entire product was added in three equal parts, each part was brought into solution by adding 70 g of 10% sodium hydroxide solution. The pH of the resulting tan cloudy solution was adjusted to 8.5 with 10% sodium hydroxide solution set to 9.0.

The mixture was filtered at 80 to 90 ° C. through a depth filter and 890 g of a clear one were obtained Solution with an E1 / 1 value of 165 (measured at 350 nm wavelength).

This approximately 80 to 85 ° C hot solution was on a laboratory two-fluid nozzle dryer with an air inlet temperature of 220 ° C and an air outlet temperature of Dried at 91 ° C. 120 g of the powder thus obtained were mixed in a laboratory mixer 1.2g hexylene glycol (comp. B1) mixed homogeneously. You got a low dust solid brightener preparation according to the invention with a medium volumetric Particle size of 25 µm, a dust filter value of 4, and a specific Absorbance (E1 / 1) of 565 and a residual moisture content of 5.4% by weight based on the solid preparation. This solid preparation showed after a storage period of 4 weeks at RT and 40 ° C only slight clumping. In particular, she let herself down moisten moderately stirring in water at room temperature very lightly and distribute, was very soluble in concentrations up to 20% by weight and formed clear solutions.

The untreated spray-dried powder had a dust value of 1 and showed considerable clumping and a considerably longer dissolving time when entering water despite more intensive stirring.

1 shows the X-ray diffraction spectrum of the solid brightener preparation (reflection diffractometer D5000, Siemens AG, with automatic aperture diaphragm). The preparation showed no crystalline portions of the brightener and was X-ray amorphous.

Example 2

According to the procedure described in Example 1, about 300 kg of a clear one Solution of the same brightener prepared and after the depth filtration at a temperature of 90 ° C 0.5% by weight Baykanol®SL (Bayer AG, formaldehyde condensation product Comp. d) based on sulfonated ditolyl ether) based on the brightening agent added with stirring and completely dissolved.

This approximately 90 ° C hot solution was on a single-component atomizer dryer with an air inlet temperature of 210 ° C and an air outlet temperature of Dried at 78 ° C. A swirl chamber nozzle type SD with 0.56 was used Inch bore from Delavan, the atomization pressure was 21 bar and Nozzle throughput about 105 l / h.

5 kg of the microgranules obtained in this way were mixed in a mixer (Lödige, 201 Capacity) with 0.5% by weight hexylene glycol (comp. B1) based on microgranules homogeneously mixed. A low-dust solid according to the invention was obtained Brightener preparation with an average volumetric particle size of 98 µm, a dust filter value of 5, and a specific absorbance (E1 / 1) of 572 and a residual moisture content of 5.0% by weight based on the solid preparation. This solid preparation had no crystalline portions of the brightener and was X-ray amorphous; after a storage period of 4 weeks at RT and 40 ° C. it showed another Filter value of 5 or 4, and only slight clumping. In particular, she let herself with moderate stirring in water at room temperature and in hot water (80 ° C) wetting and distributing very easily, was very high in concentrations up to 20% by weight well soluble and formed clear solutions. A 10% solution had a pH of 8.4 and was stable for more than 2 hours.

The untreated spray-dried microgranules had a dust value of 1 and showed considerable clumping and a considerable clogging upon entry into water (RT) longer dissolving time despite more intensive stirring performance.

A brightener preparation based on example 1, DE 3523 207, based on the same untreated spray-dried microgranules had one Dust value of 5, but showed even greater clumping when entering water (RT) and a significantly longer dissolving time than the untreated product.

The solid preparation according to the invention was therefore outstandingly suitable for the continuous or discontinuous preparation of aqueous dye baths for White tones of natural and synthetic materials, especially paper in the Mass and in the surface, cellulose or acid modified acrylic fibers as well for brightening detergents.

Example 3

According to the procedure described in Example 1, about 300 kg of a clear one Solution of the same brightener made and after the deep filtration at a temperature of 90 ° C with

1.9% by weight, based on the brightening agent, of a 28% aqueous solution a formaldehyde condensation product of 4,4'-dihydroxydiphenyl sulfone and Naphthalenesulfonic acid, which by means of a cross-flow ultrafiltration filtration as in Example 5, EP-A-1 049 745 described desalted and set low residual monomer has been registered and completely resolved.

