WO1999005246A1

WO1999005246A1 - Low viscosity dispersion for paper or textile processing

Info

Publication number: WO1999005246A1
Application number: PCT/EP1998/004534
Authority: WO
Inventors: Ansgar Behler; Bernd Wahle; Ludwig BÖNNIGER; Yvonne Reichert; Almud Folge
Original assignee: Cognis Deutschland Gmbh
Priority date: 1997-07-28
Filing date: 1998-07-20
Publication date: 1999-02-04
Also published as: DE59811110D1; EP1002033A1; DE19732396A1; EP1002033B1; PT1002033E; ES2218847T3

Abstract

The invention relates to a concentrated low viscosity aqueous dispersion containing a) a nonionic softening agent selected from among glycerin monoesters or diesters with fat acids C8-22, and theirs blends; b) a polyol compound, preferably glycerin, diethylene glucol, polyethylene glycol or 1-2-propylene glucol and their blends; c) cationic and nonionic emulsifiers; d) 70 to 90 wt. % water and possibly other appropriate auxiliary agents and additives for softening paper or textile.

Description

"Low-viscosity dispersion for paper and textile treatment"

The present invention relates to concentrated, low-viscosity aqueous dispersions for the treatment of paper and textiles, a production process for this dispersion and the use of the dispersion for softening paper and textiles.

Softness plays an important role in many paper and textile technology products. So the consumer expects textiles or paper products. eg paper handkerchiefs. Household towels or hygiene items, feel as soft as possible. A large number of suitable compounds and compositions are therefore already known for the finishing of paper and textiles. From US 3,594,224 it is known that certain quaternary ammonium compounds are suitable for improving the softness of cellulose fibers. WO 96/08601 proposes a polysiloxane-containing treatment agent for tissue products, the agent besides polysiloxanes also a polyhydroxy compound. such as polyethylene glycol or glycerin. WO 94/10381 describes mixtures of quaternary ammonium compounds and polyethylene glycol or polypropylene glycol for the softening of paper products and cellulose-containing fibers. EP 569 847 AI describes alkoxylated natural oils and fats as active ingredient components for fabric softener formulations. EP 494 769 A2 describes textile plasticizers based on pentaerythritol esters. EP 698 140 B1 claims tissue paper. which is treated with a tricomponent plasticizer. Sorbitan fatty acid esters are used as the softening component. These compounds are formulated in the form of aqueous dispersions and applied to the products in a suitable manner. EP 698 140 B1 proposes a suitable emulsifier system nonionic emulsifiers, such as alkyl (oligo) glycosides or ethoxylated or propoxylated sorbitan esters in combination with selected polyhydroxy compounds.

However, these agents often only contain up to 10% by weight of active substances, since more highly concentrated dispersions can also have a significantly increased viscosity, which means that they can be processed directly, e.g. by spraying onto the textile or paper web, makes it difficult or impossible. Such highly concentrated dispersions also tend to segregate or break more quickly and have reduced storage stability.

The object of the present invention was therefore to provide concentrated but low-viscosity agents in the form of aqueous dispersions for the softening treatment of paper and textiles.

It has been found that dispersions which contain a selected plasticizer combination based on glycerol and its derivatives meet the above-mentioned requirements for low viscosity and high stability.

The present application therefore relates to concentrated, low-viscosity, aqueous dispersions for the softening of paper and textiles, which contain a) a nonionic softener component which is selected from mono- or diesters of glycerol with C.sub.g _.: fatty acids and mixtures thereof. b) a polyol compound c) cationic and nonionic emulsifiers d) 70 to 90% by weight of water and optionally further auxiliaries and additives, the weight ratio of components a) and b) being between 2.5: 1 and 1: 2.5.

The dispersions according to the invention are of low viscosity, ie they preferably have a Brookfield viscosity, measured at 20 ° C. with a spindle of 1 and 20 rpm, between 1 and 100 mPa s and in particular between 1 and 50 mPa s. Dispersions whose viscosity is below 10 mPas are particularly preferred. The water content is between 70 and 90% by weight, dispersions with less than 80% by weight water being preferred. The dispersions are finely divided and stable in storage and can be applied directly to the paper or textiles. Additional dilution or other conditioning is not necessary.

The dispersions are generally suitable for the softening treatment of paper or textiles. They can be used for permanent equipment as well as for temporary equipment. It is thus possible to use the dispersions in the manufacture or refinement of paper products or textiles or as post-treatment or fabric softening agents in machine or industrial laundry or as tumble aids.

