EP3175033A2

EP3175033A2 - Compositions for treatment of fiber materials

Info

Publication number: EP3175033A2
Application number: EP15744199.9A
Authority: EP
Inventors: Harald Chrobaczek; Tanja Refle; Günther Tschida
Original assignee: Huntsman Textile Effects Germany GmbH
Current assignee: Huntsman Textile Effects Germany GmbH
Priority date: 2014-07-31
Filing date: 2015-07-29
Publication date: 2017-06-07
Anticipated expiration: 2035-07-29
Also published as: ES2949983T3; WO2016016282A2; EP3175033B1; CN106471182A; EP2980308A1; WO2016016282A3; CN106471182B

Abstract

The compositions described are particularly useful for the treatment of textile fabrics to endow them with advantageous wearing properties, in particular enhanced hydrophilicity. The compositions comprise urea, thiourea or melamine derivatives, compounds comprising polyoxyalkylene groups and optionally an alcohol, and these components may optionally also have been reacted with each other.

Description

Compositions for treatment of fiber materials

The invention described hereinbelow relates to compositions and their use for treating fiber materials, in particular fiber materials comprising cellulose.

It is known to treat textile materials comprising cellulose with so-called cellulose crosslinkers in order to reduce the wrinkle tendency. These resin-finishing processes utilize inter alia N- methylolated products of the formula

which are obtainable by reaction of urea with glyoxal and with formaldehyde. Methylolated melamine derivatives of the formula

have also already been used for this.

The products mentioned have the disadvantage that thermal treatment during the resin-finishing process causes formaldehyde to be given off into the surroundings. Products have therefore been developed which are etherified at one or more of the hydroxyl groups. Methanol is primarily used for this. Products of the type mentioned and their use are described inter alia in WO 2004/033170 A1 , US 6 123 739 A and DE 196 33 625 A1 .

US 6 102 973 A discloses an aqueous composition comprising dimethyloldihydroxyethylene- urea (DMDHEU) and an ethoxylated alcohol as wetting agent. The composition may also comprise polysiloxanes.

US 5 242 463 A discloses an aqueous composition comprising DMDHEU, a hydroxyalkylamine and/or a quaternary hydroxyalkylammonium compound, a glycol ether and optionally an alcohol.

US 5 358 535 A discloses an aqueous composition comprising a urea-formaldehyde resin and ethoxylated nonylphenol, wherein polyalkylene glycol diesters are employed as formaldehyde collectors.

US 5 614 591 A discloses an aqueous composition comprising DMDHEU and a catalyst and, optionally, also among other possibilities a wetting agent, preferably alkylphenol ethoxylates, linear alcohol ethoxylates or fatty acid ethoxylates.

However, even the properties of the fully or partially methanol-etherified products are still not ideal. For instance, the hydrophilic properties of cellulose articles, in particular articles comprising cotton, that have been finished with the products are not always at the desired high level, as has been confirmed in wetting tests. This applies inter alia to resin-finishing processes wherein cotton articles are subjected to curing in the moist state.

The problem addressed by the present invention was that of improving existing products to the effect that the cellulose materials treated therewith are endowed with enhanced hydrophilicity while at the same time retaining a pleasantly soft hand. This particularly when the products are used in the course of a cure in the moist state. The problem addressed by the present invention was further that of finding novel, readily dispersible, reactive products capable of scavenging free radicals. The problem addressed by the present invention was further that of providing novel reactive fluorosurfactants. The problem addressed by the present invention was further that of providing novel reactive compounds having optically brightening properties.

The problem was solved by a composition comprising at least one compound of formula (II) or of formula (III) or of formula (IV) or of formula (V)

R— N— CH— O— R²

I I I

R-O-CH— N— C .C— N— CH— O— R² ('")

I / I

I 3 ^{N 1} 3

R³ R HC CH

/ \ (IV) CH„— N ,N— CH,

II

x

R— N— C— N— R³ (V)

X

and at least one compound of formula (VII) or one amine of formula (VIII) or (IX) or one oligo- or polyorganosiloxane, having polyoxyalkylene groups, of general formula (X) or one compound of formula (XI), preferably of formula (XIa),

and optionally further comprising an alcohol of formula (VI),

R⁴— OH (VI) where all R and R² each independently stand for H or for linear or branched alkyl of 1 to 5 carbon atoms, preferably for CH₃ or C₂H₅ or C₃H₇, or for or for

-CH— CH— O- ^■R where m is a number from 4 to 8 and t is 0 or 1 and p is a number from 8 to 20 and q is a number from 1 to 3,

all R³ each independently stand for H or for— CH₂— O— R²,

where in formula (V) at least one R³ stands for— CH₂— O— R²,

X stands for O or S,

where in a formula (V) where X stands for S, R³ may also stand for -CH₂-0-R¹⁴, in which R ⁴ stands for a moiety resulting from a phenolsulfonic acid or from a salt of a phenolsulfonic acid, in particular p-phenolsulfonic acid or one of its salts, by etherification of a methylolated thiourea with said phenolsulfonic acid or a salt thereof, or R³ may also stand for -CH₂-R¹⁵, in which R ⁵ stands for a moiety resulting from a phenolsulfonic acid or from a salt of a phenolsulfonic acid, in particular p-phenolsulfonic acid or one of its salts, by reaction of a methylol group of a methylolated thiourea with a methine group of said phenolsulfonic acid or a salt thereof to form a methylene bridge between the nitrogen atom of the thiourea and a carbon atom of the phenolsulfonic acid or of a salt thereof,

R⁴ stands for a linear or optionally branched alkyl of 1 to 18, preferably 1 to 4, carbon atoms, more preferably for CH₃ or C₂H₅,

R⁵ stands for linear or branched alkyl or alkenyl of 4 to 18, preferably 8 to 18 carbon atoms, more preferably for branched alkyl of 13 carbon atoms, or for an aromatic moiety optionally substituted by one or more hydrocarbyl moieties, in particular for phenyl, tolyl or benzyl, where k + y is = 2 and k has the value 1 or 2, one of R⁶ and R⁷ stands for H while the other stands for H or for CH₃, 1 stands for a number from 0 to 20, preferably from 2 to 20, more preferably from 2 to 8, in particular for 2 to 6, where in the presence of a compound of formula (VII) with I = 0 a compound of formula (VII) with I >= 2 must also be present, n stands for a number from 2 to 20, preferably from 2 to 8, more preferably from 2 to 6, and R⁸ stands for H or for

where one of R⁹ and R ⁰ stands for H while the other stands for H or CH₃ or C₂H₅ or CH₂OH, where r is a number from 2 to 15, s is a number from 0 to 20, v is a number from 1 to 18 and R stands for H or CH₃ and where in the siloxane of formula (X) not only the dimethylsiloxy units but also the methylsiloxy units comprising moieties including polyoxyalkylene groups may be randomly distributed across the siloxane chain,

where R ² stands for H or linear or optionally branched alkyl of 1 to 4 carbon atoms, preferably for CH₃ or t-C₄H₉, more preferably for H,

where R ³ stands for H or a linear or optionally branched alkyl of 1 to 4 carbon atoms, preferably for H or n-C₄H₉,

where w stands for a number from 2 to 9, preferably from 3 to 8, u is 0 or preferably 1 , Y is a divalent moiety comprising carbon and hydrogen and optionally sulfur and/or nitrogen and/or oxygen,

wherein the composition comprises a reaction product of one or more compounds of formulae (II) to (V) with one or more compounds of formula (VII) and optionally of formula (VI) in the event at least that a compound of formula (VII) with I = 6-8 and t = 0 is present, and by an aqueous composition comprising such a composition.

Examples are R ⁴ and R ⁵ moieties derived from p-phenolsulfonic acid, once as acid and once as salt, although the R ⁵ moiety may also be substituted by reaction with further molecules of formaldehyde and phenolsulfonic acid or a salt thereof. Useful salts include those with customary alkalis, e.g., sodium, potassium and/or ammonium salts.

R

Such compositions not only have the advantage of conferring enhanced hydrophilicity on cellulose articles, but they also lead to lower emissions of R²-OH alcohol. In addition, compositions according to the present invention are less prone to cleave ether bonds present, which results in a lower tendency to oligomerize, which leads to more stable products. They are therefore particularly useful for treatment of fiber materials comprising natural fibers, preferably cellulose or wool, or synthetic fibers, in particular polyester, polyamide, polyacrylonitrile, polyacrylate and viscose, and also mixtures thereof, but in particular of fiber materials that are 50 to 100 wt% cellulose. Cotton articles in particular acquire excellent properties as a result of treatment with the recited compositions by virtue of the surfactant character thereof. The fiber materials concerned are particularly in the form of wovens.

A particularly suitable field of application for compositions according to the present invention and/or aqueous compositions comprising such compositions is the moist cure of articles comprising cellulose fibers.

A number of compositions according to the present invention are miscible with comparatively long-chain alkoxylated primary amines, including primary amines of the JEFFAMINE^® range from Huntsman. This miscibility means that the resultant formulations can be used in processes wherein the finishing agent is used as a solution in supercritical carbon dioxide. The finishing of fiber articles using solutions in liquid supercritical carbon dioxide offers various advantages over finishing with aqueous systems. Processes of this type are described inter alia in WO 94/18264 AL EP 1 126 072 A2 and EP 846 803 B1 .

