WO2025201396A1

WO2025201396A1 - Alkoxylated iso-nonanol

Info

Publication number: WO2025201396A1
Application number: PCT/CN2025/085010
Authority: WO
Inventors: Laszlo Szarvas; Si Jun ZHU; Lin Niu; Chu HU; Xu Lu; Hui Wang; Qing Shi; Yang Ye; Sheng Hao HU
Original assignee: BASF China Co Ltd; BASF SE
Current assignee: BASF China Co Ltd; BASF SE
Priority date: 2024-03-27
Filing date: 2025-03-26
Publication date: 2025-10-02
Anticipated expiration: 2026-09-27

Abstract

The present invention relates to an alkoxylated iso-nonanol. The new alkyloxylated iso-nonanol comprising propylene oxide segments and ethylene oxide segments leads to a comprehensive performance with respect to dynamic surface tension property, emulsifying ability property, wet-ting property, foaming behavior, viscosity, stability and detergency and/or cleaning properties.

Description

ALKOXYLATED ISO-NONANOL

Technical Field

The invention relates to an alkoxylated iso-nonanol. The new alkoxylated iso-nonanol leads to improved surfactant properties and achieves improved technical effects for various applications.

Background

Nonionic surfactants are widely used in various fields, for example household and personal care products, due to their advantages like resistance to water hardness, good oil and grease removing capability, and compatibility with other surfactants. As a large family of nonionic surfactants, alkoxylated aliphatic alcohols have been developed for several decades, which consist of a hy-drophobic group derived from an alcohol such as fatty alcohol, Guerbet alcohol or oxo alcohol, and a hydrophilic chain or segment derived from varying amounts of alkylene oxide such as eth-ylene oxide, propylene oxide and/or butylene oxide. The alkoxylated aliphatic alcohols have ex-cellent permeability, emulsification, foam and detergency properties, and are environmentally friendly due to their lower toxicity risks and higher biodegradability rates.

Notwithstanding the widespread use of alkoxylated aliphatic alcohols, the research of this type of nonionic surfactant generally focused on alkoxylated long-chain alcohol such as C₁₂ to C₁₈ or higher alcohols. Fewer researchers and manufacturers looked at alkoxylated alcohols with less carbon numbers, especially having branched chains, although some products are already com-mercially available, for example, alkyl polyethylene glycol ether based on C₁₀-Guerbet alcohol and ethylene oxide manufactured and sold under LUTENSOL^TM XP by BASF.

Alkoxylated aliphatic alcohols vary in wetting, foaming, detergency and other properties for their applications in cleaning products, depending on a great extent on the type of alcohol and on the type and amount of alkylene oxide adducts.

There is a need to find a new alkoxylated aliphatic alcohol nonionic surfactant which can endow desirable comprehensive properties including for example, dynamic surface tension, foaming property, wetting property, emulsifying ability, viscosity, stability and some detergency and/or cleaning properties.

Summary of Invention

It is an object of the present invention to find an alkoxylated iso-nonanol comprising propylene oxide segments and ethylene oxide segments which can exhibit a comprehensive performance with respect to dynamic surface tension property, emulsifying ability property, wetting property, foaming behavior, viscosity, stability and detergency and/or cleaning properties.

In the first aspect, it was found by the inventors that the object can be achieved by an alkoxylated iso-nonanol, wherein the alkylene oxide segments are comprised of propylene oxide segments and ethylene oxide segments. Preferably the alkoxylated iso-nonanol of the present invention has a degree of propoxylation in the range of 0.9 to 7 and has a degree of ethoxylation in the range of 3 to 17.

It was found by the inventors that the object can be achieved by an alkoxylated iso-nonanol ob-tained by alkoxylation of a mixture of isomeric nonanols, preferably the mixture of isomeric nona-nols has a degree of branching (ISO index) in the range of 1.1 to 1.5, more preferably in the range of 1.1 to 1.4.

Accordingly, the present invention relates to a formulation comprising an alkoxylated iso-nonanol of the present invention, wherein the alkylene oxide segments are comprised of propylene oxide segments and ethylene oxide segments, preferably the alkoxylated iso-nonanol is obtained by alkoxylation of a mixture of isomeric nonanols having a degree of branching in the range of 1.1 to 1.5, preferably from 1.1 to 1.4.

Particularly, the present invention relates to a formulation which can be, for example, laundry detergent composition and industrial and institutional cleaning composition, fabric and home care composition, cosmetic or personal care composition, oil field-formulation such as crude oil emul-sion breaker, ink, electro-plating composition, cementitious composition, lacquer or paint, textile auxiliary composition, emulsion polymerization composition and agrochemical composition, com-prising the alkoxylated iso-nonanol of the present invention. Preferably the alkoxylated iso-nona-nol is obtained by alkoxylation of a mixture of isomeric nonanols having a degree of branching in the range of 1.1 to 1.5, preferably from 1.1 to 1.4.

In the second aspect, the present invention relates to use of the alkoxylated iso-nonanol of the present invention in a cleaning formulation for home care cleaning, household cleaning or institu-tional cleaning, preferably the alkoxylated iso-nonanol is obtained by alkoxylation of a mixture of isomeric nonanols having a degree of branching in the range of 1.1 to 1.5, preferably from 1.1 to 1.4.

Detailed Description

The singular forms “a” , “an” and “the” include plural referents unless the context clearly dictates otherwise. The terms “comprise (s) ” , “comprising” , etc. are used interchangeably with “contain (s) ” , “containing” , etc. and are to be interpreted in a non-limiting, open manner. That is, e.g., further components or elements can be present. The expressions “consist (s) of” or “consisting of” or cognates can be embraced within “comprise (s) ” or “comprising” or cognates. The terms “in-clude (s) ” , “including” , etc. are to be interpreted in a non-limiting, open manner.

Herein, the term “iso-nonanol” is intended to mean an isomeric mixture of C₉ oxo alcohols, which is generally produced commercially by the hydroformylation of a C₈ olefin mixture.