In the context of the present application, textiles are understood to mean all textile piece goods which contain synthetic or natural fibers, e.g. Contain wool, cotton, polyamide, polyester or polyacrylic fibers or mixtures of these fibers. However, the textile fibers themselves can also be treated with the dispersions. In addition to paper and paper products, cellulose-containing fibers, e.g. Cellular and wood pulp fibers as well as nonwovens made from these fibers are treated with the dispersions. The use of the dispersions for the softening of paper or paper products is preferred. This includes e.g. Tissue paper. which in the manufacture of pocket. Kitchen or household towels, as well as hygiene items such as tampons, toilet paper and diapers are used.

In the treatment of paper or textiles, all methods known to the person skilled in the art for applying liquid treatment agents can be used, for example by printing, spraying, splashing or padding. Size presses, air nozzles, squeegees, rollers or engraving. As a rule, textile or paper webs are brought into contact with the dispersions in suitable machines and the dispersion is applied to the textile material or paper in suitable amounts. In the treatment of textile goods, pulling-on processes are also possible, in which the textile goods remain in the aqueous dispersion and the active substances are thereby pulled onto the fibers. The dispersions can if necessary also in hot condition, ie at temperatures up to 80 ° C.

Such processes are described for paper finishing, for example in the Handbook of Paperboard and Board, R.R.A. Higham, BB Ltd., London 1970, pages 142 to 169 or for textile technology in finishing of textiles, VEB Fachbuchverlag Leipzig 1990, pages 193 to 228.

The dispersions contain mono- or diesters of glycerol with C ₈ as nonionic softening component a). ₂₂ fatty acids. the C ₈ . ₂₂ fatty acids can be linear or branched, saturated or unsaturated. Glycerol esters based on saturated, linear fatty acids, such as, for example, lauric, myristic, palmitic, stearic, arachic or behenic acid or mixtures of these acids, are particularly suitable. The mono- or diglycerides can also be used in the form of mixtures as they arise due to the technical production process. The glycerides can also be contained in any mixtures of mono- and diglycerides. Dispersions are preferred, however. based on the plasticizer component a), contain at least 60% by weight diglycerides. The dispersions preferably contain the nonionic plasticizer component a) in amounts of between 1 and 14% by weight. wherein such dispersions are preferred which contain the plasticizer in amounts of 5-10% Gev ^■ .-%.

As a further essential ingredient, the dispersions contain at least one poly compound b) in amounts such that the weight ratio between the nonionic plasticizer component and the polyol compound is in the range from 2.5: 1 to 1: 2.5 and preferably in the range from 2.0: 1 to 1 : 1 lies. Polyol compound is understood to mean organic compounds with at least two carbon atoms and at least two hydroxyl groups in the molecule, the hydroxyl group not being derivatized. Suitable polyol compounds are, for example, glycerol and its dimers or trimers. Glycols and their polymers, pentaerythritol, di- and trimethylolpropane. Sorbitan. Manitol. Xylitol, glucose, mannose or fructose. The dispersions preferably contain glycerol, diethylene glycol, polyethylene glycol or 1,2-propylene glycol and mixtures thereof as the polyol compound. Also preferred are those dispersions which contain polyethylene glycol with an average molecular weight between 200 and 1000 and preferably between 200 and 600.

The proportion of polyol compounds b) is preferably in the range from 1.0 to 12.0% by weight and in particular in the range between 5 and 10% by weight. Mixtures of glycerol with polyethylene glycol and in particular mixtures in which the weight ratio between glycerol and polyethylene glycol is between 10: 1 and 6: 1 are particularly suitable. The glycols are preferably present in amounts between 0.1 and 2.0% by weight and in particular between 0.1 and 1.0% by weight.

As emulsifiers c) for the nonionic plasticizers, the dispersions according to the invention contain a system of cationic and nonionic emulsifiers. Particularly suitable nonionic emulsifiers are fatty acids and fatty alcohols or their derivatives, in particular their reaction products with alkoxides such as ethylene oxide, propylene oxide and / or butylene oxide. Cationic emulsifiers are preferably compounds with at least one cationically charged nitrogen atom.