This approximately 90 ° C hot solution was on a single-component atomizer dryer with an air inlet temperature of 210 ° C and an air outlet temperature of Dried at 78 ° C as in Example 2. 5 kg of the microgranules thus obtained were in a mixer (Lödige, 201 capacity) with 0.5% by weight hexylene glycol (Comp. B1) homogeneously mixed based on microgranules. You got one low-dust solid brightener preparation according to the invention with a medium volumetric particle size of 95 µm, a dust filter value of 5, and one specific extinction (E1 / 1) of 565 and a residual moisture of 6.5% by weight based on the solid preparation. This solid preparation had no crystalline Portions of the brightener and was X-ray amorphous; after a storage period of 4 weeks at RT and 40 ° C a filter value of 5 or 4, and only low, easily dissolvable clumping. In particular, she let herself in with moderate stirring Very lightly wet water at room temperature and in hot water (80 ° C) and distribute, was very soluble in concentrations up to 20 wt .-% and formed clear solutions. A 10% solution had a pH of 8.7 and was above one Stable for more than 6 hours.

The solid preparation according to the invention was therefore outstandingly suitable for the continuous or discontinuous preparation of aqueous dye baths for White tones of natural and synthetic fiber materials, especially paper in the mass and in the surface, cellulose or acid modified acrylic fibers and to lighten detergents.

Example 4

5 kg of microgranules obtained by the same method as in Example 2 were in a mixer (Lödige, 201 capacity) with 1.0% by weight of polyethylene glycol dimethyl ether (comp. B1) based on microgranules homogeneously mixed. A low-dust solid brightener preparation according to the invention was obtained with an average volumetric particle size of 102 µm, one Dust filter value of 5, and a specific absorbance (E1 / 1) of 558 and one Residual moisture of 5.2% by weight based on the solid preparation. This solid preparation had no crystalline parts of the brightener and was X-ray amorphous; she showed a filter value after a storage time of 4 weeks at RT and 40 ° C of 5 and no significant clumping. In particular, she let herself down moderate stirring in water at room temperature and in hot water (80 ° C) very slightly wetted and distributed, was very good in concentrations up to 20% by weight soluble and formed clear solutions. A 10% solution had a pH of 8.5 and was stable for more than 6 hours.

The solid preparation according to the invention was therefore outstandingly suitable for the continuous or discontinuous preparation of aqueous dye baths for White tones of natural and synthetic fiber materials, especially paper in the mass and in the surface, cellulose or acid modified acrylic fibers and to lighten detergents.

Example 5

5 kg of microgranules obtained by the same method as in Example 3 were in a mixer (Lödige, 201 capacity) with 1.0 % By weight of polyethylene glycol dimethyl ether (molecular weight 270 to 280 g / mol, comp. b1) homogeneously mixed based on microgranules. You got a low dust solid brightener preparation according to the invention with a medium volumetric Particle size of 107 µm, a dust filter value of 5, and a specific one Absorbance (E1 / 1) of 560 and a residual moisture content of 4.7% by weight based on the solid preparation. This solid preparation had no crystalline parts of the Brightener and was X-ray amorphous; it showed after a storage period of 4 weeks at RT and 40 ° C a filter value of 5 and no significant clumping. In particular, it could be mixed with moderate stirring in water at room temperature and in hot water (80 ° C) wetting and distributing very easily, was in concentrations up to 20% by weight very soluble and formed clear solutions. A 10% Solution had a pH of 8.4 and was over a period of more than 6 hours stable.

The solid preparation according to the invention was therefore outstandingly suitable for the continuous or discontinuous preparation of aqueous dye baths for White tones of natural and synthetic fiber materials, especially paper in the mass and in the surface, cellulose or acid modified acrylic fibers and to lighten detergents.