The finishing with products according to the present invention leads to minimal emissions of | j Q|_| Q|_|

formaldehyde when the ² groups of the melamine derivatives of formula (III) or of the urea derivatives of formula (II) or (V) are in an etherified state. In addition, the emissions of low alcohols, in particular methanol, are also reduced versus existing processes, since the OH groups of the urea or melamine derivatives are not exclusively etherified with methanol. Cotton products finished with compositions according to the present invention and/or aqueous compositions thereof lead to a pleasantly soft hand for the final articles. Particularly articles whose cotton content is in the range from 50 to 100 wt% acquire outstanding properties. The articles are preferably wovens.

Mixtures according to the present invention are obtainable by the following general method:

Ν,Ν'-dimethylolurea of the formula

HO-CH-NH-C-NH-CH— OH

2 II ²

O

is reacted with glyoxal at about pH 5 in the presence of water to form

dimethyloldihydroxyethyleneurea of formula (I)

Admixing an excess of an R⁴-OH alcohol and simultaneously admixing a compound of formula (VII)

results in an etherification to produce a mixture of the present invention.

Other compositions according to the present invention, for example those comprising

compounds of formulae (II), (III), (IV) or (V) and/or their reaction products with alcohol of formula (VI) and compounds of formula (VII), are obtainable by similar methods familiar to a chemist. It is similarly also possible to prepare compositions according to the present invention which comprise an amine of formula (VIII) or (IX) or an oligo- or polyorganosiloxane, having

polyoxyalkylene groups, of general formula (X) or a compound of formula (XI), preferably of formula (XIa), and/or reaction products thereof. When a compound of formula (VII) or a siloxane of formula (X) or a compound of formula (XI), preferably of formula (XIa), is not just added but also chemically reacted, it is necessary to employ such compounds of this type as have R ² = H. R⁴ in the R⁴-OH alcohol stands for linear or optionally branched alkyl of 1 to 18, preferably 1 to 4, carbon atoms, more preferably for CH₃ or C₂H₅, R⁴-OH is preferably methanol. R⁵ in the compound of formula (VII) stands for linear or branched alkyl or alkenyl of 4 to 18, preferably 8 to 18 carbon atoms, and isotridecyl is particularly preferable. Further, in formula (VII), one of R⁶ and R⁷ stands for hydrogen while the other stands for hydrogen or methyl. In formula (VII), I is a number from 0 to 20, preferably from 2 to 20, more preferably from 2 to 8, in particular from 2 to 6, and in the presence of a compound of the formula (VII) with I = 0 a compound of formula (VII) with I >= 2 also has to be present.

The reaction described above is performable as follows: An aqueous glyoxal solution

established at about pH 5 is admixed with Ν,Ν'-dimethylolurea, then 37% aqueous

formaldehyde and R⁴-OH alcohol and heated to 40 'Ό. The pH is then adjusted to about 7 with NaOH before an excess of R⁴-OH alcohol and a compound of formula (VII) are added. This is followed by the addition of some acid, for example hydrochloric acid, and an etherification takes place as the temperature goes up. The etherification is then discontinued by admixture of NaOH. It is advantageous to then admix an alkanolamine, for example triethanolamine.

Preferably excess R⁴-OH alcohol is then distilled off. After pH adjustment to about 6, a distillation is carried out at a temperature of 60 ° to 70 ^ under reduced pressure to remove excess alcohol R⁴-OH and water. R⁴-OH is preferably methanol.

When the starting material used is a urea derivative of formula (II), (IV) or (V) or a melamine derivative of formula (III), the synthesis proceeds in similar fashion, by etherification with a mixture of R⁴-OH alcohol and compound of formula (VII). Instead of the compound of formula (VII), however, an amine of formula (VIII) or (IX) or a siloxane of formula (X) or a compound of formula (XI), preferably of formula (Xla), may also be used.

Owing to the known fact that etherifications lead to an equilibrium, it is normally not all the OH groups of the starting and final compounds which are in an etherified state during the

preparation of mixtures according to the present invention, but only some. It is further possible that, in the syntheses described above, initially no etherification takes place with compound of formula (VII), but only with alcohol R⁴-OH. The partial etherification with compound of formula (VII) only takes place in this case during the distillative removal of R⁴-OH alcohol. In the mixture of the present invention, then, a proportion of the original OH groups have etherified with R⁴-OH alcohol, while another portion have reacted, i.e. undergone etherification in this case, with compound of formula (VII).

The same also applies here on employing an amine of formula (VIII) or (IX) or a siloxane of formula (X) or a compound of formula (XI), preferably of formula (Xla).

Analytical studies have shown that, when R⁴-OH is methanol and the compound of formula (VII) is an alcohol of formula (Vila),

(Vi la) i.e. isotridecyl alcohol incorporating on average 3 mol of ethylene oxide, the following compound is among those detectable (by chromatography/mass spectrometry analysis) in the composition of the present invention:

and also derivatives thereof in each of which one or more of the free OH groups are methanol- etherified, and oligomers of said compounds.

What distinguishes the compositions of the present invention from known compositions prepared using, for example, dimethyloldihydroxyethyleneurea and methanol is the fact that, in addition to low molecular weight alcohol, the invention further employs a comparatively high molecular weight compound of formula (VII) or its ether and/or an amine of formula (VIII) or (IX) or an oligo- or polyorganosiloxane of general formula (X) or a compound of formula (XI), preferably of formula (XIa).

The mixture of an alcohol of the formula R⁴-OH and a compound of formula (VII) will normally contain an excess of the alcohol of the formula R⁴-OH. Preferably, from 0.01 to 0.5 mol of compound of formula (VII) or amine of formula (VIII) or (IX) or oligo- or polyorganosiloxane, having polyoxyalkylene groups, of general formula (X) or compound of formula (XI), preferably of formula (XIa), is reacted per mol of R⁴-OH alcohol. In formula (VII), R⁵ preferably stands for branched alkyl of 13 carbon atoms and I preferably stands for a number from 2 to 20, more preferably from 2 to 8, in particular from 2 to 6. Compositions according to the present invention are conveniently obtainable by mixing and/or reacting at least one of said compounds of formula (II), (III), (IV) and (V) with a mixture of at least one alcohol of formula (VI) and at least one compound of formula (VII) or one amine of formula (VIII) or (IX) or one oligo- or polyorganosiloxane, having polyoxyalkylene groups, of general formula (X) or one compound of formula (XI), preferably of formula (XIa). This is done at a temperature in the range from 30 to 130°C, preferably from 30 to 80 °C, more preferably of 40-70 'Ό, and the final distilling step likewise takes place in this temperature range.

A transetherification or, respectively, an amination takes place during the distillative removal of alcohol of formula (VI). Advantageously, temperature, pressure and pH are so chosen that distillative removal of alcohol of formula (VI) shifts the reaction equilibrium in favor of reaction products comprising a larger proportion of compound of one of formulae (II) to (V) which has been reacted with a compound of one of formulae (VII) to (XIa), and preferably the compound of one of formulae (VII) to (XIa) is only admixed to the reaction after some of the excess alcohol of formula (VI) has already been distilled off.

The etherification with alcohol of formula (VI) is carried out at a pH of 0.3 to 1 , preferably of 0.45 to 0.75. This pH can be achieved by admixing concentrated hydrochloric acid for example. The subsequent reaction with a compound of formula (VII) where R ² = H or an amine of formula

(VIII) or (IX) or an oligo- or polyorganosiloxane, having polyoxyalkylene groups, of the general formula (X) where R ² = H or a compound of formula (XI) where R ² = H, preferably of formula (XIa), is carried out at a pH of 5 to 7, preferably of 5.6 to 6.4. This pH is achievable by stopping the etherification with alcohol of formula (VI) by, for example, admixing aqueous sodium hydroxide solution and triethanolamine as buffer. The reaction with a compound of formula (VII) where R ² = H or an amine of formula (VIII) or (IX) or an oligo- or polyorganosiloxane, having polyoxyalkylene groups, of general formula (X) where R ² = H or a compound of formula (XI) where R ² = H, preferably of formula (XIa), is advantageously carried out in vacuo, at an absolute pressure of 50 to 1000 mbar, preferably of 50 to 175 mbar. This reaction is a transetherification on using a compound of formula (VII) where R ² = H or an amine of formula

(IX) or an oligo- or polyorganosiloxane, having polyoxyalkylene groups, of general formula (X) where R ² = H or a compound of formula (XI) where R ² = H, preferably of formula (XIa), or an amination on employing an amine of formula (VIII).

A particularly preferred form of the invention consists in a composition comprising a product obtainable by reacting a compound of formula (II) or of formula (III) or of formula (IV) or of formula (V) with a mixture of alcohols of formula (VI) and a compound of formula (VII) or an amine of formula (VIII) or (IX) or an oligo- or polyorganosiloxane, having polyoxyalkylene groups, of general formula (X) or a compound of formula (XI), preferably of formula (XIa). This reaction is preferably carried out at a temperature in the range from 40 to 70 ^ and at an acid pH. In a further advantageous embodiment, the product obtained after the reaction is neutralized and excess alcohol of formula (VI) is distilled off thereafter.

The compositions of the present invention are usable to particular advantage in the form of aqueous compositions comprising one or more of the compositions described above, preferably with a water content of 20 to 60 wt%.

It is advantageous in some cases when the aqueous compositions, in addition to compositions of the present invention, further comprise NaCI, KCI or LiCI, preferably in amounts of 0.5 to 5 wt%, because this may yield better results for the cellulose crosslinkage in particular.