Herein, the term “degree of alkoxylation” refers to the number of moles of alkylene oxide reacted with one mole of iso-nonanol to produce the alkoxylated iso-nonanol nonionic surfactant and is intended to mean number average degree of alkoxylation. Similarly, the term “degree of ethoxylation” is intended to mean the average number of moles of ethylene oxide unit per mole of alkoxylated iso-nonanol and the term “degree of propoxylation” is intended to mean the average number of moles of propylene oxide unit per mole of alkoxylated iso-nonanol.

Herein, the term “degree of branching” means the sum of branching number multiplying with the proportion of the respective alkyl alcohol (nonanol) in the mixture of isomeric alkyl alcohols (iso-nonanols) . For example, the branching degree of nonanol-1 is 0; 2-ethyl-2-methylhexanol-1 is 2 and 2, 3, 4-trimethylhexanol-1 is 3. The degree of branching of the isomeric nonanols is the sum of all values which are obtained by multiplying the branching number with the proportion of the respective nonanol.

In the first aspect, the present invention provides an alkoxylated iso-nonanol, wherein the alkylene oxide segments are comprised of propylene oxide segments and ethylene oxide segments. Par-ticularly, the alkylene oxide segments consist of propylene oxide segments and ethylene oxide segments.

The alkoxylated iso-nonanol according to the present invention may be represented by the for-mula (I) :

RO- (PO) _n- (EO) _m-H (I)

wherein

R is a linear or branched C₉-alkyl, preferably R is a C₉-alkyl originating from iso-nonanol,

PO is propyleneoxy and EO is ethyleneoxy, and

n is a number in the range of 0.9 to 7, preferably in the range of 1.1 to 5,

m is a number in the range of 3 to 17, preferably in the range of 3 to 14;

preferably, the alkoxylated iso-nonanol is obtained by alkoxylation of a mixture of isomeric nona-nols having a degree of branching in the range of 1.1 to 1.5, preferably in the range of 1.1 to 1.4.

The alkylene oxide segment represented by “- (PO) _n- (EO) _m-” in the formula (I) , may have a block polymeric structure or a random polymeric structure.

It will be understood that “- (PO) _n- (EO) _m-” in formula (I) is just intended to represent alkylene oxide segments having propyleneoxy units at a total number of “n” ( “n” means “degree of propoxylation” ) and ethyleneoxy units at a total number of “m” ( “m” means “degree of ethoxylation” ) , which are not intended to impose any limitation of the polymeric structure.

It will be understood that the alkoxylated iso-nonanol is a mixture of alkoxylates of iso-nonanol in view of that fact that iso-nonanol is an isomeric mixture. The alkoxylated iso-nonanol may also be a mixture of alkoxylates with respect to the degree of alkoxylation.

Particularly, the alkoxylated iso-nonanol can be prepared by adding alkylene oxide, in this case, adding ethylene oxide and propylene oxide to iso-nonanol in a conventional manner in the pres-ence of a conventional alkali catalyst, such as potassium hydroxide or sodium hydroxide. Partic-ularly, the alkoxylated iso-nonanol can be prepared by adding propylene oxide first and then add-ing ethylene oxide to form the alkoxylated iso-nonanol according to the formula (I) .

In another aspect of the present invention, the alkoxylated iso-nonanol may be represented by the formula (II) :

RO- (PO) _n- (EO) _m- (PO) _k-H (II)

wherein

PO is propyleneoxy and EO is ethyleneoxy, and

n is a number in the range of 0.9 to 7, preferably in the range of 1.1 to 5,

m is a number in the range of 3 to 17, preferably in the range of 3 to 14;

k is a number in the range of 0 to 5, preferably in the range of 0.5 to 3;

The alkylene oxide segment represented by “- (PO) _n- (EO) _m- (PO) _k” in the formula (II) , may have a block polymeric structure or a random polymeric structure.

It will be understood that “- (PO) _n- (EO) _m- (PO) _k” in formula (II) is just intended to represent alkylene oxide segments having the first propyleneoxy units at a total number of “n” ( “n” means “degree of propoxylation” ) and ethyleneoxy units at a total number of “m” ( “m” means “degree of ethoxyla-tion” ) , and the second propyleneoxy units at a total number of “k” ( “k” means “degree of propox-ylation” , which are not intended to impose any limitation of the polymeric structure.

Particularly, the alkoxylated iso-nonanol can be prepared by adding alkylene oxide, in this case, adding ethylene oxide and propylene oxide to iso-nonanol in a conventional manner in the pres-ence of a conventional alkali catalyst, such as potassium hydroxide or sodium hydroxide. Partic-ularly, the alkoxylated iso-nonanol can be prepared by adding propylene oxide first and then add-ing ethylene oxide, and finally adding propylene oxide again to form the alkoxylated iso-nonanol according to the formula (II) .

Suitable iso-nonanol (i.e., the isomeric mixture of C₉ oxo alcohols) for preparing the alkoxylated iso-nonanol according to the present invention may be commercially available, for example from BASF. The iso-nonanol prepared in accordance with known method via the hydroformylation route may also be used for preparing the alkoxylated iso-nonanol according to the present inven-tion.

In any one embodiment of the present invention, the isomeric mixture of nonanols has degree of branching within 1.1 to 1.5, preferably within 1.1 to 1.4.

Generally, the method for preparing iso-nonanol involves two or more steps and starts from butenes. In a first step, the butenes are dimerized to give a mixture of isomeric octenes. The octene mixture is then hydroformylated to give C₉ aldehydes and then hydrogenated to give a nonanol isomer mixture, often referred to as iso-nonanol. Details of suitable methods with respect to hydrocarbon feed as the source of butenes, catalysts, process conditions, etc. can be found in many patent applications, for example in DE19924339A1, WO 01/48049 A1 or US9090553B2.