Example 6

5 kg of one obtained by the same method as in Example 2 Microgranules were mixed in a mixer (Lödige, 201 capacity) 0.7% by weight of a reaction product of nonyl decyl alcohol with 5 mol units Ethylene oxide and then 5 mol units of propylene oxide (Diadavin® NW 400%, Bayer AG, comp. B1) homogeneously mixed based on microgranules. you received a low-dust solid brightener preparation according to the invention with a mean volumetric particle size of 94 µm, a dust filter value of 5, and a specific absorbance (E1 / 1) of 570 and a residual moisture of 4.3 % By weight based on the solid preparation. This solid preparation had none crystalline portions of the brightener and was X-ray amorphous; she pointed to one Storage time of 4 weeks at RT and 40 ° C still a filter value of 5 or 4 and only very little clumping that was easy to dissolve. In particular, she let with moderate stirring in water at room temperature and in hot water (80 ° C) very easy to wet and distribute, was in concentrations up to 15 % By weight very readily soluble and formed clear solutions. Had a 10% solution pH 8.6 and was stable for more than 2 hours.

The solid preparation according to the invention was therefore outstandingly suitable for the continuous or discontinuous preparation of aqueous dye baths for White tones of natural and synthetic fiber materials, especially paper in the mass and in the surface, cellulose or acid modified acrylic fibers and to lighten detergents.

Example 7

The procedure was as shown in Example 6, but using 0.7% by weight of the sodium salt of a mixture of different alkanesulfonates with an average chain length of C ₁₃ (Mersolat® W40, Bayer AG), and also low-dust and very readily soluble inventive solid brightener preparations which were very suitable for brightening cellulose or acid-modified acrylic fibers and in particular for brightening detergents.

Example 8 Use according to the invention in pulp dyeing

200 ml of a 2.5% aqueous cellulose mixture, containing 30 parts of Nordic long fiber sulfate pulp and 70 parts Nordic short fiber sulfate pulp submitted with 800 ml of deionized water refilled. Then 0.15% by weight, based on the solids content, was added the pulp mixture of the solid brightener preparations according to the invention of Examples 2-5 introduced with stirring and after 10 minutes of stirring Hand sheet shaped on the sieve; the leaves obtained were then opened carefully dried in a drying cylinder at a temperature of 95 ° C and for a period of 12 hours at 23 ° C and 50% relative humidity conditioned.

These handmade paper sheets showed a high white aspect and excellent Levelness.

Example 9 use according to the invention in paper coating

60 Teile Calciumcarbonat

40 Teile Kaolin

10 Teile SBR-Latex

1 Teil Polyvinylalkohol

0,25 Teile Polyacrylsäure

Brightener-free and wood-free A4 base papers (basis weight 80 g / m ² ) were coated on a laboratory doctor device (Erichsen, K-Control-Coater, model K 202) with coating colors of the following composition:

60 parts calcium carbonate

40 parts of kaolin

10 parts of SBR latex

1 part polyvinyl alcohol

0.25 part polyacrylic acid

The pH of the coating color was adjusted to 8 to 8.5 with dilute sodium hydroxide solution adjusted and the solids content of the coating color to 60 by adding water set to 65%. The coating color was divided into 3 parts and one part each The solid color according to the invention described in Examples 2 to 5 became coating slip Brightener preparations in an amount of 3 g each based on 1 kg of coating color introduced homogeneously and over a period of 10 min. mixed.

The sheets coated in this way were 1 min. dried at 95 ° C in a drying cylinder and then stored for 3 hours at 23 ° C and a humidity of 50%, before they were measured. In all 4 cases papers with a very high result good whiteness and levelness.

Example 10 Use according to the invention in the paper size press

50 g/l Stärke und

0,5 g/l festen Aufhellerpräparationen gemäß den Beispielen 2 bis 5.

Brightener-free and wood-free DIN A4 base papers (basis weight 80 g / m ² ) were each wetted with aqueous liquors on a laboratory size press (Werner Matthis AG, TYPE No. HF 18374)

50 g / l starch and

0.5 g / l solid brightener preparations according to Examples 2 to 5.