Suitable cationic emulsifiers are preferably selected from the group of the quaternary ammonium compounds of the formulas (I) and (II)

R ¹ CH ₃

R - N - R ^{: +} X ^" R ³ OC-O- (CH ₂ ) _n - N - (CH ₂ ) _n -O-COR ^{3 +} X ^"

RR ⁴ - (CH ₂ ) _n

(I) (II)

where R is an acyclic alkyl radical having 12 to 24 carbon atoms, R ^{1 is} a saturated C, -C ₄ alkyl or hydroxyalkyl radical, R ^{2 is} either R or R ¹ and COR ^{3 is} is an aliphatic acyl radical having 12 to 22 carbon atoms with 0, 1, 2 or 3 double bonds and R ⁴ is hydrogen or OH, where n is 1, 2 or 3 and X is either a halide, methosulfate, metophosphate or Is phosphate ion, as well as mixtures of these compounds. Compounds which contain alkyl radicals having 16 to 18 carbon atoms are particularly preferred.

Examples of cationic emulsifiers of the formula (I) are didecyldimethylammonium chloride, ditallowdimethylamonium chloride or dihexadecydimethylammonium chloride. Examples of compounds of the formula (II) are methyl-N, N- bis (acyloxyethyl) -N- (2-hydroxyethyl) ammonium methosulfate, methyl-N- (2-hydroxyethyl) -N, N-di ( tallow acyloxyethyl) ammonium rnethosulfate and bis (palmitoyl) ethyl hydroxyethyl methyl ammonium methosulfate or. In addition to the compounds of the formulas (I) and (II), it is also possible to use short-chain, water-soluble, quaternary ammonium compounds, such as, for example, trihydroxyethyl-methyl-ammonium methosulfate or cetyl-trimethyl-ammonium chloride. Protonated alkylamine compounds which have a plasticizing effect are also suitable.

If quaternized compounds of the formula (II) are used which have unsaturated alkyl chains, preference is given to the acly groups whose corresponding fatty acids have an iodine number between 5 and 25, preferably between 10 and 25 and in particular between 15 and 20 and which have a cis / trans isomer ratio (in% by weight) of 30:70, preferably greater than 50:50 and in particular greater than 70:30.

In addition to the quaternary compounds described above, other known compounds can also be used, such as quaternary compounds

Imidazolinium compounds of formula (III)

where R ^{5 is} a saturated alkyl radical having 12 to 18 carbon atoms, R ^{6 is} an alkyl radical having 1 to 4 carbon atoms or hydrogen and Z is an NH group or oxygen and A is an anion.

Further suitable quaternary compounds are described by formula (IV)

(R ⁷ ), N - <CH ₂ ) _n - CH - OOCR ⁸

CH, - OOCR ^s

(IV)

where R 'is independently selected for a C alkyl, alkenyl or hydroxyalkyl group, R ^{8 is} each independently selected for a C ₈ . _{28 represents} alkyl group and n is a number between 0 and 5. X stands for an anion, for example a halide, methosulfate, metophosphate or phosphate ion. The dispersions according to the invention preferably contain the cationic emulsifiers in amounts between 0.5 and 3.0% by weight and in particular between 1.0 and 2.0% by weight.

The dispersions also contain nonionic emulsifiers, preferably from the group of the alkoxylated fatty acids with 8 to 22 C atoms, the alkoxylated fatty acid esters from fatty acids with 8 to 22 C atoms with monohydric alcohols with 1 to 10 C atoms and the alkoxylated fatty alcohols with 8 to 22 carbon atoms, the alkoxylated compounds having HLB values between 3 and 20 and preferably between 8 and have 16. The HLB value (hydrophilic-lipophilic balance) is a measure of the water or oil solubility of nonionic surfactants (cf. Römpp Chemie Lexikon, Volume 3, 9th edition 1990, page 1812-13). It is defined by the following equation:

VZ

HLB = 20] \ - -

SZ

where SZ stands for the acid number and VZ for the saponification number of the corresponding compound.

The fatty acid ester alkoxylates are known compounds which are described, for example, in US Pat. No. 2,678,935, US Pat. No. 3,539,518, US Pat. No. 4,022,808 or GB 1,050,497, the disclosure of which is also part of the present application.

The alkoxylated fatty acid esters can be prepared by all methods known to those skilled in the art, e.g. by esterification of fatty acids with alkoxylated methanol, as described, for example, in US Pat. No. 3,539,518. Another possibility is the direct reaction of fatty acid esters with alkylene oxides in the presence of transition metal catalysts, as described in US Pat. No. 4,022,808. However, the fatty acid alkyl ester alkoxylates are preferably prepared by heterogeneously catalyzed direct alkoxylation of fatty acid alkyl esters with ethylene oxide and / or propylene oxide on hydrophobicized hydrotalcites. This synthesis method is described in detail in the laid-open publications WO 90/13533 and WO 91/15441, the disclosure of which is also part of the present application. The resulting products are characterized by a low OH number, the reaction is carried out in one step and light-colored products are obtained. The fatty acid alkyl esters used as starting materials can be obtained from natural oils and fats or produced synthetically.