In some preferred embodiments, suitable iso-nonanol for preparing the alkoxylated iso-nonanol according to the present invention may have the following composition, based on the total sum of the components of 100%by weight, as described in US9090553B2:

● from 6.0 to 16.0%by weight, preferably from 7.0 to 15.0%by weight, particularly preferably from 8.0 to 14.0%by weight, of n-nonanol;

● from 12.8 to 28.8%by weight, preferably from 14.8 to 26.8%by weight, particularly preferably from 15.8 to 25.8%by weight, of 6-methyloctanol;

● from 12.5 to 28.8%by weight, preferably from 14.5 to 26.5%by weight, particularly preferably from 15.5 to 25.5%by weight, of 4-methyloctanol;

● from 3.3 to 7.3%by weight, preferably from 3.8 to 6.8%by weight, particularly preferably from 4.3 to 6.3%by weight, of 2-methyloctanol;

● from 5.7 to 11.7%by weight, preferably from 6.3 to 11.3%by weight, particularly preferably from 6.7 to 10.7%by weight, of 3-ethylheptanol;

● from 1.9 to 3.9%by weight, preferably from 2.1 to 3.7%by weight, particularly preferably from 2.4 to 3.4%by weight, of 2-ethylheptanol;

● from 1.7 to 3.7%by weight, preferably from 1.9 to 3.5%by weight, particularly preferably from 2.2 to 3.2%by weight, of 2-propylhexanol;

● from 3.2 to 9.2%by weight, preferably from 3.7 to 8.7%by weight, particularly preferably from 4.2 to 8.2%by weight, of 3, 5-dimethylheptanol; from 6.0 to 16.0%by weight, preferably from 7.0 to 15.0%by weight, particularly preferably from 8.0 to 14.0%by weight, of 2, 5-dimethyl-heptanol;

● from 1.8 to 3.8%by weight, preferably from 2.0 to 3.6%by weight, particularly preferably from 2.3 to 3.3%by weight, of 2, 3-dimethylheptanol;

● from 0.6 to 2.6%by weight, preferably from 0.8 to 2.4%by weight, particularly preferably from 1.1 to 2.1%by weight, of 3-ethyl-4-methylhexanol;

● from 2.0 to 4.0%by weight, preferably from 2.2 to 3.8%by weight, particularly preferably from 2.5 to 3.5%by weight, of 2-ethyl-4-methylhexanol; and

● from 0.5 to 6.5%by weight, preferably from 1.5 to 6%by weight, particularly preferably from 1.5 to 5.5%by weight, of other alcohols having 9 carbon atoms.

In some embodiments, suitable iso-nonanol for preparing the alkoxylated iso-nonanol according to the present invention may have the following composition, based on the total sum of the com-ponents of 100%by weight:

● from 7.0 to 15.0%by weight of n-nonanol;

● from 14.8 to 26.8%by weight of 6-methyloctanol;

● from 14.5 to 26.5%by weight of 4-methyloctanol;

● from 3.8 to 6.8%by weight of 2-methyloctanol;

● from 6.3 to 11.3%by weight of 3-ethylheptanol;

● from 2.1 to 3.7%by weight of 2-ethylheptanol;

● from 1.9 to 3.5%by weight of 2-propylhexanol;

● from 3.7 to 8.7%by weight of 3, 5-dimethylheptanol;

● from 7.0 to 15.0%by weight, of 2, 5-dimethyl-heptanol;

● from 2.0 to 3.6%by weight of 2, 3-dimethylheptanol;

● from 0.8 to 2.4%by weight of 3-ethyl-4-methylhexanol;

● from 2.2 to 3.8%by weight of 2-ethyl-4-methylhexanol; and

● preferably from 1.5 to 6%by weight of other alcohols having 9 carbon atoms.

In some other embodiments, suitable iso-nonanol for preparing the alkoxylated iso-nonanol ac-cording to the present invention may have the following composition, based on the total sum of the components of 100%by weight,

● from 8.0 to 14.0%by weight of n-nonanol;

● from 15.8 to 25.8%by weight of 6-methyloctanol;

● from 15.5 to 25.5%by weight of 4-methyloctanol;

● from 4.3 to 6.3%by weight of 2-methyloctanol;

● from 6.7 to 10.7%by weight of 3-ethylheptanol;

● from 2.4 to 3.4%by weight of 2-ethylheptanol;

● from 2.2 to 3.2%by weight of 2-propylhexanol;

● from 4.2 to 8.2%by weight of 3, 5-dimethylheptanol;

● from 8.0 to 14.0%by weight of 2, 5-dimethyl-heptanol;

● from 2.3 to 3.3%by weight of 2, 3-dimethylheptanol;

● from 1.1 to 2.1%by weight of 3-ethyl-4-methylhexanol;

● from 2.5 to 3.5%by weight of 2-ethyl-4-methylhexanol; and

● from 1.5 to 5.5%by weight of other alcohols having 9 carbon atoms.

According to any one embodiment of the present invention, the degree of branching indicates the sum of branching number multiplying with the proportion of the respective alkyl alcohol in the mixture of isomeric alkyl alcohol. For example, the branching degree of nonanol-1 is 0, 2-ethyl-2-methylhexanol-1 is 2 and 2, 3, 4-trimethylhexanol-1 is 3. The branching numbers of the respective nonanol can refer to the below table.

The degree of branching of the isomeric nonanols is the sum of all values which are obtained by multiplying the branching number with the proportion of the respective nonanol in the mixture of isomeric nonanols.

The present invention further relates to a composition comprising the alkoxylated iso-nonanol as nonionic surfactant. There is no particular restriction to type of the formulations according to the present invention. The alkoxylated iso-nonanol as described herein can be used in some compo-sitions such as cleaning composition including laundry detergent compositions, industrial and in-stitutional cleaning compositions, fabric and home care compositions, cosmetic or personal care compositions, oil field-formulations such as crude oil emulsion breaker, inks, electro plating com-positions, cementitious compositions, lacquers or paints, textile auxiliary compositions, emulsion polymerization compositions and/or agrochemical compositions.

Particularly, the present invention provides a cleaning composition including laundry detergent composition, industrial and institutional cleaning composition, or a fabric and home care compo-sition comprising the alkoxylated iso-nonanol of the present invention as nonionic surfactant. Pref-erably, the alkoxylated iso-nonanol suitable to be used in a cleaning composition or a fabric and home care composition has a degree of propoxylation in the range of 1.1 to 7, preferably in the range of 1.5 to 7 (for example 1.5, 2, 3, 4, 5, 6 and 7) and has a degree of ethoxylation in the range of 3 to 14, preferably in the range of 3 to 10, more preferably in the range of 3 to 9. Partic-ularly, the most suitable alkoxylated iso-nonanol to be used in a cleaning composition or a fabric and home care composition, is obtained by alkoxylation of a mixture of isomeric nonanols having a degree of branching in the range of 1.1 to 1.5, preferably in the range of 1.1 to 1.4.