Compositions according to the present invention are very useful for the treatment of fiber materials comprising natural fibers, preferably cellulose or wool, or synthetic fibers, in particular polyester, polyamide, polyacrylonitrile, polyacrylate and viscose, and also mixtures thereof, in particular fiber materials that are 50 to 100 wt% cellulose. Particularly preferred materials are cotton articles in the form of wovens for various fields of use, for example for shirting. Other materials are synthetic wovens, for example for the fabrication of awnings.

Compositions of the present invention and/or aqueous compositions thereof are very useful for the moist cure of cotton materials. This moist cure can be carried out according to known methods.

Compositions according to the present invention may comprise further products known to a person skilled in the art which are typically employed to achieve various effects on textiles.

When products according to the present invention are employed on textiles together with hydrophobic polymers, for example polysiloxanes not functionalized to be hydrophilic or with polyethylene waxes, a further enhancement of the hydrophilic properties of the textiles is achievable. One reason for this might be the inversion of the orientation of the surfactant compounds on the fiber materials thus finished.

In one possible use of compositions according to the present invention, a composition comprising a proportion of at least one converted compound of one of the formulae (VII) or (VIII) or (IX) or (X) or preferably (XI), in particular (Xla), in combination with polymers suitable for generating barrier effects on textiles is employed and the composition thus obtained is employed for the treatment of fiber materials to produce enhanced barrier effects. Barrier effect refers to the ability of textiles to reject certain media, particularly aqueous and oily liquids, but also dirt, i.e. to prevent penetration thereof into the fibers in the event of contact. Various polymers are suitable for this. These include polymers having perfluoroalkyi groups, for example polyurethanes or poly(meth)acrylates and also their copolymers, which contain still further monomers. Also suitable for this are, for example, polyorganosiloxanes having certain functional groups.

In one possible use of compositions according to the present invention, a composition comprising a proportion of at least one converted compound of one of the formulae (VII) or (VIII) or (IX) or (X) or (XI), preferably (Xla), in combination with polymers suitable for generating barrier effects on textiles is employed and the composition thus obtained is employed for the treatment of fiber materials to produce or enhance soil release effects. It is thus possible to employ compositions of the present invention and polymers that are suitable for generating barrier effects on textiles but that in themselves do not enable any soil release effects to achieve a certain level of soil release properties on textiles. On employing compositions of the present invention together with polymers that are suitable for generating barrier effects on textiles and that in themselves already enable soil release effects, it is possible to further enhance these soil release effects. In the last two applications, the compositions of the present invention can be employed as a surfactant or co-surfactant in the emulsification of the polymers, but they can also be added to the polymer emulsions after emulsification, where they then, in the treatment of fiber materials, act as a carrier to provide for better importation of the polymers into the fiber materials. In a further possible application, a composition according to the present invention is employed to import free radical scavengers onto fiber materials, in particular a composition comprising a proportion of a converted compound of formulae (II), (IV) or (V) where X = S, examples of free radical scavengers being vitamin C or vitamin E, which have an antioxidative effect.

In a further possible application, a composition comprising an optical brightener, in particular an optical brightener based on a stilbene structure, or a UV absorber, preferably in converted form, is employed to import optical brighteners, in particular optical brighteners based on a stilbene structure, or UV absorbers onto fiber materials.

One example of a suitable UV absorber is TINUVIN^® 1 130 from BASF. Suitable UV absorbers further include the compounds 2-(2-hydroxy-5-methylphenyl)benzotriazole and 2-hydroxy-4- methoxybenzophenone and also polyethylene glycol mono(distyrylphenyl) ether.

A number of compositions according to the present invention are also employable as defoamers.

Selected compositions according to the present invention are also useful as additives for adhesives in that advantages accrue, for example in conforming the crosslinking time by the molecular structure and the polarity of the side chains, which has an effect on the evaporation rate of the water, to the particular requirements.

Selected compositions according to the present invention are similarly also useful as phase transfer catalysts. Where compositions according to the present invention contain the abovementioned reaction products, the latter are immobilizable by reaction with hydroxyl and/or amino groups.

It is known that wood alone and also in combination with other materials can be optimized with respect to its quality and performing ability and also in its processing and design possibilities. This is of interest because wood-based structural and functional materials, such as laminated veneer lumber for example, become more stable, more flexible, more elastic, lighter in weight, more efficient in terms of strength utilization, and also more weather and fire resistant.

Appropriately selected products according to the present invention are advantageous here in the form of additives to adhesive compositions as based, for example, on polyvinyl acetate and MUF resins, because their use makes it possible to adjust the porosity, the agglomeration characteristics and the wash-off characteristics of as yet uncrosslinked adhesive compositions in the desired manner. A larger porosity for layers enhances thermally insulating properties of, for example, laminated veneer lumber, which is made up of layers. A punctuately stronger agglomeration of the adhesive composition leads punctuately to a greater contact pressure and hence to stronger punctuate adherence. Compositions according to the present invention are also useful, for example, in the manufacture of chipboard for crosslinking or as additive for adhesives in the manufacture of laminated veneer lumber.

Compositions according to the present invention are also employable as components in the manufacture of amino resins.

A further aspect of the invention is a compound of formula (XII),

where R³ stands for H or for— CH₂— O— R²,

all R and R² each independently stand for H or for linear or branched alkyl of 1 to 5 carbon atoms, preferably for CH₃ or C₂H₅ or C₃H₇, or for or for

-(-CH₂-CH-O^ R ¹³ where m is a number from 4 to 8 and q is a number from 1 to 3 and

where R ³ stands for H or linear or optionally branched alkyl of 1 to 4 carbon atoms, preferably for H or n-C₄H₉,

with the proviso that at least one of the R or R² moieties present does not stand for H.

The compounds of formula (XII) are obtainable by similar methods to the preparation of the prior art compounds of the following formula: where thiourea is chosen as starting compound instead of urea. The examples which follow illustrate the invention.

Example 1 (inventive)

207.3 g of an aqueous 60% glyoxal solution were initially charged at room temperature and adjusted with a dilute sodium hydroxide solution to pH 5.0.

At this point 279.9 g of dimethylolurea were admixed by stirring. This resulted in a white pasty mass. Thereafter, 21 .8 g of a 37% formalin solution and 72.6 g of methanol were admixed and the admixture was heated up to 40

The initial charge was subsequently adjusted to pH 7.0 with dilute sodium hydroxide solution and/or hydrochloric acid and heated to 70 °C. The initial charge turned into a thin, clear and bright yellow liquid in the process.

After one hour at 70 ^<€, the batch was cooled to 50 ^<€.

Thereafter, 183.7 g of MARLIPAL^® O 13/50 (oxo process alcohol C13 with 5 mol of EO, obtainable from Sasol) and 265.9 g of methanol were admixed.

The etherification was started at 50 'Ό by admixture of 5.0 g of concentrated hydrochloric acid (31 -33 wt%). The exothermic reaction resulted in a temperature rise of about δ'Ό. After 7 minutes, the etherification was stopped by admixture of 2.0 g of a 50% sodium hydroxide solution and 0.3 g of triethanolamine (99% strength).

The initial charge was subsequently adjusted to pH 5.9 with dilute sodium hydroxide solution and/or hydrochloric acid. This was followed by 6 hours at max. 70^ in vacuo down to an absolute pressure of 100 mbar to remove 228 g of a methanol-water mixture by distillation. The result after cooling to room temperature was a relatively thin, clear, bright yellow liquid product.

To test the properties of the composition according to the present invention, an aqueous finishing liquor was made up from 220 g/l of composition according to Example 1 , 1 10 g/l of KNITTEX CATALYST UMP (available from Huntsman) and 1 g/l of concentrated hydrochloric acid (31 -33 wt%). An aqueous finishing liquor was made up for comparison from 220 g/l of KNITTEX^® FA CONC (dimethyloldihydroxyethyleneurea, methanol etherified, available from Huntsman), 1 10 g/l of KNITTEX CATALYST UMP (aqueous solution of several organic and inorganic acidic compounds, available from Huntsman) and 1 g/l of concentrated hydrochloric acid (31 -33 wt%). Swatches of a woven shirting fabric in 100% cotton with a basis weight of 1 10 g/m², bleached but not optically brightened, were impregnated with aqueous liquors in the abovementioned compositions on a laboratory pad-mangle to a wet pick-up of 66 wt%, then dried to a residual moisture content of 7% and thereafter stored at 30 °C for 20 hours.

Thereafter, the samples were washed at 40 °C for 10 minutes with an aqueous solution of 10 g/l sodium carbonate, then neutralized once with hot water, thereafter once with cold water, further with an aqueous solution of 0.5 g/l INVATEX^® AC (aqueous solution of citric acid having a low polymer content, available from Huntsman), then rinsed with cold water and finally dried at 1 10° for 10 minutes. The hydrophilic properties of the textile swatches thus finished and also in each case of a non-finished textile swatch were subsequently evaluated as per the Water Drop Test AATCC Test Method 79, Absorbency of Textiles (drop test) and the wicking properties as per Wicking Test, AATCC Test Method 197-201 1 (height of rise test to evaluate the capillarity of textiles). In the drop test, lower values in seconds signify better hydrophilic properties. In this test, a drop of water is applied to a fabric and the wetting of the fabric is observed. The value in seconds describes the time of complete wetting by the drop of water. In the wicking test, a textile sample is dipped vertically at the lower edge into water and it is observed how high the liquid has risen in the fabric after a certain time. The fabric is presented once with the warp in the vertical direction and once with the weft in the vertical direction. The composition according to Inventive Example No. 1 shows clearly better hydrophilic effects in this than the comparative test based on KNITTEX FA CONC, see Tables 1 and 2. Table 1

Untreated As per KNITTEX

Ex. 1 FA CONC

Water Drop Test

AATCC Test Method 79, Absorbency of Textiles

completely wetted after (seconds) 1 1 10 60

Table 2

Wicking Test Untreated As per KNITTEX (height of rise in cm) Ex. 1 FA CONC

AATCC test method warp after 1 min 2.5 3 0.2 197-201 1 after 5 min 5 5.5 1 .3 after 10 min 6.3 7 2.5 after 1 min 2.5 2.5 0.2 weft after 5 min 4.5 4.7 0.7 after 10 min 5.5 5.7 1 .5

The distillative removal of the methanol as per Example 1 can be effected across different time intervals. As the distillation time increases, there is also an increase in the degree of reaction of MARLIPAL^® O 13/50 with the dimethyloldihydroxyethyleneurea (DMDHEH). Accordingly, the reaction is controllable so as to produce products having different properties.