Examples of particularly suitable nonionic emulsifiers are C ₁₂ . ₁₈ fatty alcohols with 7 to 14 moles of ethylene oxide per mole of alcohol or cetyl / stearyl alcohol with 20 moles Ethylene oxide and C ₁₂ . ₁₈ fatty acids or fatty acid esters with C alcohols, which contain between 8 and 16 moles of ethylene oxide per mole of fatty acid or ester.

Further suitable nonionic emulsifiers are selected from the group of the alkyl (oligo) glycosides of the formula RO- [Z] _x in which R is an alkyl radical having 8 to 22 carbon atoms, Z is a sugar radical having 5 or 6 carbon atoms and x stands for a number between 1 and 10. Alkyl (oligo) glycosides, their preparation and use as surface-active substances are known, for example, from DE 19 43 689 AI or from DE 38 27 543 AI.

Regarding the glycoside residue, both monoglycosides in which a sugar residue is glycosidically bound to the fatty alcohol and oligomeric glycosides with an average degree of oligomerization of up to about 2 are particularly suitable. The glucoside residue is contained in the commercially available alkyl oligoglycosides as the glycoside residue.

The proportion of nonionic emulsifiers is preferably between 0.1 and 3.0% by weight and in particular between 0.5 and 1.5% by weight.

The dispersions contain, as solvent d), water in amounts between 70 and 90% by weight. Desalinated water is preferably used. Tap water can also be used. The pH of the dispersions is preferably in the range from 4.5 to 7.5 and in particular in the range between 5.0 and 6.5 and can be achieved by adding suitable acids. e.g. HC1 or bases, such as aqueous sodium hydroxide solution, can be set.

In addition to the described substances a) to d), the dispersions according to the invention may also contain other auxiliaries and additives customary in paper or textile technology. These include, for example, biocides, preservatives, dyes, pearlescent agents, defoamers, soil release compounds, UV absorbers, perfume oils or fragrances and other additives derived from native sources, such as vitamins or plant extracts. The dispersions described can be prepared in any manner known to those skilled in the art. However, it is preferred to add the nonionic plasticizer and the cationic emulsifier together to a mixture of the remaining components (nonionic emulsifier, glycerol and water and, if appropriate, auxiliaries and additives), which may be necessary depending on the melting points of the individual components to heat the mixtures, usually to temperatures between 40 and 80 ° C. The raw dispersion is then mixed intensively.

The dispersions are finely divided and contain at least 90% (number distribution) of particles which are smaller than 1000 nm, preferably smaller than 500 nm. Therefore, only those homogenizers can be used that transmit sufficiently high shear forces to obtain the desired finely divided dispersions. Suitable devices are, for example, high pressure or ultrasonic homogenizers.

It has been shown that the use of certain homogenizers leads to dispersions with particularly advantageous properties.

The present application therefore also relates to a process for the preparation of the dispersions described above, components a) to c) and any auxiliaries which may be present being dispersed in water first, and this crude dispersion then using a high-pressure homogenizer known to the person skilled in the art. such as that from APV Homogenizer GmbH. Lübeck, is produced, is homogenized at pressures between 10 and 600 bar. In this case, it is particularly preferred to carry out the homogenization at pressures between 25 and 250 bar.

As is usual when using high-pressure homogenizers, the raw dispersion is initially at low pressures, ie in the range from 10 to 50 bar and then at higher pressures, above 50 bar. homogenized. It may be advantageous to homogenize the dispersions several times at different pressures. It is further preferred to carry out the homogenization at temperatures between 20 and 100 ° C., preferably between 25 and 70 ° C. Depending on the auxiliary and used It may therefore also be preferred to add additives to the dispersions only after homogenization.

Examples

Three different dispersions were prepared by first melting the nonionic plasticizer with the cationic emulsifier at 70 ° C. This melt was then added to the remaining components, which were placed in a stirred kettle at 70 ° C., and stirred for 15 minutes. The raw dispersion obtained in this way was cooled to room temperature and then homogenized at 40 ° C. using a high-pressure homogenizer from APV Homogenizator GmbH, Luebeck, model LAB 60/60 once at 50 bar and twice at 200 bar. The pH of the dispersion was 5.5.