The term “cleaning composition” as used herein includes compositions and formulations designed for cleaning any soiled material, which includes, but are not limited to laundry detergent compo-sitions, industrial and institutional cleaning compositions for use of cleaning for example hard surfaces such as tiles, carpets, PVC-surfaces, wooden surfaces, metal surfaces, lacquered sur-faces. The term “fabric and home care compositions” includes for example fabric softening com-positions, fabric enhancing compositions, fabric freshening compositions, laundry prewash, laun-dry pretreat, laundry additives, spray products, dry cleansing compositions, laundry additives, laundry rinse additives, wash additives, post-rinse fabric treatment compositions, ironing aids, dish washing compositions (including auto dishwashing composition and manual dishwashing composition) , hard surface cleansing compositions, unit dose formulations, delayed delivery for-mulations, detergents contained on or in a porous substrate or nonwoven sheet, light-duty and heavy-duty liquid detergent compositions, bleaching compositions.

Particularly, in some laundry detergent compositions, the alkoxylated iso-nonanol of the present invention used as non-ionic surfactant has a degree of propoxylation in the range of 1.5 to 7, preferably in the range of 1.5 to 5, and has a degree of ethoxylation in the range of 3 to 10, preferably in the range of 3 to 9, more preferably in the range of 5 to 9. Particularly, the most suitable alkoxylated iso-nonanol to be used in laundry detergent compositions, is obtained by alkoxylation of a mixture of isomeric nonanols having a degree of branching in the range of 1.1 to 1.5, preferably in the range of 1.1 to 1.4.

Particularly, in some laundry detergent composition and, industrial and institutional cleaning com-position, the alkoxylated iso-nonaol of formula (I) of the present invention is the most suitable to be used as non-ionic surfactant and the alkoxylated iso-nonanol has a degree of propoxylation in the range of 1.5 to 7, preferably in the range of 1.5 to 5, and has a degree of ethoxylation in the range of 3 to 9, preferably in the range of 3 to 7, more preferably from 5 to 7.

Particularly, in some laundry detergent composition and, industrial and institutional cleaning com-position, the alkoxylated iso-nonaol of formula (II) of the present invention is also suitable to be used as non-ionic surfactant.

Particularly, in some dishwashing compositions including auto dishwashing compositions and manual dishwashing compositions, the suitable alkoxylated iso-nonanol of the present invention used as non-ionic surfactant has a degree of propoxylation in the range of 1.5 to 7, preferably in the range of 1.5 to 5, and has a degree of ethoxylation in the range of 3 to 10, preferably in the range of 3 to 9, more preferably in the range of 3 to 7. Particularly, the most suitable alkoxylated iso-nonanol to be used in a dishwashing composition, is obtained by alkoxylation of a mixture of isomeric nonanols having a degree of branching in the range of 1.1 to 1.5, preferably in the range of 1.1 to 1.4.

Particularly, in some dishwashing composition including auto dishwashing composition and man-ual dishwashing compositions, the suitable alkoxylated iso-nonanol of formula (II) according to the present invention as non-ionic surfactant has a degree of propoxylation (the first propyleneoxy units) in the range of 1.1 to 3, and has a degree of ethoxylation in the range of 3 to 10, preferably in the range of 3 to 7, and has a degree of propoxylation (the second propyleneoxy units) in the range of 0.5 to 2. Particularly, the most suitable alkoxylated iso-nonanol to be used in a dish washing composition, is obtained by alkoxylation of a mixture of isomeric nonanols having a de-gree of branching in the range of 1.1 to 1.5, preferably in the range of 1.1 to 1.4.

According to any one embodiment of the present invention, the alkoxylated iso-nonanol is present in the composition as nonionic surfactant in an amount varying in the range of 0.5%to 90%, preferably 1%to 80%, based on the total weight of the composition.

< A cleaning composition comprising the alkoxylated iso-nonanol>

According to the present invention, a cleaning composition comprising the alkoxylated iso-nona-nol may lead to improved foaming property, emulsification ability, formulation stability and satis-fied detergency performance.

Various types of cleaning compositions and fabric and home care compositions are known in the art. Any conventional formulations of those compositions may be applied with including the alkox-ylated iso-nonanol according to the present invention. The alkoxylated iso-nonanol according to the present invention may be used in those compositions in addition to or in place of an active or additive ingredient having a similar functional property.

In some embodiments, the present invention provides a laundry detergent composition and a fabric and home care composition comprising the alkoxylated iso-nonanol as described herein as nonionic surfactant, preferably a liquid laundry detergent composition such as a laundry care composition or a laundry washing composition, or a liquid fabric and home care composition.

The alkoxylated iso-nonanol can be used in combination with other surfactants, which may be selected from anionic surfactants, cationic surfactants, non-ionic surfactants, amphoteric surfac-tants, zwitterionic surfactants and any combinations thereof. The cleaning composition of the pre-sent invention may –and preferably does -further comprise from about 1%to about 70%by weight of the composition of a surfactant system.

Nonlimiting examples of anionic surfactants may include C₉-C₂₀ linear alkylbenzene sulfonates (LAS) , C₁₀-C₂₀ primary, branched chain and random alkyl sulfates (AS) ; C₁₀-C₁₈ secondary (2, 3) alkyl sulfates of the formula CH₃ (CH₂) _x (CHOSO₃ ^-M⁺) CH₃ and CH₃ (CH₂) _y (CHOSO₃ ^-M⁺) CH₂CH₃ where x and (y+1) are integers of at least about 7 and M is a water-solubilizing cation; unsaturated sulfates such as oleyl sulfate; C₁₀-C₁₈ alkyl alkoxy sulfates (AExS) wherein x is from 1 to 30; C₁₀-C₁₈ alkyl alkoxy carboxylates comprising 1 to 5 ethoxy units; mid-chain branched alkyl sulfates as described in US 6,020,303 and US 6,060,443; mid-chain branched alkyl alkoxy sulfates as described in US 6,008,181 and US 6,020,303; modified al-kylbenzene sulfonate (MLAS) as described in WO 99/05243, WO 99/05242 and WO 99/05244; methyl ester sulfonate (MES) ; and alpha-olefin sulfonate (AOS) .