Example 1 was repeated using different time intervals for the distillation time, the corresponding values for this are found below in Table 3.

Table 3

Of the products obtained, an aqueous dispersion having a 200 g/l content was prepared. This aqueous dispersion was vigorously shaken and then left to stand for 30 minutes. It can be seen from the aqueous dispersions that their sudsing increases with increasing distillation time, see Figure 1 .

After prolonged standing and disappearance of the foam, the aqueous dispersions were seen to become clearer and/or more transparent with increasing distillation time and/or increasing degree of transetherification, see Figure 2.

Both tests indicate that increasing distillation time and hence greater conversion of MARLIPAL^® O 13/50 leads to reaction products having enhanced surfactant properties. As the distillation time increases, the viscosity of the product obtained in each case also increases. Example 2 (inventive)

150.0 g of an aqueous 60% glyoxal solution were initially charged at room temperature and adjusted with a dilute sodium hydroxide solution to pH 5.0.

At this point 202.5 g of dimethylolurea were admixed by stirring. This resulted in a white pasty mass. Thereafter, 15.8 g of a 37% formalin solution and 52.5 g of methanol were admixed and the admixture was heated up to 40 °C.

After one hour at 70 °C, the batch was cooled to 50 °C.

Thereafter, 202.5 g of methanol were admixed.

The etherification was started at 50 °C by admixture of 3.6 g of concentrated hydrochloric acid (31 -33 wt%). The exothermic reaction resulted in a temperature rise of about 8°C. After 7 minutes, the etherification was stopped by admixture of 1 .4 g of a 50% sodium hydroxide solution and 0.2 g of triethanolamine (99% strength).

The initial charge was subsequently adjusted to pH 5.9 with dilute sodium hydroxide solution and/or hydrochloric acid. This was followed by 2 hours at max. 70 °C in vacuo down to an absolute pressure of 100 mbar to remove 197 g of a methanol-water mixture by distillation. After cooling to room temperature, 132.9 g of MARLIPAL^® O 13/50 were stirred in. The essential difference from Example 1 is therefore that the oxo process alcohol C13 with 5 mol of EO was admixed after distillative removal of methanol, i.e. no etherification took place with oxo process alcohol C13 with 5 mol of EO.

The result was a relatively thin, clear and bright yellow liquid product.

To test the properties of the composition according to the present invention, an aqueous finishing liquor was made up from 220 g/l of composition according to Example 2, 100 g/l of KNITTEX CATALYST UMP, 1 g/l of concentrated hydrochloric acid (31 -33 wt%) and 50 g/l of TURPEX^® ACN NEW (aqueous dispersion of a wax, a customary recipe component for the crosslinking of cotton fabric, available from Huntsman). An aqueous finishing liquor was made up for comparison from 220 g/l of KNITTEX^® FA CONC, 100 g/l of KNITTEX CATALYST UMP, 1 g/l of concentrated hydrochloric acid (31 -33 wt%) and 50 g/l of TURPEX^® ACN NEW.

Swatches of a woven shirting fabric in 100% cotton poplin, dyed but not optically brightened, were impregnated with aqueous liquors in the abovementioned compositions on a laboratory pad-mangle to a wet pick-up of 66 wt%, then dried to a residual moisture content of 7% and thereafter stored at 30 °C for 20 hours. Thereafter, the samples were washed at 40 °C for 10 minutes with an aqueous solution of 10 g/l sodium carbonate, then washed once with hot water, thereafter with cold water, further neutralized with an aqueous solution of 0.5 g/l INVATEX^® AC, then rinsed with cold water and finally dried at 1 10° for 10 minutes. The hydrophilic properties of the textile swatches thus finished and also in each case of a non-finished textile swatch were subsequently evaluated as per the Water Drop Test AATCC Test Method 79, Absorbency of Textiles (drop test) and the wicking properties as per Wicking Test, AATCC Test Method 197- 201 1 (height of rise test to evaluate the capillarity of textiles). The formaldehyde content on the fabric was additionally also tested to J IS L 1041 :201 1 , a Japanese standard (corresponds to ISO 14184-1 :1998). The composition according to Inventive Example No. 2 shows clearly better hydrophilic effects and lower formaldehyde content in this than the comparative test based on KNITTEX FA CONC, see Tables 4 und 5.

Table 4

Example 3 (inventive) 177.5 g of an aqueous 60% glyoxal solution were initially charged at room temperature and adjusted with a dilute sodium hydroxide solution to pH 5.0.

At this point 239.6 g of dimethylolurea were admixed by stirring. This resulted in a white pasty mass. Thereafter, 18.7 g of a 37% formalin solution and 62.2 g of methanol were admixed and the admixture was heated up to 40^.

After one hour at 70 ^<C, the batch was cooled to 50 ^<C.

Thereafter, 78.6 g of MARLIPAL^® O 13/50 (oxo process alcohol C₁₃ with 5 mol of EO) and 227.6 g of methanol were admixed. The etherification was started at 50 'Ό by admixture of 4.3 g of concentrated hydrochloric acid (31 -33 %). The exothermic reaction resulted in a temperature rise of about 9 'Ό. After 8 minutes, the etherification was stopped by admixture of 1 .7 g of a 50% sodium hydroxide solution and 0.2 g of triethanolamine (99% strength).

The initial charge was subsequently adjusted to pH 5.9 with dilute sodium hydroxide solution and/or hydrochloric acid.

This was followed by the admixture of 36.7 g of trans-4-hydroxystilbene 98%. During the subsequent heating to 70 °C, the appearance of the initial charge changed from cloudy and orange to clear and bright yellow.

This was followed by 6 hours at max. 70^ in vacuo down to an absolute pressure of 100 mbar to remove 195.2 g of a methanol-water mixture by distillation.

The batch was then cooled down. On reaching about 45 °C, it was admixed with 45 g of demineralized water.

Thereafter, the initial charge was adjusted with dilute sodium hydroxide solution from pH 5.2 to pH 6.5.

The result on cooling to room temperature was a pasty, milkily cloudy and cream-colored product.

Example 4 (inventive) A reactor was initially charged with 80.2 g of methanol, 243.2 g of aqueous formaldehyde at 37 wt% and 1 14.3 g of thiourea at room temperature. The pH was adjusted to 8.2 with dilute sodium hydroxide solution. The batch was heated to 54 ^<Ό for 5 hours at pH 8.2.

Thereafter, 137 g of MARLIPAL^® O 13/50 (oxo process alcohol C₁₃ with 5 mol of EO) and 174.3 g of methanol were admixed. The temperature was 47 °C.

The etherification was started by admixture of 19.5 g of concentrated hydrochloric acid (32%).

The exothermic reaction resulted in a temperature rise of 9°C. After 9 minutes the etherification was stopped by admixture of 7.5 g of 50% sodium hydroxide solution.

The initial charge was then adjusted to pH 6.0 with dilute sodium hydroxide solution and/or hydrochloric acid. This was followed by 6.5 hours at max. 70 ^ in vacuo down to an absolute pressure of 90 mbar at the end of the time interval to remove 445 ml of a methanol/water mixture by distillation.

The result after cooling to room temperature was a very thick, cloudy product having a dry- matter content of 98 wt%.

Use example: 1 . Dyeing:

Mercerized pieces of cotton were dyed by the pad-batch process (using a pad-mangle) with a dye solution containing 2.4 g/l of NOVACRON® Blue C-R (reactive dye from HUNTSMAN), 15 ml/l of sodium hydroxide 36°B, 70 ml/l of sodium silicate 38-40 °B, 2 g/l of LYOPRINT® RG (dyeing auxiliary from HUNTSMAN) and 1 g/l of CIBAFLOW® PAD (dyeing auxiliary from

HUNTSMAN). After pad-mangling to a wet pick-up of 70 wt%, the textile pieces were stored at room temperature for 16 hours, then rinsed three times with water (cold, at the boil, cold) and dried.

2. Wako Test The BPO fastness was determined using the "Wako Test", (internal test method of

HUNTSMAN). BPO here stands for benzoyl peroxide or, to be more precise, dibenzoyl peroxide, which is used in dermatological products and after application to the skin may harm the color of textiles because it tends to form free radicals. To this end, 50 g of water, 0.1 g of Wako V50 (2,2'-azobis[2-methylpropionamidine] dihydrochloride, CAS NO. 2997-92-4), 0.15 g of the inventive composition prepared as described above and 1 g of a dyed swatch were stirred at 65-70 °C for 2 hours. The swatch was then rinsed and dried. Thereafter, the swatch was in a slightly decolorized state.