Only the dispersion 1 according to the invention has the desired low viscosity, while the comparative dispersions 2 and 3 showed a viscosity which can no longer be determined. The composition of concentrates 1 to 3 is shown in Table 1:

Table 1 (amounts in% by weight of active substance)

* not determined, as dispersion cannot be homogenized at 40 ° C

** Brookfield, spindle 1, 20 ° C. 20 rpm. Viscometer type RVF, Brookfield Eng Ltd

Dehyquart Au 46 methyl-N.N-bis (acyloxyethyl) -N (2-hydroxyethyl) ammonium methosulfate (from Henkel) Stantex S 6030 ethoxylated methyl laurate with 12 parts of ethylene oxide (from Henkel)

Claims

claims

1. Concentrated, low-viscosity, aqueous dispersion for the softening of textiles or paper, which contains a) a nonionic softener component which consists of mono- or diesters of glycerol with C ₈ . ₂₂ fatty acids and mixtures thereof is selected, b) a polyol compound, c) cationic and nonionic emulsifiers, d) 70 to 90% by weight of water and optionally further auxiliaries and additives, characterized in that the weight ratio of components a) and b) is between 2.5: 1 and 1: 2.5.

2. Dispersion according to claim 1, characterized in that the dispersion has a Brookfield viscosity, measured at 20 ° C with spindle 1 at 20 rpm, between 1 and 100 mPa s and preferably between 1 and 50 mPa s.

3. Dispersion according to claim 1 or 2, characterized in that the polyol compound is selected from glycerol, diethylene glycol, polyethylene glycol or 1,2-propylene glycol and mixtures thereof.

4. Dispersion according to one of claims 1 to 3, characterized in that quaternary ammonium compounds of the formulas (I) or (II) are contained as cationic emulsifiers

R 'CH ₃

R - N - R ^{2 +} X ^" R OC-O- (CH ₂ ) _n - N - (CH ₂ ) _n -O-COR ^{3 +} X ^"

I I

RR ⁴ - (CH ₂ ) _n

(I) (II)

where R is an acyclic alkyl radical having 12 to 24 carbon atoms, R ^{1 is} a saturated C, -C ₄ alkyl or hydroxyalkyl radical, R ^{2 is} either R or R ¹ and COR ^{3 is} an aliphatic acyl radical having 12 to 22 carbon atoms with 0, 1, 2 or 3 double bonds, and R ⁴ is hydrogen or OH, where n is 1, 2 or 3 and X is either a halide -, methosulfate or metophosphate ion.

5. Dispersion according to one of claims 1 to 4, characterized in that as nonionic emulsifiers alkoxylated fatty acids with 8 to 22 C atoms, alkoxylated fatty acid esters from fatty acids with 8 to 22 C atoms with alcohols with 1 to 10 C atoms and / or alkoxylated fatty alcohols with 8 to 22 carbon atoms are contained, the alkoxylated compounds having HLB values between 3 and 20.

6. Dispersion according to one of claims 1 to 5, characterized in that the nonionic plasticizer component a) is contained in amounts between 1 and 14 wt .-% and preferably in amounts between 5 and 10 wt .-%.

7. Dispersion according to one of claims 1 to 6, characterized in that the nonionic emulsifier is contained in amounts of 0.1 to 3.0 wt .-%.

8. Dispersion according to one of claims 1 to 7, characterized in that the cationic emulsifier is contained in amounts of 0.5 to 3.0 wt .-%.

9. Dispersion according to one of claims 1 to 8, characterized in that a mixture of glycerol and polyethylene glycol is contained as component b).

10. Dispersion according to claim 9, characterized in that the weight ratio between glycerol and polyethylene glycol is between 10: 1 and 6: 1.

1 1. A process for the preparation of dispersions according to claim 1, characterized in that component a) to c) and any auxiliary substances present are dispersed in water and this raw dispersion is then homogenized with a high-pressure homogenizer at pressures between 10 and 600 bar.

12. The method according to claim 1 1, characterized in that the raw dispersion is homogenized at pressures of 25 to 250 bar.

13. Use of dispersions according to claim 1 for the softening of paper.

14. Use of dispersions according to claim 1 for the softening finish of textile piece goods.

15. Use of dispersions according to claim 1 as fabric softener.