Preferable examples of suitable anionic surfactants are alkali metal and ammonium salts of C₈-C₁₂-alkyl sulfates, of C₁₂-C₁₈-fatty alcohol ether sulfates, of C₁₂-C₁₈-fatty alcohol polyether sulfates, of sulfuric acid half-esters of ethoxylated C₄-C₁₂-alkylphenols (ethoxylation: 3 to 50 mol of ethylene oxide/mol) , of C₁₂-C₁₈-alkylsulfonic acids, of C₁₂-C₁₈ sulfo fatty acid alkyl esters, for ex-ample of C₁₂-C₁₈ sulfo fatty acid methyl esters, of C₁₀-C₁₈-alkylarylsulfonic acids, preferably of n-C₁₀-C₁₈-alkylbenzene sulfonic acids, of C₁₀-C₁₈ alkyl alkoxy carboxylates and of soaps such as for example C₈-C₂₄-carboxylic acids. Preference is given to the alkali metal salts of the aforemen-tioned compounds, particularly preferably the sodium salts.

For example, an anionic surfactant selected from C₁₀-C₁₅-linear alkylbenzenes sulfonates, C₁₀-C₁₈-alkylether sulfates with 1 to 5 ethoxy units and C₁₀-C₁₈-alkylsulfates may be used.

The cleaning composition or the fabric and home care composition may comprise one or more anionic surfactants in an amount in the range of 1%to 50%, preferably 2%to 30%, more prefer-ably 3%to 25%, and most preferably 5%to 25 %, based on the total weight of the composition.

Non-limiting examples of non-ionic surfactants may include C₈-C₁₈ alkyl ethoxylates, such as NE-non-ionic surfactants from Shell; ethylenoxide/propylenoxide block alkoxylates, such as from BASF; C₁₄-C₂₂ mid-chain branched alkyl alkoxylates, BAEx, wherein x is from 1 to 30, as described in US 6,153,577, US 6,020,303 and US 6,093,856; alkylpolysaccharides as described in U.S. 4,565,647; specifically alkylpolyglycosides as described in US 4,483,780 and US 4,483,779; polyhydroxy fatty acid amides as described in US 5,332,528; and ether capped poly (oxyalkylated) alcohol surfactants as described in US 6,482,994 and WO 01/42408.

The non-ionic surfactants are in particular alkoxylated alcohols and alkoxylated fatty alcohols, di-and multiblock copolymers of ethylene oxide and propylene oxide and reaction products of sorbi-tan with ethylene oxide or propylene oxide, furthermore alkylphenol ethoxylates, alkyl glycosides, polyhydroxy fatty acid amides (glucamides) .

The cleaning composition or the fabric and home care composition may comprise one or more non-ionic surfactants in an amount in the range of 1%to 50%, preferably 2%to 40%, more pref-erably 3%to 30%, and most preferably 5%to 25 %, based on the total weight of the composition.

Non-limiting examples of amphoteric surfactants may include water-soluble amine oxides and water-soluble sulfoxides, especially water-soluble amine oxides. Preferred amine oxides are alkyl dimethyl amine oxides and alkyl amido propyl dimethyl amine oxides, more preferably coco di-methyl amino oxide and coco amido propyl dimethyl amine oxide. Amine oxides may have a linear or mid-branched alkyl moiety.

Typical linear amine oxides include water-soluble amine oxides containing one C₈-C₁₈-alkyl moi-ety and two moieties selected from C₁-C₃-alkyl groups and C₁-C₃-hydroxyalkyl groups. The amine oxides of formula R₁-N (R₂) (R₃) O in which R₁ is a C₈-C₁₈-alkyl and R₂ and R₃ are selected from methyl, ethyl, propyl, isopropyl, 2-hydroxethyl, 2-hydroxypropyl and 3-hydroxypropyl. The linear amine oxide surfactants in particular may include linear C₁₀-C₁₈-alkyl dimethyl amine oxides and linear C₈-C₁₂-alkoxy ethyl dihydroxy ethyl amine oxides.

Typical mid-branched amine oxides have one alkyl moiety having n₁ carbon atoms and one alkyl branch having n₂ carbon atoms wherein the alkyl branch is located on the α or β carbon from the nitrogen. This type of branching for the amine oxide is also known in the art as an internal amine oxide. The sum of n₁ and n₂ is in the range of 10 to 24, preferably from 12 to 20, and more pref-erably 10 to 16. The number of carbon atoms for the one alkyl moiety (n₁) should be approximately the same number of carbon atoms as the one alkyl branch (n₂) such that the one alkyl moiety and the one alkyl branch are symmetric. Here “symmetric” means that (n₁-n₂) is less than or equal to 5, preferably 4, most preferably from 0 to 4 carbon atoms in at least 50 wt%, more preferably at least 75 wt%to 100 wt%of the mid-branched amine oxides. The amine oxide further comprises two moieties, independently selected from a C₁-C₃-alkyl, a C₁-C₃-hydroxyalkyl group, or a poly-ethylene oxide group containing an average of 1 to 3 ethylene oxide groups.

Preferably, the amphoteric surfactants may be selected from C_8-18-alkyl dimethyl aminoxides and C₈-C₁₈-alkyl di (hydroxyethyl) aminoxide.