For reference, 50 g of water, 0.1 g of Wako V50 and 1 g of dyed swatch were stirred at 65-70 °C for 2 hours. The swatch was then rinsed and dried. Thereafter the swatch was in a very severely decolorized state.

Colorimetric evaluation.

Scale: Rating 1 to 5 (1 = very bad, 5 = very good)

The test shows that the inventive composition prepared as described above clearly has the properties of a free radical scavenger.

3. Aftertreatment

A dyed swatch was finished with 20 g/l of the inventive composition prepared as described above, by the pad-dry-thermofix process (described e.g. in DE 4133995) at a pH of 4 to 8 and wet pick-up of 100 wt%, then dried at 1 10°C for 1 minute and thermofixed at 170°C for 2 minutes.

Example 5 (inventive)

159.7 g of an aqueous 60% glyoxal solution were initially charged at room temperature and adjusted with a dilute sodium hydroxide solution to pH 5.0.

At this point 215.8 g of dimethylolurea were admixed by stirring. This resulted in a white pasty mass. Thereafter, 16.8 g of a 37% formalin solution and 56.0 g of methanol were admixed and the admixture was heated up to 40 'Ό.

After one hour at 70 ^<€, the batch was cooled to 50 ^<€.

Thereafter, 107.6 g of MARLIPAL^® O 13/50 (oxo process alcohol C₁₃ with 5 mol of EO) and 109.7 g of ZONYL® Fluorosurfactant FS-300 (40% in water, an ethoxylated perfluoroalkylethyl alcohol available from DuPont) and 203.5 g of methanol were admixed in succession.

The etherification was started at 50 'Ό by admixture of 7.8 g of concentrated hydrochloric acid (31 -33 wt%). The exothermic reaction resulted in a temperature rise of about Θ 'Ό. After 9 minutes, the etherification was stopped by admixture of 4.8 g of a 50% sodium hydroxide solution and 0.2 g of triethanolamine (99% strength).

The initial charge was subsequently adjusted to pH 5.8 with dilute sodium hydroxide solution and/or hydrochloric acid.

Thereafter, the initial charge was heated to 70 °C.

This was followed by 6 hours at max. 70^ in vacuo down to an absolute pressure of 100 mbar to remove 175.8 g of a methanol-water mixture by distillation.

Thereafter, the batch was cooled. After reaching about 45^ it was admixed with 47 g of demineralized water.

Thereafter, the initial charge was adjusted with dilute sodium hydroxide solution to pH 5.2 to pH 6.5.

The result after cooling to room temperature was a bright yellow, clear product. Example 6 a) (inventive)

107.6 g of an aqueous 60% glyoxal solution were initially charged at room temperature and adjusted with a dilute sodium hydroxide solution to pH 5.0.

At this point 145.3 g of dimethylolurea were admixed by stirring. This resulted in a white pasty mass. Thereafter, 1 1 .3 g of a 37% formalin solution and 37.9 g of methanol were admixed and the admixture was heated up to 40 'Ό. The initial charge was subsequently adjusted to pH 7.0 with dilute sodium hydroxide solution and/or hydrochloric acid and heated to 70 °C. The initial charge turned into a thin, clear and bright yellow liquid in the process.

After one hour at 70 ^<€, the batch was cooled to 50 °C.

Thereafter, 130.0 g of JEFFAMINE^® M-600 (polyether amine with 9 mol of propylene oxide and 1 mol of ethylene oxide, methyl etherified and pH 12, obtainable from Huntsman) were admixed portionwise while the pH was maintained in the range 5.1 -6.4 by portionwise admixture of concentrated hydrochloric acid (31 -33%). After admixture of altogether 18.0 g of concentrated hydrochloric acid (31 -33%) for this, the initial charge had a pH of 5.3. Then, 132.0 g of methanol were admixed. The etherification was started at 50 °C by admixture of 10.7 g of concentrated hydrochloric acid (31 -33%). The exothermic reaction resulted in a temperature increase of about 7^qC. After 9 minutes, the etherification was stopped by admixture of 4.1 g of 50% sodium hydroxide solution and 0.2 g of triethanolamine (99%).

The initial charge was subsequently adjusted to pH 5.9 with dilute sodium hydroxide solution and/or hydrochloric acid. This was followed by 6 hours at max. 65 'Ό in vacuo down to an absolute pressure of 100 mbar to remove 163 g of a methanol-water mixture by distillation. The result after cooling down to room temperature was a relatively thick, clear and dark red liquid product having a viscosity of 7000 mPa^»s, as measured at 25^qC.

Example 6 b) (inventive) Example 6 a) was repeated except that JEFFAMINE^® M-600 was admixed after the reaction, not before.

At this point 145.3 g of dimethylolurea were admixed by stirring. This resulted in a white pasty mass. Thereafter, 1 1 .3 g of a 37% formalin solution and 37.9 g of methanol were admixed and the admixture was heated up to 40 'Ό.

After one hour at 70 ^<€, the batch was cooled to 50 °C.

Then, 132.0 g of methanol were admixed.

The etherification was started at 50 'Ό by admixture of 5.5 g of concentrated hydrochloric acid (31 -33 wt%). The exothermic reaction resulted in a temperature increase of about δ'Ό. After 9 minutes, the etherification was stopped by admixture of 3.5 g of 50% sodium hydroxide solution and 0.2 g of triethanolamine (99%).

The initial charge was subsequently adjusted to pH 5.9 with dilute sodium hydroxide solution and/or hydrochloric acid. This was followed by 3 hours at max. 70^ in vacuo down to an absolute pressure of 100 mbar to remove 156 g of a methanol-water mixture by distillation. The result after cooling down to room temperature was a relatively thin, clear and bright yellow liquid product having a viscosity of 500 mPa^»s, as measured at 25 °C.

Thereafter, 130.0 g of JEFFAMINE^® M-600 were admixed portionwise while the pH was maintained in the range 5.1 -6.4 by portionwise admixture of concentrated hydrochloric acid (31 -33%). After admixture of altogether 18.0 g of concentrated hydrochloric acid (31 -33%) for this, the initial charge had a pH of 5.3. The end product was clear, dark red and had a viscosity of 600 mPa^»s, as measured at 25°C. Table 6 hereinbelow shows once more the essential differences between Example 6 a) and Example 6 b).

Table 6

The products obtained were used to prepare an aqueous dispersion having a content of 200 g/l. These dispersions were vigorously shaken and then left to stand for 30 minutes. Afterwards, the aqueous dispersions were temperature regulated to 45^ in a water bath. The comparatively strong cloudiness in the product of Example 6 a) shows that the reaction reduces the HLB value, see Figure 3.

Example 7 a) (inventive) 168.14 g of melamine were initially charged at room temperature. At this point 0.53 g of triethanolamine (99%) and 342.16 g of a 37% formalin solution and 84.07 g of diethylene glycol were admixed by stirring. Then, 0.14 g of a 25% sodium hydroxide solution was stirred in. The pH of the initial charge rose from 9.0 to 10.0 in the process.

Thereafter, the initial charge was heated up to 70^ and maintained at 70^ for 10 minutes. The batch was subsequently cooled down to 65 °C and admixed with 254.5 g of methanol.

The batch temperature decreased to about 55 °C in the process. After the batch temperature had come back up to 65^, the alkaline etherification was started by admixing 17.5 g of a 50% sodium hydroxide solution.

Thereafter, the initial charge was heated up to 70^ and maintained at 70^ for 40 minutes. The etherification was subsequently stopped by mixing 17.7 g of 60% acetic acid. The pH was adjusted to 10.7 (tolerance +/- 0.3%) in the process.

Thereafter, 157.0 g of MARLIPAL^® O 13/50 were stirred in. This was followed by 6 hours at max. 65 'Ό in vacuo down to an absolute pressure of 100 mbar to remove 380 g of a methanol- water mixture by distillation.

The result after cooling down to room temperature was a thick, clear and colorless liquid product having a viscosity of 35 000 mPa^»s, as measured at 25^qC, and a pH of 9.2.

Example 7 b) (inventive)

Example 7 a) was repeated except that MARLIPAL^® O 13/50 was admixed after the reaction, not before.

168.14 g of melamine were initially charged at room temperature. At this point 0.53 g of triethanolamine (99%) and 342.16 g of a 37% formalin solution and 84.07 g of diethylene glycol were admixed by stirring. Then, 0.14 g of a 25% sodium hydroxide solution was stirred in. The pH of the initial charge rose from 9.0 to 10.0 in the process.

Thereafter, the initial charge was heated up to 70^ and maintained at 70^ for 40 minutes. The etherification was subsequently stopped by admixing 17.7 g of 60% acetic acid. The pH was adjusted to 10.7 (tolerance +/- 0.3%) in the process.

This was followed by 3 hours at max. 65 'Ό in vacuo down to an absolute pressure of 100 mbar to remove 351 g of a methanol-water mixture by distillation.

The result after cooling down to room temperature was a relatively thin, clear and bright yellow liquid product having a viscosity of 600 mPa^»s, as measured at 25 °C.

Thereafter, 157.0 g of MARLIPAL^® O 13/50 were stirred in. The end product was likewise a relatively thin, clear and colorless liquid having a viscosity of 800 mPa^»s, as measured at 25°C, and a pH of 9.3.

Table 7 hereinbelow shows once more the essential differences between Example 7 a) and Example 7 b). Table 7

The products obtained were used to prepare an aqueous dispersion having a content of 200 g/l. These dispersions were vigorously shaken and then left to stand for 30 minutes. Afterwards, the aqueous dispersions were temperature regulated to 53^ in a water bath. The clearer appearance for the product of Example 7 a) shows that the reaction increases the HLB value, see Figure 4.