The pH of the liquors was about 7. The wet absorption was about 50 to 60%.

The leaves were then dried in a drying cylinder at 95 ° C. for 1 min then stored for 3 hours at 23 ° C and a humidity of 50% before they were measured. In all cases, papers with a very good result resulted Whiteness.

Example 11 Continuous Process of Continuous Dissolution and Use in Bulk Paper Dyeing According to the Invention

The solid brightener preparation described in Example 2 was used over a period of time of 1 hour (stationary operation) continuously using a dosing screw a quantity of 120 kg / h (average over 10 min. discharge time for solid Screw speed) by means of a hold-up disperser together with 880 l / h water (RT) introduced into a 500 l stirred tank with a propeller stirrer from above and at the same time 1000 kg / h of the mixture obtained on the bottom side by means of a rotor-stator pump taken. The stirrer speed was set low in foam, so that floating particles of the solid brightener preparation are avoided has been. In the steady state, the container filling was about 300 l, the middle one Residence time of the mixture in the stirred container 0.3 hours. Samples taken at intervals from 5 min. removed behind the discharge pump contained the desired one clear solution of the solid brightener preparation, none were not solved Preparation particles found. The E1 / 1 values of the samples of the solution were in the Range of 66 +/- 2, the stability of the solution against precipitation was more than 6 Hours. The concentrated solution thus obtained was therefore outstandingly suitable for in the material flow of a paper machine continuously in the desired ratio (desired concentration of the brightening agent) to be metered.

With the method described, it was also possible to provide sufficiently stable, adjust clear solutions up to a concentration of more than 22% by weight.

With the same procedure, the fixed Auheller preparations could also be made Examples 3 to 5 can be solved continuously with a comparable good result.

Example 12 (application to cotton, block drying process)

14 g/l Aufhellerwirkstoff aus den Beispielen 2-6

3 g/l Natriumsulfat enthielten.

Boiled and bleached cotton fabrics were padded on the laboratory foulard with various aqueous liquors, each

14 g / l brightening agent from Examples 2-6

3 g / l sodium sulfate contained.

The whitening agent was added with stirring by adding the corresponding amount of solid brightener preparations according to the invention from the Examples 2-6 and subsequent addition of sodium sulfate.

The liquor pick-up of the fabric was done by squeezing between the paddle rollers set to approx. 80%. The goods were then dried immediately through a stenter passage at 100 ° C for 30 seconds. Through this treatment a very good brightening effect was achieved on the goods.

Example 13 (application to cotton, dry crosslinking)

14 g/l Aufhellerwirkstoff aus Beispiel 2 bis 6 und

105 g/l einer Kunstharzvorkondensatmischung bestehend aus

80 g/l Fixapret®NF (Produkt der BASF) und

25 g/l Condensol® N (Produkt der BASF).

Boiled and bleached cotton poplin was impregnated on the laboratory pad with various aqueous liquors of the following composition, based on the solid preparations of Examples 2-6:

14 g / l brightening agent from Examples 2 to 6 and

105 g / l of a synthetic resin precondensate mixture consisting of

80 g / l Fixapret®NF (product from BASF) and

25 g / l Condensol® N (product from BASF).

The whitening agent was added with stirring by adding the corresponding amount of solid brightener preparation according to the invention from the Examples 2 to 6.

The goods were between rolls on a fleet absorption of about 80% of the Squeezed dry weight. Then the drying on the Stenter frame at 100 ° C for 30 seconds. Condensation was also carried out on the Stenter at 150 ° C for 4 minutes.

This treatment resulted in a very good lightening effect on the goods achieved.