Non-limiting examples of zwitterionic surfactants may include betaines such as alkyl betaines, alkylamidobetaines, amidazoliniumbetaines, sulfobetaines (INCI Sultaines) as well as phos-phobetaines. Preferred betaines are, for example alkylbetaines and sulfobetaines. Examples of suitable alkylbetaines and sulfobetaines include (designated in accordance with INCI) : Almon-damidopropyl Betaines, Apricotamidopropyl Betaines, Avocadamidopropyl Betaines, Babas-suamidopropyl Betaines, Behenamidopropyl Betaines, Behenyl Betaines, Canolamidopropyl Be-taines, Capryl/Capramidopropyl Betaines, Carnitine, Cetyl Betaines, Cocamidoethyl Betaines, Cocamidopropyl Betaines, Cocamidopropyl Hydroxysultaine, Coco-Betaines, Coco-Hydroxysul-taine, Coco/Oleamidopropyl Betaines, Coco-Sultaine, Decyl Betaines, Dihydroxyethyl Oleyl Glycinate, Dihydroxyethyl Soy Glycinate, Dihydroxyethyl Stearyl Glycinate, Dihydroxyethyl Tallow Glycinate, Dimethicone Propyl PG-Betaines, Erucamidopropyl Hydroxysultaine, Hydrogenated Tallow Betaines, Isostearamidopropyl Betaines, Lauramidopropyl Betaines, Lauryl Betaines, Lau-ryl Hydroxysultaine, Lauryl Sultaine, Milkamidopropyl Betaines, Minkamidopropyl Betaines, Myristamidopropyl Betaines, Myristyl Betaines, Oleamidopropyl Betaines, Oleamidopropyl Hy-droxysultaine, Oleyl Betaines, Olivamidopropyl Betaines, Palmamidopropyl Betaines, Palmitami-dopropyl Betaines, Palmitoyl Carnitine, Palm Kernelamidopropyl Betaines, Polytetrafluoroeth-ylene Acetoxypropyl Betaines, Ricinoleamidopropyl Betaines, Sesamidopropyl Betaines, Soyami-dopropyl Betaines, Stearamidopropyl Betaines, Stearyl Betaines, Tallowamidopropyl Betaines, Tallowamidopropyl Hydroxysultaine, Tallow Betaines, Tallow Dihydroxyethyl Betaines, Undecyle-namidopropyl Betaines And Wheat Germamidopropyl Betaines.

Non-limiting examples of cationic surfactants may include quaternary ammonium surfactants, which can have up to 26 carbon atoms, for example alkoxylated quaternary ammonium (AQA) surfactants as described in US 6,136,769; dimethyl hydroxyethyl quaternary ammonium as de-scribed in US 6,004,922; dimethyl hydroxyethyl lauryl ammonium chloride; polyamine cationic surfactants as described in WO 98/35002, WO 98/35003, WO 98/35004, WO 98/35005, and WO 98/35006; cationic ester surfactants as described in US patents Nos. 4,228,042, 4,239,660 4,260,529 and US 6,022,844; and amino surfactants as described in US 6,221,825 and WO 00/47708, specifically amido propyldimethyl amine (APA) .

The compositions of the invention may comprise adjunct additives (also abbreviated herein as “adjuncts” ) , such adjuncts being preferably in addition to the surfactant as described hereinabove. Suitable adjuncts may include builders, fatty acids and/or salts thereof, structurants, thickeners and rheology modifiers, clay/soil removal/anti-redeposition agents, polymeric soil release agents, dispersants such as polymeric dispersing agents, polymeric grease cleansing agents, solubilizing agents, amphiphilic copolymers, chelating agents, enzymes, enzyme stabilizing systems, encap-sulated benefit agents such as encapsulated perfume, bleaching compounds, bleaching agents, bleach activators, bleach catalysts, catalytic materials, brighteners, malodor control agents, pig-ments, dyes, opacifiers, pearlescent agents, hueing agents, dye transfer inhibiting agents, fabric softeners, carriers, suds boosters, suds suppressors (antifoams) , color speckles, silver care, anti-tarnish and/or anti-corrosion agents, alkalinity sources, pH adjusters, pH-buffer agents, hy-drotropes, scrubbing particles, anti-bacterial and anti-microbial agents, preservatives, anti-oxi-dants, softeners, carriers, fillers, solvents, processing aids, pro-perfumes, and perfumes.

In the context of the present invention, no distinction will be made between builders and such components elsewhere called “co-builders” . Examples of builders include complexing agents, ion-exchange compounds, dispersing agents, scale inhibiting agents and precipitating agents.

Builders may be selected from citrates, phosphates, silicates, carbonates, phosphonates, amino carboxylates and polycarboxylates.

Suitable citrates include mono-, di-and tri-alkali metal salts of citric acid, ammonium or substituted ammonium salts of citric acid, as well as citric acid. Citrates can be used as the anhydrous com-pound or as a hydrate, for example as trisodium citrate dihydrate. Any amount of citrates, when used, is calculated referring to anhydrous trisodium citrate.

Suitable phosphates include sodium metaphosphate, sodium orthophosphate, sodium hy-drogenphosphate, sodium pyrophosphate and polyphosphates such as sodium tripolyphosphate. However, it is preferred that the compositions according to the invention is free from phosphates, polyphosphates, and hydrogenphosphates.

Suitable silicates include sodium disilicate and sodium metasilicate, aluminosilicates such as for example zeolites and sheet silicates, in particular those of the formula α-Na₂Si₂O₅, β-Na₂Si₂O₅, and δ-Na₂Si₂O₅.

Suitable carbonates include alkali metal carbonates and alkali metal hydrogen carbonates, pref-erably sodium salts.

Suitable phosphonates are hydroxyalkanephosphonates and aminoalkanephosphonates. Among the hydroxyalkanephosphonates, 1-hydroxyethane-1, 1-diphosphonate (HEDP) is of particular im-portance as the builder. It is preferably used as sodium salt, the disodium salt being neutral and the tetrasodium salt being alkaline (pH 9) . Suitable aminoalkanephosphonates are preferably eth-ylene diaminetetramethylenephosphonate (EDTMP) , diethylenetriaminepentamethylene-phosphonate (DTPMP) , and also their higher homologues. The phosphonates are preferably used in the form of the neutrally reacting sodium salts, e.g. as hexasodium salt of EDTMP or as hepta-and octa-sodium salts of DTPMP.