Example 8 a) (inventive)

1 16.8 g of an aqueous 60% glyoxal solution were initially charged at room temperature and adjusted with a dilute sodium hydroxide solution to pH 5.0.

At this point 157.7 g of dimethylolurea were admixed by stirring. This resulted in a white pasty mass. Thereafter, 12.2 g of a 37% formalin solution and 41 .1 g of methanol were admixed and the admixture was heated up to 40 'Ό.

After one hour at 70 ^<€, the batch was cooled to 50 ^<€.

Thereafter, 123.2 g of Emulgator EL emulsifier (castor oil polyglycol ether with 36 mol of EO, obtainable from Scharer & Schlapfer AG) and 144.0 g of methanol were admixed.

The etherification was started at 50 'Ό by admixture of 5.5 g of concentrated hydrochloric acid (31 -33%). The exothermic reaction resulted in a temperature increase of about 9°C. After 9 minutes, the etherification was stopped by admixture of 3.4 g of 50% sodium hydroxide solution and 0.2 g of triethanolamine (99%).

The initial charge was subsequently adjusted to pH 5.9 with dilute sodium hydroxide solution and/or hydrochloric acid. This was followed by 5 hours at max. 65 'Ό in vacuo down to an absolute pressure of 100 mbar to remove 177 g of a methanol-water mixture by distillation. The result after cooling down to room temperature was a thick, clear and bright yellow liquid product having a viscosity of 24 000 mPa^»s, as measured at 25 °C, and a pH of 6.1 . Example 8 b) (inventive)

Example 8 a) was repeated except that Emulgator EL emulsifier was admixed after the reaction, not before.

After one hour at 70 ^<€, the batch was cooled to 50 ^<€.

Subsequently, 144.0 g of methanol were admixed.

The etherification was started at 50 'Ό by admixture of 5.9 g of concentrated hydrochloric acid (31 -33 wt%). The exothermic reaction resulted in a temperature increase of about 10°C. After 9 minutes, the etherification was stopped by admixture of 3.6 g of 50% sodium hydroxide solution and 0.2 g of triethanolamine (99%). The initial charge was subsequently adjusted to pH 5.9 with dilute sodium hydroxide solution and/or hydrochloric acid. This was followed by 3 hours at max. 65 °C in vacuo down to an absolute pressure of 100 mbar to remove 169 g of a methanol-water mixture by distillation.

The result after cooling down to room temperature was a relatively thick, clear and bright yellow liquid product having a viscosity of 500 mPa^»s, as measured at 25 °C.

Thereafter, 123.2 g of Emulgator EL emulsifier were stirred in and the pH was then adjusted to pH 6.1 by admixture of dilute hydrochloric acid.

The end product was clear, bright yellow and had a viscosity of 3500 mPa^»s at 25°C.

Table 8 shows once more the essential differences between Example 8 a) and Example 8 b).

Table 8

The products obtained were used to prepare samples with the compositions itemized in table 9. Table 9 A B C D E F

Example 8 a) 10 g - - - - -

Example 8 b) - 10 g - - - -

Emulgator EL emul¬

- - 3.0 g - - - sifier

Example 8 b)

without Emulgator - - - 7.0 g - - EL emulsifier

methyl isobutyl ke¬

10 g 10 g 10.0 g 10.0 g 10.0 g - tone

water 10 g 10 g 10.0 g 10.0 g 10.0 g 10.0 g

After simultaneous vigorous shaking, samples A, B and C give rise to dispersions having a pasty consistency.

The amount of Emulgator EL emulsifier in samples A, B and C is the same.

Sample D is a non-inventive comparator based on Example 8 b) without addition of Emulgator EL emulsifier. After shaking, sample D remains a thin liquid and immediately separates into 2 clear phases, see Figure 5.

After standing for 6 hours, the initially pasty dispersions A and B were found to have liquefied, while dispersion C is still pasty, see Figure 6.

After standing for 1 day, both the inventive reaction product of Example 8 a) (in sample A) and the inventive mixture of Example 8 b) (in sample B) can be clearly seen to be phase transfer catalysts, see Figure 7.

This is apparent from the volume increases (depicted in Figure 7 via measured phase heights in cm) of the MIBK phases (top) in samples A and B, while the reaction product of Example 8 a) emulsifies water in the form of a microemulsion (clear top phase) and the mixture of

Example 8 b) emulsifies water in the form of a macroemulsion (milky top phase), in contrast to the non-inventive mixture C with castor oil polyglycol ether alone, which has remained pasty, and mixture D with product of Example 8 b) without emulsifier addition in the solvent mixture of MIBK and water, which do not lead to a volume increase of the MIBK phase. The visual images of samples A-F are additionally supported by infrared-spectroscopic analyses, as shown in Figure 8.

The spectra in the wavenumber region of 3000-4000 cm^"1 show the distinct presence of water in the respective MIBK phases of inventive samples A and B, in contrast to samples D and E. Non-inventive mixture C with castor oil polyglycol ether alone was not measured, since it remained pasty.

Example 9 a) (inventive)

120.2 g of an aqueous 60% glyoxal solution were initially charged at room temperature and adjusted with a dilute sodium hydroxide solution to pH 5.0.

At this point 162.3 g of dimethylolurea were admixed by stirring. This resulted in a white pasty mass. Thereafter, 12.6 g of a 37% formalin solution and 42.3 g of methanol were admixed and the admixture was heated up to 40 'Ό.

After one hour at 70 ^<€, the batch was cooled to 50 ^<€.

Thereafter, 1 14.7 g of Genamin^® C 050 (C8/C18 cocofatty amine ethoxylate with 5 mol of ethylene oxide and pH 9-10, obtainable from Clariant) were admixed portionwise while the pH was maintained in the range 5.1 -6.4 by portionwise admixture of concentrated hydrochloric acid (31 -33%). After admixture of altogether 28.9 g of concentrated hydrochloric acid (31 -33%) for this, the initial charge had a pH of 5.3.

Then, 148.0 g of methanol were admixed.

The etherification was started at 50 'Ό by admixture of 7.5 g of concentrated hydrochloric acid (31 -33%). The exothermic reaction resulted in a temperature increase of about 7°C. After 9 minutes, the etherification was stopped by admixture of 3.7 g of 50% sodium hydroxide solution and 0.2 g of triethanolamine (99%).

The initial charge was subsequently adjusted to pH 5.9 with dilute sodium hydroxide solution and/or hydrochloric acid. This was followed by 5 hours at max. 65 'Ό in vacuo down to an absolute pressure of 100 mbar to remove 182 g of a methanol-water mixture by distillation.

The result after cooling down to room temperature was a relatively thick, clear and bright brown liquid product having a viscosity of 4100 mPa^»s, as measured at 25^qC.

Example 9 b) (inventive)

Example 9 a) was repeated except that Genamin^® C 050 was admixed after the reaction, not before.

At this point 162.3 g of dimethylolurea were admixed by stirring. This resulted in a white pasty mass. Thereafter, 12.6 g of a 37% formalin solution and 42.3 g of methanol were admixed and the admixture was heated up to 40 'Ό. The initial charge was subsequently adjusted to pH 7.0 with dilute sodium hydroxide solution and/or hydrochloric acid and heated to 70 °C. The initial charge turned into a thin, clear and bright yellow liquid in the process.

After one hour at 70 ^<€, the batch was cooled to 50 °C.

Then, 132.0 g of methanol were admixed.

The etherification was started at 50 'Ό by admixture of 6.1 g of concentrated hydrochloric acid (31 -33 wt%). The exothermic reaction resulted in a temperature increase of about δ'Ό. After 9 minutes, the etherification was stopped by admixture of 3.7 g of a 50% sodium hydroxide solution and 0.2 g of triethanolamine (99%).

The initial charge was subsequently adjusted to pH 5.9 with dilute sodium hydroxide solution and/or hydrochloric acid. This was followed by 3 hours at max. 65 'Ό in vacuo down to an absolute pressure of 100 mbar to remove 173 g of a methanol-water mixture by distillation. The result after cooling down to room temperature was a relatively thin, clear and bright yellow liquid product having a viscosity of 500 mPa^»s, as measured at 25 °C.

Thereafter, 1 14.7 g of Genamin^® C 050 were admixed portionwise while the pH was maintained in the range 5.1 -6.4 by portionwise admixture of concentrated hydrochloric acid (31 -33%). After admixture of altogether 28.9 g of concentrated hydrochloric acid (31 -33%) for this, the initial charge had a pH of 5.3.

The end product was clear, bright brown and had a viscosity of 550 mPa^»s, as measured at 25°C.

Table 10 hereinbelow shows once more the essential differences between Example 9 a) and Example 9 b).

Table 10

The products obtained were used to prepare dispersions having a content of 330 g/l, by mixing with a mixture consisting of 335 ml of water and 335 ml of methyl isobutyl ketone (MIBK).

Following simultaneous vigorous shaking, not only the product of Example 9 a) but also the product of Example 9 b) display the phase transfer catalyst effect.

Directly after shaking, Example 9 a) produces a milky emulsion, where the product of

Example 9 b) is slightly cloudy, see Figure 9. After standing for 1 minute and/or 2 minutes, distinct separation is apparent for Example 9 a), see Figures 10.

After standing for 5 minutes, Example 9 a) and Example 9 b) each have a clear top, mainly MIBK-containing phase.