Claims (21)

Containing solid, particular brightener preparations a) 81 to 99.45% by weight of at least one brightening agent, b) 0.05 to 9% by weight, in particular 0.1 to 5% by weight, based on the solid preparation, of at least one compound from the group b1) the glycols and / or polyglycols with a boiling point above 150 ° C., in particular di- and / or tripropylene glycol, alkanediols with 4 to 8 carbon atoms and / or polyglycols or diols with terminal groups other than hydrogen, preferably methoxy groups, b2) the surface-active compounds with an HLB value of less than 12, in particular less than 10, and / or b3) the alkyl sulfonates with an average hydrocarbon chain length of C ₁₃ to C ₁₅ , preferably their sodium salts and c) 0.5 to 18.95% by weight, in particular 1 to 16% by weight, of residual moisture,
characterized in that the sum of components a), b) and c) is> 85% by weight, preferably> 90% by weight and in particular> 95% by weight, based on the solid preparation. Solid brightener preparations according to claim 1, containing as component b1) Tripropylene glycol and / or at least one alkanediol with 4 to 8 carbon atoms. Solid brightener preparations according to claim 1 to 2, containing as a comp. b1) tripropylene glycol, hexylene glycol, neopentene glycol and / or 1,3-butylene glycol, especially hexylene glycol and / or neopentyl glycol. Solid brightener preparations according to claim 1, containing as component b1) Polyethylene glycol methyl ether and / or dimethyl ether preferably with a molecular weight of <1000 g / mol, preferably <500 g / mol. Solid brightener preparations according to Claim 1, containing as component b2) a nonionic surface-active agent with an HLB value of less than 12, in particular less than 10, selected from the group of the reaction products of alkylene oxides with alkylatable compounds, such as, for example, fatty alcohols, fatty amines, fatty acids, Phenols, alkylphenols, carboxamides and resin acids. These are, for example, alkylene oxide adducts from the class of the reaction products of ethylene oxide and / or propylene oxide with: i) saturated and / or unsaturated fatty alcohols with 6 to 25 carbon atoms or j) alkylphenols with 4 to 12 carbon atoms in the alkyl radical or k) saturated and / or unsaturated fatty amines with 14 to 20 carbon atoms or l) saturated and / or unsaturated fatty acids with 14 to 22 carbon atoms or m) hydrogenated and / or unhydrogenated resin acids, or n) esterification and / or arylation products which are produced from natural or modified, optionally hydrogenated castor oil fatty bodies and which are optionally linked to repeating structural units by esterification with dicarboxylic acids. Solid brightener preparations according to claim 1 and 5, containing as a comp. b2) a nonionic surfactant based on the compounds i) to l) by mixed and / or block reaction with ethylene and Propylene oxide can be obtained, especially a final one (Poly) propylene oxide block with 1 to 10, preferably 2 to 8 mol units Contain propylene oxide. Solid brightener preparations according to claim 1, containing as component b3) an alkyl sulfonate and / or mixtures of alkyl sulfonates of the general formula Z- SO ₂ -OH with Z = alkane, cycloalkane, alkene, especially paraffin,
and their salts, in particular sodium salts. Solid brightener preparations according to at least one of Claims 1 to 7, characterized in that the water-soluble optical brightener of component a) is selected from the group of the stilbene compounds containing sulfo and / or carboxyl groups. Solid brightener preparations according to at least one of claims 1 to 7, characterized in that the optical brightener of component a) is selected from the group consisting of the distilbenes or the triazinylflavonates of the general formula (I)

wherein

R ¹ , R ² and R ³

independently phenoxy; mono- or disulfonated phenoxy; phenylamino; mono- or disulfonated phenylamino; Phenylamino substituted by C ₁ -C ₃ alkyl, cyano, halogen, COOR, CONH-R, NH-COR, SO ₂ NH-R, OR; morpholino; piperidino; pyrrolidino; -OC ₁ -C ₄ alkyl; -NH (C ₁ -C ₄ alkyl); -N (C ₁ -C ₄ alkyl) ₂ ; -NHC ₂ -C ₄ alkylene-OR; -N (C ₂ -C ₄ hydroxyalkyl) ₂ ; -NHC ₂ -C ₄ alkylene-OC ₂ -C ₄ alkylene-OR; an amino acid or an amino acid amide from whose amino group a hydrogen atom has been removed;
-NHCH ₂ CH ₂ OH; -N (CH ₂ CH ₂ OH) ₂ ; -N (CH ₃ ) (CH ₂ CH ₂ OH); -NH ₂ ; -OCH ₃ ; -SC ₁ -C ₄ alkyl; -S-aryl; -Cl; -NH-CH ₂ CH ₂ SO ₃ H; -N (CH ₂ CH ₂ SO ₃ H) ₂ ; or
-N (CH ₂ CH ₂ OH) CH ₂ CH ₂ CONH ₂ mean, and

R

H or C ₁ -C ₃ alkyl and M represents the remainder of an alkali, alkaline earth, ammonium or amine salt.