Suitable amino carboxylates and polycarboxylates are nitrilotriacetates, ethylene diamine tetraac-etate, diethylene triamine pentaacetate, triethylenetetraamine hexaacetate, propylene diamine tetraacetic acid, ethanol-diglycines, methylglycine diacetate, and glutamine diacetate. The amino carboxylates and polycarboxylates are preferably used in the form of respective non-substituted or substituted ammonium salts and the alkali metal salts such as the sodium salts, in particular in respective fully neutralized salts form.

The compositions according to the invention may comprise an alkali carrier. The alkali carrier can ensure, for example, a pH of at least 9 if an alkaline pH is desired. Suitable alkali carriers are for example, alkali metal carbonates, alkali metal hydrogen carbonates, and alkali metal metasili-cates, and alkali metal hydroxides. Preferably the alkali metal is potassium in each case, more preferably sodium. In the present invention, a pH >7 may also be adjusted by using amines, preferably alkanolamines, more preferably triethanolamine.

The compositions according to the present invention may comprise an enzyme, preferably a de-tergent enzyme.

In one embodiment, the enzyme is classified as an oxidoreductase (EC 1) , a transferase (EC 2) , a hydrolase (EC 3) , a lyase (EC 4) , an isomerase (EC 5) , or a ligase (EC 6) . The EC-numbering is according to Enzyme Nomenclature, Recommendations (1992) of the Nomenclature Commit-tee of the International Union of Biochemistry and Molecular Biology including its supplements published 1993-1999. Preferably, the enzyme is a hydrolase (EC 3) .

The enzyme may be selected from proteases, amylases, lipases, cellulases, mannanases, hem-icellulases, phospholipases, esterases, pectinases, lactases, peroxidases, xylanases, cutinases, pectate lyases, keratinases, reductases, oxidases, phenoloxidases, lipoxygenases, ligninases, pullulanases, tannases, pentosanases, malanases, beta-glucanases, arabinosidases, hyaluroni-dases, chondroitinases, laccases, nucleases, DNase, phosphodiesterases, phytases, carbohy-drases, galactanases, xanthanases, xyloglucanases, oxidoreductase, perhydrolases, aminopep-tidase, asparaginase, carbohydrase, carboxypeptidase, catalase, chitinase, cyclodextrin glyco-syltransferase, alpha-galactosidase, beta-galactosidase, glucoamylase, alpha-glucosidase, beta-glucosidase, invertase, ribonuclease, transglutaminase, and dispersins, and combinations of at least two of the foregoing types. More preferably, the enzyme is selected from the group consist-ing of proteases, amylases, lipases, cellulases, mannanases, xylanases, DNases, dispersins, pectinases, oxidoreductases, and cutinases, and combinations of at least two of the foregoing types. Most preferably, the enzyme is a protease, preferably, a serine protease (EC 3.4.21) , more preferably, a subtilisin protease (EC 3.4.21.62) . Alternatively, the enzyme is an amylase (alpha and/or beta) of bacterial or fungal origin (EC 3.2.1.1 and 3.2.1.2, respectively) . Preferably, amyl-ases are selected from the group of alpha-amylases (EC 3.2.1.1) .

Preferably, the protease is a protease with at least 90%sequence identity to SEQ ID NO: 22 of EP1921147B1 and having the amino acid substitution R101E (according to BPN’ numbering) . Preferably, the amylase is an amylase with at least 90%sequence identity to SEQ ID NO: 54 of WO2021032881A1.

The composition of the present invention can comprise one type of enzyme or more than one enzyme of different types, e.g., an amylase and a protease, or more than one enzyme of the same type, e.g., two or more different proteases, or mixtures thereof, e.g., an amylase and two different proteases.

The enzyme, when present, may be present in the compositions according to the present inven-tion in an amount sufficient to provide an effective amount for achieving a beneficial effect, pref-erably for primary washing effects and/or secondary washing effects, like antigreying or antipilling effects (e.g., in case of cellulases) . Preferably, the enzyme may be present in an amount of 0.00001%to 5%, preferably 0.00001%to 2%, more preferably 0.0001%to 1%, or even more preferably 0.001%to 0.5%enzyme protein based on the total weight of the compositions.

Preferably, an enzyme-containing compositions may further comprise an enzyme stabilizing sys-tem. The enzyme-containing composition may comprise 0.001%to 10%, 0.005%to 8%, or 0.01%to 6%of an enzyme stabilizing system, based on the total weight of the compositions. The enzyme stabilizing system can be any stabilizing system which is compatible with the enzyme.

Preferably, the enzyme stabilizing system comprises at least one compound selected from the group consisting of polyols (preferably, ethylene glycol, 1, 2-propanediol, 1, 3-propanediol, glycerol or sorbitol) , salts (preferably, CaCl₂, MgCl₂ or NaCl) , short chain (preferably, C₁-C₆) carboxylic acids or salts thereof (preferably, formic acid, formate (preferably, sodium formate) , acetic acid, acetate, or lactate) , borate, boric acid, boronic acids (preferably, 4-formyl phenylboronic acid (4-FPBA) ) , peptide aldehydes, peptide acetals, and peptide aldehyde hydrosulfite adducts. Prefera-bly, the enzyme stabilizing system comprises a combination of at least two of the compounds selected from the group consisting of salts, polyols, and short chain carboxylic acids and prefer-ably one or more of the compounds selected from the group consisting of borate, boric acid, boronic acids (preferably, 4-formyl phenylboronic acid (4-FPBA) ) , peptide aldehydes, peptide ac-etals, and peptide aldehyde hydrosulfite adducts. In particular, if proteases are present in the composition, protease inhibitors may be added, preferably selected from borate, boric acid, bo-ronic acids (preferably, 4-FPBA) , peptide aldehydes (preferably, peptide aldehydes like Z-VAL-H or Z-GAY-H) , peptide acetals, and peptide aldehyde hydrosulfite adducts.

The compositions according to the invention may further comprise a bleaching agent, which is preferably selected from sodium perborate, anhydrous or as the monohydrate or as the tetrahy-drate or as the so-called dihydrate, sodium percarbonate, anhydrous or as the monohydrate, and sodium persulfate.