The bottom, mainly water-containing phase is still slightly cloudy in Example 9 a), but clear in Example 9 b), see Figure 1 1 .

Example 10 a) (inventive)

1 15.7 g of an aqueous 60% glyoxal solution were initially charged at room temperature and adjusted with a dilute sodium hydroxide solution to pH 5.0.

At this point 156.2 g of dimethylolurea were admixed by stirring. This resulted in a white pasty mass. Thereafter, 12.1 g of a 37% formalin solution and 40.7 g of methanol were admixed and the admixture was heated up to 40 'Ό.

After one hour at 70 ^<€, the batch was cooled to 50 ^<€.

Thereafter, 123.6 g of TEGOPREN^® 5847 (polyether-polymethylsiloxane copolymer with 80:20 wt% of EO/PO in the polyether, available from Evonik) and 144.5 g of methanol were admixed.

The etherification was started at 50 'Ό by admixture of 4.0 g of concentrated hydrochloric acid (31 -33%). The exothermic reaction resulted in a temperature increase of about 9°C. After 9 minutes, the etherification was stopped by admixture of 2.5 g of 50% sodium hydroxide solution and 0.2 g of triethanolamine (99%).

The initial charge was subsequently adjusted to pH 5.9 with dilute sodium hydroxide solution and/or hydrochloric acid. This was followed by 6 hours at max. 65 'Ό in vacuo down to an absolute pressure of 100 mbar to remove 176 g of a methanol-water mixture by distillation. The result after cooling down to room temperature was a relatively thick, clear and bright yellow liquid product having a viscosity of 6300 mPa^»s, as measured at 25^qC.

Example 10 b) (inventive) Example 10 a) was repeated except that TEGOPREN^® 5847 was admixed after the reaction, and not before.

After one hour at 70 ^<€, the batch was cooled to 50 °C.

Then, 144.5 g of methanol were admixed.

The etherification was started at 50 'Ό by admixture of 5.9 g of concentrated hydrochloric acid (31 -33 wt%). The exothermic reaction resulted in a temperature increase of about δ'Ό. After 9 minutes, the etherification was stopped by admixture of 3.7 g of 50% sodium hydroxide solution and 0.2 g of triethanolamine (99%).

The initial charge was subsequently adjusted to pH 5.9 with dilute sodium hydroxide solution and/or hydrochloric acid. This was followed by 3 hours at max. 65 'Ό in vacuo down to an absolute pressure of 100 mbar to remove 168 g of a methanol-water mixture by distillation. The result after cooling down to room temperature was a relatively thin, clear and bright yellow liquid product having a viscosity of 500 mPa^»s, as measured at 25 °C.

Thereafter, 123.6 g of TEGOPREN^® 5847 were stirred in and then the pH was adjusted to pH 6.1 by admixture of dilute hydrochloric acid.

The end product was clear, bright yellow and had a viscosity of 880 mPa^»s, as measured at 25 °C.

Table 1 1 hereinbelow shows once more the essential differences between Example 10 a) and Example 10 b).

Table 1 1

The products obtained were used to prepare aqueous dispersions having a content of 200 g/l and 2 g/l of concentrated hydrochloric acid (31 -33 wt%).

Following simultaneous and vigorous stirring, not only the product of Example 10 a) but also the product of Example 10 b), to which the TEGOPREN^® 5847 was admixed as a blending component, not as a reactant, have a similar appearance with comparable foam height and a clear, aqueous phase in each case, see Figure 12. After standing for 1 minute, foam height is distinctly reduced in Example 10 a) and there is some visible clouding, see Figure 13.

After standing for 15 minutes, the product of Example 10 a) has made the foam disappear and cloudiness has increased. In contradistinction, in the product of Example 10 b), foam is still clearly visible and the aqueous phase underneath has remained clear. Figure 14 thus demonstrates the possibility of employing the reaction product as defoamer.

To test the properties of inventive examples when used as additives in wood adhesives, a selection of inventive examples were used to prepare the mixtures of table 12.

In effect, a 10 wt% fraction of product was stirred in each case into Ponal Express (aqueous wood adhesive dispersion based on polyvinyl acetate, available from Henkel) until

homogeneous.

Table 12

In order to visualize the different structures of the adhesive compositions with respect to porosity and agglomeration, 0.1 g of each of these adhesive compositions was applied atop a glass plate in a punctuate manner. A second glass plate was then laid down flat on the first glass plate and lightly pressed down by hand. Thereafter, the top plate was moved about 5 cm parallel to the bottom plate and after about 1 minute lifted off at right angles to the bottom plate, see Figures 15 A to G. It is known that a larger porosity for layers enhances thermally insulating properties of, for example, laminated veneer lumber, which is made up of layers.

Particularly Figures 15 B, D and E show for the respective mixtures B, D and E versus

Figure 15 C, regarding the comparative example with wood adhesive dispersion without additive, stronger structuring of the adhesive compositions. This suggests that greater porosity for the adhesive layers and hence advantageously better heat-insulating properties versus the comparative example result.

It is likewise known that stronger agglomeration of the adhesive composition leads punctuately to a greater contact pressure and hence to stronger punctuate adherence. Particularly Figure 15 G, which relates to mixture G, shows distinctly stronger agglomeration of the adhesive composition versus Figure 15 C, which relates to the comparative example.

This suggests that this leads to a punctuately stronger adherence.

Mixtures A, B and D to G have the advantage over Comparative Example C of better removability with water before setting. Example 1 1 (inventive)

A reactor was initially charged with 32 g of methanol, 97.3 g of 37.5 wt% aqueous formaldehyde and 45.7 g of thiourea at room temperature. The pH was adjusted to 8.2 with dilute sodium hydroxide solution (10 wt%). The batch was heated to 54 ^<C at pH 8.2 for 5 hours.

Thereafter, 54.8 g of JEFFAMINE^® M-600 and 60 g of methanol were admixed. The

temperature was 50 'Ό and the pH was 9.6.

Then, 18 g of concentrated hydrochloric acid (32 wt%) were admixed. The exothermic reaction resulted in a temperature increase of about δ'Ό. After 9 minutes, the reaction was stopped by admixing 15.6 g of 30 wt% sodium hydroxide solution. This was followed by heating at 50 °C at pH 6 for 90 minutes. The solution turned cloudy after about 20 minutes. Methanol and water were then distilled off at max. 70 °C in vacuo down to an absolute pressure of 90 mbar.

The result after cooling down to room temperature was a slightly viscous, cloudy product. On standing, there was gradual sedimentation of the salts, which were separated off to obtain a slightly viscous, cloudy product having a solids content of 88 wt%. Example 12 (inventive)

A reactor was initially charged with 133.8 g of 65 wt% aqueous phenolsulfonic acid and 134.2 g of water. About 166 g of 16% sodium hydroxide solution were added to achieve a neutral pH 7. The temperature rose to about 40 ^.

At this point, 76.1 g of thiourea and 120 g of 37.5 wt% aqueous formaldehyde were admixed. The pH was adjusted to 8.5 with 16% sodium hydroxide solution and the batch was heated to 70°C at pH 8.5 for 3 hours.

The result on cooling down to room temperature was a clear product.

This was mixed with 34.2 g of MARLIPAL^® O 13/70 (oxo process alcohol C13 with 7 mol of EO, available from Sasol) followed by stirring at room temperature for 30 minutes to obtain a clear product.

Example 13 (inventive)

A reactor was initially charged with 66.9 g of 65 wt% aqueous phenolsulfonic acid and 33 g of water. About 83 g of 16% sodium hydroxide solution were added to achieve a neutral pH 7.1 . The temperature rose to about 39 'Ό.

At this point, 38 g of thiourea, 50 ml of methanol and 60 g of 37.5 wt% aqueous formaldehyde were admixed. The pH was adjusted to 8.5 with 16% sodium hydroxide solution and the batch was heated to 70 ^<€ at pH 8.5 for 3 hours.

At this point, 15 g of MARLIPAL^® O 13/70 and 50 ml of methanol were admixed. At δΟ 'Ό, 23.1 g of approximately 32 wt% hydrochloric acid were then admixed. The pH dropped to 0.8 and the product came down as a precipitate after about 7 minutes.

This was followed by stirring at 65 °C for 1 hour. The pH was adjusted to 7.6 with 21 .1 g of 30% sodium hydroxide solution to obtain a fine, homogeneous dispersion.

The methanol was then distilled off in a total amount of 120 g of methanol/water. The fine product dispersion was ground in the presence of 3% BAYKANOL SL (available from Lanxess) until a particle size of 5 μηι was attained.

The product was in the form of an aqueous dispersion having an active product content of 26.5 wt%.

Example 14 (inventive) A reactor was initially charged with 66.9 g of 65 wt% aqueous phenolsulfonic acid and 33 g of water. About 84.9 g of 16% sodium hydroxide solution were added to achieve a neutral pH 7.3.

At this point, 38.05 g of thiourea and 60 g of 37.5 wt% aqueous formaldehyde were admixed. The pH was adjusted to 8.5 with 16% sodium hydroxide solution and the batch was heated to 70°C at pH 8.5 for 3 hours. At this point, 15 g of MARLIPAL^® O 13/70 were admixed.

At 50 °C, 25.9 g of approximately 32 wt% hydrochloric acid were then admixed. The pH dropped to 0.6 and the product came down as a precipitate.

This was followed by stirring at 70 °C for 2 hours. 13.9 g of 30% sodium hydroxide solution were admixed to attain pH 7 and a coarse, homogeneous dispersion.