Solid brightener preparations according to at least one of claims 1 to 7, characterized in that the optical brightener of component a) is selected from the group of the triazinylflavonates of the formula (I)

wherein

R ¹ , R ² and R ³

independently of one another -NH ₂ , -NH-CH ₃ , -NH-C ₂ H ₅ , -N (CH ₃ ) ₂ , -N (C ₂ H ₅ ) ₂ , -NH-CH ₂ CH ₂ OH, -NH- C ₂ -C ₄ hydroxyalkyl, -N (C ₂ -C ₄ hydroxyalkyl) ₂ , -NH-CH ₂ CH ₂ SO ₃ H; -NH-CH ₂ -CH ₂ -O-CH ₂ -CH ₂ -OH, -OCH ₃ , -OCH (CH ₃ ) ₂ , -O-CH ₂ -CH ₂ -O-CH ₃ , -N (CH ₂ -CH ₂ -OH) ₂ , -N (CH ₂ -CHOH-CH ₃ ) ₂ , morpholino, -SCH ₃ , -N (CH ₂ -CH ₂ -OH) CH ₂ -CH ₂ -CONH ₂ and one of the following leftovers

and M represents the remainder of an alkali, ammonium or amine salt. Solid brightener preparations according to claim 10, characterized in that

R ¹ and R ²

for -N (CH ₂ -CH ₂ -OH) ₂ ,

R ³

For

and

M

has the above meaning, in particular stands for Na ⁺ or K +.

Solid brightener preparations according to at least one of claims 1 to 11, characterized in that the brightener preparations are powder and have an average mass-related particle size of more than 5 µm, in particular more than 15 µm. Solid brightener preparations according to at least one of claims 1 to 10, characterized in that the brightener preparations are granules or microgranules with an average mass-based particle size of more than 15 µm, in particular more than 40 µm. Solid brightener preparations according to at least one of claims 1 to 13, characterized in that they are free of crystalline brightener particles, in particular their hydrate forms. Solid brightener preparations according to at least one of claims 1 to 14, characterized in that they additionally contain d) 0.1 to 5% by weight based on the solid preparation of at least one condensation product based on A) sulfonated aromatics, B) aldehydes and / or ketones and optionally C) one or more compounds from the group of unsulfonated aromatics, urea and urea derivatives. Solid brightener preparations according to claim 15 containing as component d) a condensation product based on A) ditolyl ether sulfonic acid and B) formaldehyde and / or A) naphthalenesulfonic acid, B) formaldehyde and C) 4,4'-diphenyl sulfone. Use of solid brightener preparations according to claim 1 in aqueous Media for optically brightening natural and synthetic materials, especially fiber materials as well as detergents and sunscreens. Use of solid brightener preparations according to claim 1 for optical Lighten paper in bulk. Use of solid brightener preparations according to claim 1 for optical Lightening paper in the surface, especially in paper coating colors and glue or film press fleets. Use of solid brightener preparations according to claim 1 for the optical brightening of paper in bulk, characterized in that a solution of the solid brightener preparation in water with a concentration of 0.01 to 40 wt .-%, based. on component a), in particular 1 to 25% by weight at a temperature of 10 to 75 ° C., in particular 15 to 55 ° C., and a pH of 6.0 to 12, in particular 6.5 to 11, very particularly 6.5 to 9.5 produced and added to the paper pulp in each stage of the paper manufacturing process before drying or the paper coating slip or glue or film press liquor. Use according to claim 1 for the optical brightening of paper in the mass, characterized in that the preparation of the solution in water and the addition (dosage) to the paper mass takes place continuously.

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