The product dispersion was ground in the presence of 3% BAYKANOL SL until a particle size of 2 μηι was attained.

The product was in the form of an aqueous dispersion having an active product content of 25 wt%. Wako Test

The products from Examples 1 1 to 14 were also subjected to the Wako Test as described above (for Example 4). In each case, x g (see table 13) of the composition prepared as described above in Examples 1 1 to 14 and 1 g of a blue-dyed swatch were employed, the reference was as described in Example 4. Evaluation was by colorimetric measurement. The results are shown in table 13.

Table 13

Scale: Rating 1 to 5 (1 = very bad, 5 = very good) Chlorine test (ISO 105/E03, 20 ppm of active chlorine)

The chlorine tests were carried out using the same blue-dyed swatches as for the Wako Test. The products were applied to the swatch by the pad-dry-thermofix process: usage amount: 40 g/l of product pH 5

15 g/l of KNITTEX CAT MO (available from Huntsman)

wet pick-up 70%

drying: 2 minutes at 1 10 °C

- fixing: 2 minutes at 170°C

Part of the swatch thus treated was washed at 50 'Ό with soap for 30 minutes to test its color fastness to washing.

A swatch which had not been aftertreated was used as reference.

Evaluation was by colorimetric measurements. The results are shown in table 14. Table 14

Scale: Rating 1 to 5 (1 = very bad, 5 = very good)

Claims

1 . Composition comprising at least one compound of formula (II) or of formula (III) or of formula (IV) or of formula (V)

R 0 ^ Ρ

HC CH

(IV)

CH₃— N / \ — CH,

C X

R³ R³

R— N I— C— N I— R (V)

X and at least one compound of formula (VII) or one amine of formula (VIII) or (IX) or one oligo- or polyorganosiloxane, having polyoxyalkylene groups, of general formula (X) or one compound of formula (XI), preferably of formula (Xla),

and optionally further comprising an alcohol of formula (VI),

where m is a number from 4 to 8 and t is 0 or 1 and p is a number from 8 to 20 and q is a number from 1 to 3,

all R³ each independently stand for H or for— CH₂— O— R², where in formula (V) at least one R³ stands for— CH₂— O— R²,

X stands for O or S,

where in a formula (V) where X stands for S, R³ may also stand for -CH₂-0-R¹⁴, in which R ⁴ stands for a moiety resulting from a phenolsulfonic acid or from a salt of a

phenolsulfonic acid, in particular p-phenolsulfonic acid or one of its salts, by etherification of a methylolated thiourea with said phenolsulfonic acid or a salt thereof, or R³ may also stand for -CH₂-R¹⁵, in which R ⁵ stands for a moiety resulting from a phenolsulfonic acid or from a salt of a phenolsulfonic acid, in particular p-phenolsulfonic acid or one of its salts, by reaction of a methylol group of a methylolated thiourea with a methine group of said phenolsulfonic acid or a salt thereof to form a methylene bridge between the nitrogen atom of the thiourea and a carbon atom of the phenolsulfonic acid or of a salt thereof,

R⁵ stands for linear or branched alkyl or alkenyl of 4 to 18, preferably 8 to 18 carbon atoms, more preferably for branched alkyl of 13 carbon atoms, or for an aromatic moiety optionally substituted by one or more hydrocarbyl moieties, in particular for phenyl, tolyl or benzyl,

where k + y is = 2 and k has the value 1 or 2, one of R⁶ and R⁷ stands for H while the other stands for H or for CH₃, 1 stands for a number from 0 to 20, preferably from 2 to 20, more preferably from 2 to 8, in particular for 2 to 6, where in the presence of a compound of formula (VII) with I = 0 a compound of formula (VII) with I >= 2 must also be present, n stands for a number from 2 to 20, preferably 2 to 8, more preferably from 2 to 6, and R⁸ stands for H or for

where one of R⁹ and R ⁰ stands for H while the other stands for H or CH₃ or C₂H₅ or

CH₂OH,

where r is a number from 2 to 15, s is a number from 0 to 20, v is a number from 1 to 18 and R stands for H or CH₃ and where in the siloxane of formula (X) not only the dimethylsiloxy units but also the methylsiloxy units comprising moieties including polyoxyalkylene groups may be randomly distributed across the siloxane chain,

wherein the composition comprises a reaction product of one or more compounds of formulae (II) to (V) with one or more compounds of formula (VII) and optionally of formula (VI) in the event at least that a compound of formula (VII) with I = 6-8 and t = 0 is present.

2. Composition according to Claim 1 , characterized in that R⁵ stands for branched alkyl of 13 carbon atoms and I stands for a number from 2 to 8, in particular from 2 to 6, and t = 0.

3. Composition according to Claim 1 or 2, characterized in that it comprises a product

obtainable by reacting at least one compound of formula (II) or of formula (III) or of formula (IV) or of formula (V) with a mixture of at least one alcohol of formula (VI) and at least one compound of formula (VII) where R ² = H or an amine of formula (VIII) or (IX) or an oligo- or polyorganosiloxane, having polyoxyalkylene groups, of general formula (X) where R ² = H or a compound of formula (XI) where R ² = H, preferably of formula (XIa), wherein from 0.01 to 0.5 mol of at least one of the compounds of formulae (VII) to (XIa) is preferably used per mole of alcohol of formula (VI).

4. Composition according to one or more of Claims 1 to 3, characterized in that it comprises an optical brightener, in particular an optical brightener based on a stilbene structure, or a UV absorber, preferably in converted form.

5. Composition according to Claim 3 or 4, characterized in that the product obtained after the reaction is neutralized and in that excess alcohol of formula (VI) is distilled off thereafter.

6. Aqueous composition comprising one or more compositions according to one or more of Claims 1 to 5, preferably having a water content of 20 to 60 wt%.

7. Process for preparing a composition according to Claim 3, wherein a compound of formula (II) or formula (III) or formula (IV) or formula (V) is reacted with an alcohol of formula (VI), characterized in that a compound of formula (VII) where R ² = H or an amine of formula

(VIII) or (IX) or an oligo- or polyorganosiloxane, having polyoxyalkylene groups, of general formula (X) where R ² = H or a compound of formula (XI) where R ² = H, preferably of formula (XIa), is additionally reacted, and the compound having one of the formulae (VII) to (XIa) may be added at the start of the reaction of a compound of formulae (I) to (V) with alcohol of formula (VI) or later.

8. Process according to Claim 7, characterized in that temperature, pressure and pH are

chosen such that distillative removal of alcohol of formula (VI) shifts the reaction equilibrium in favor of reaction products comprising a larger proportion of compound of one of formulae (II) to (V) which has been reacted with a compound of one of formulae (VII) to (Xla), and preferably the compound of one of formulae (VII) to (Xla) is only admixed to the reaction after some of the excess alcohol of formula (VI) has already been distilled off.

9. Process according to Claim 7 or 8, characterized in that it is carried out at a temperature of 30 to 130 °C, preferably of 30 to 80 °C, more preferably of 40 to 70 ^<C.

10. Process according to one or more of Claims 7 to 9, characterized in that the etherification with alcohol of formula (VI) is carried out at a pH of 0.3 to 1 , preferably of 0.45 to 0.75, and the reaction with a compound of formula (VII) where R ² = H or an amine of formula (VIII) or (IX) or an oligo- or polyorganosiloxane, having polyoxyalkylene groups, of the general formula (X) where R ² = H or a compound of formula (XI) where R ² = H, preferably of formula (Xla), is carried out at a pH of 5 to 7, preferably of 5.6 to 6.4, and an absolute pressure of 50 to 1000 mbar, preferably of 50 to 175 mbar, is employed in the case of the latter reaction.

1 1 . Use of a composition according to one or more of Claims 1 to 6 for treatment of fiber

materials comprising natural fibers, preferably cellulose or wool, or synthetic fibers, in particular polyester, polyamide, polyacrylonitrile, polyacrylate and viscose, and also mixtures thereof.

12. Use according to Claim 1 1 , characterized in that the fiber materials are 50 to 100 wt%

cellulose, in particular cotton.

13. Use according to Claim 1 1 or 12, characterized in that a composition comprising a

proportion of at least one converted compound of one of the formulae (VII) or (VIII) or (IX) or (X) or preferably (XI), in particular (Xla), in combination with polymers suitable for generating barrier effects on textiles is employed and the composition thus obtained is employed for the treatment of fiber materials to produce enhanced barrier effects.

14. Use according to Claim 1 1 or 12, characterized in that a composition comprising a

proportion of at least one converted compound of one of the formulae (VII) or (VIII) or (IX) or (X) or (XI), preferably (Xla), in combination with polymers suitable for generating barrier effects on textiles is employed and the composition thus obtained is employed for the treatment of fiber materials to produce or enhance soil release effects.

15. Use according to Claim 1 1 or 12, characterized in that the composition is employed to

import free radical scavengers onto fiber materials, in particular a composition comprising a proportion of a converted compound of formulae (II), (IV) or (V) where X = S.

16. Use according to Claim 1 1 or 12, characterized in that a composition according to Claim 4 is employed to import optical brighteners, in particular optical brighteners based on a stilbene structure, or UV absorbers onto fiber materials.

17. Use of a composition according to one or more of Claims 1 to 6 as phase transfer catalyst.

18. Use of a composition according to one or more of Claims 1 to 6 as additive for adhesives.

19. Compound of formula (XII),

where R³ stands for H or for— CH₂— O— R²,

-(-CH.-CH-O-^R ¹³ where m is a number from 4 to 8 and q is a number from 1 to 3 and