The compositions according to the invention may further comprise a bleach catalyst, which is preferably selected from oxaziridinium-based bleach catalysts, bleach-boosting transition metal salts or transition metal complexes such as, for example, manganese-, iron-, cobalt-, ruthenium-or molybdenum-salen complexes or carbonyl complexes. Manganese, iron, cobalt, ruthenium, molybdenum, titanium, vanadium and copper complexes with nitrogen-containing tripod ligands and also cobalt-, iron-, copper-and ruthenium-amine complexes can also be used as bleach cat-alysts.

The compositions according to the invention can comprise a bleach activator, for example tetraac-etyl ethylene diamine, tetraacetylmethylene diamine, tetraacetylglycoluril, tetraacetylhexylene di-amine, acylated phenolsulfonates such as for example n-nonanoyl-or isononanoyloxybenzene sulfonates, N-methylmorpholinium-acetonitrile salts ( “MMA salts” ) , trimethylammonium acetoni-trile salts, N-acylimides such as, for example, N-nonanoylsuccinimide, 1, 5-diacetyl-2, 2-dioxohex-ahydro-1, 3, 5-triazine ( “DADHT” ) or nitrile quats (trimethylammonium acetonitrile salts) .

The compositions according to the invention may comprise a corrosion inhibitor, for example se-lected from triazoles, in particular benzotriazoles, bisbenzotriazoles, aminotriazoles, alkyla-minotriazoles, also phenol derivatives such as, for example, hydroquinone, pyrocatechol, hydrox-yhydroquinone, gallic acid, phloroglucinol or pyrogallol.

The compositions according to the invention may comprise some cleaning polymers and/or soil release polymers and/or anti-graying polymers.

The cleaning polymers may include, without limitation, “multifunctional polyethylene imines” (for example BASF’s HP20) and/or “multifunctional diamines” (for example BASF’s HP96) .

Suitable multifunctional polyethylene imines are typically ethoxylated polyethylene imines with a weight-average molecular weight Mw in the range from 3,000 to 250,000, preferably 5,000 to 200,000, more preferably 8,000 to 100,000, more preferably 8,000 to 50,000, more preferably 10,000 to 30,000, and most preferably 10,000 to 20,000 g/mol. Suitable multifunctional polyeth-ylene imines have 80 wt%to 99 wt%, preferably 85 wt%to 99 wt%, more preferably 90 wt%to 98 wt%, most preferably 93 wt%to 97 wt%or 94 wt%to 96 wt%ethylene oxide side chains, based on the total weight of the materials. Ethoxylated polyethylene imines are typically based on a polyethylene imine core and a polyethylene oxide shell. Suitable polyethylene imine core molecules are polyethylene imines with a weight-average molecular weight Mw in the range of 500 to 5,000 g/mol. Preferably employed is a molecular weight from 500 to 1,000 g/mol, even more preferred is a Mw of 600 to 800 g/mol. The ethoxylated polymer then has on average 5 to 50, preferably 10 to 35 and even more preferably 20 to 35 ethylene oxide (EO) units per NH-functional group.

Suitable multifunctional diamines are typically ethoxylated C₂-C₁₂-alkylene diamines, preferably hexamethylene diamine, which are further quaternized and optionally sulfated. Typical multifunc-tional diamines have a weight-average molecular weight Mw in the range from 2,000 to 10,000, more preferably 3,000 to 8,000, and most preferably 4,000 to 6,000 g/mol. Particularly, ethox-ylated hexamethylene diamine, furthermore quaternized and sulfated, may be employed, which contains on average 10 to 50, preferably 15 to 40 and even more preferably 20 to 30 ethylene oxide (EO) groups per NH-functional group, and which preferably bears two cationic ammonium groups and two anionic sulfate groups.

Suitable anti-graying polymers include copolymers of acrylic or maleic acid and styrene, graft polymers of acrylic acid onto maltodextrin or carboxymethylated cellulose and their alkali metal salts, in particular sodium salts thereof.

The compositions according to the present invention may also comprise a complexing agent, which is preferably selected from methylglycinediacetic acid (MGDA) and glutamic acid diacetic acid (GLDA) and salts thereof. MGDA and GLDA may be present as racemate or as enantiomeri-cally pure compounds. GLDA is preferably selected from L-GLDA or enantiomerically enriched mixtures of L-GLDA in which at least 80 mol%, preferably at least 90 mol%, of L-GLDA is present. Suitable salts are ammonium salts and alkali metal salts, particularly preferably potassium and in particular sodium salts.

The compositions according to the present invention may also comprise an antimicrobial agent and/or preservative. An antimicrobial agent is a chemical compound that kills microorganisms or inhibits their growth or reproduction. Microorganisms can be bacteria, yeasts or molds. A preserv-ative is an antimicrobial agent which may be added to aqueous products and compositions to maintain the original performance, characteristics and integrity of the products and compositions by killing contaminating microorganisms or inhibiting their growth. Examples of preservatives are as listed on pages 35 to 39 in patent application WO2021/115912 A1.

Especially of interest are the following antimicrobial agents and/or preservatives:

· 4, 4’ -Dichloro-2-hydroxydiphenyl ether (Synonyms: 5-chloro-2- (4-chlorophenoxy) phenol, Diclo-san, DCPP) ;

· 2-Phenoxyethanol (Synonyms: Phenoxyethanol, Methylphenylglycol, Phenoxetol, ethylene gly-col phenyl ether, Ethylene glycol monophenyl ether, 2- (phenoxy) ethanol, 2-phenoxy-1-etha-nol) ;

· 2-Bromo-2-nitropropane-1, 3-diol (Synonyms: 2-bromo-2-nitro-1, 3-propanediol, Bronopol) ;

· glutaraldehyde (Synonyms: 1, 5-pentandial, pentane-1, 5-dial, glutaral, glutardialdehyde) ;

· Glyoxal (Synonyms: ethandial, oxylaldehyde, 1, 2-ethandial) ;

· 2-Butyl-benzo [d] isothiazol-3-one (BBIT) ;

· 2-Methyl-2H-isothiazol-3-one (MIT) ;

· 2-Octyl-2H-isothiazol-3-one (OIT) ;

· 5-Chloro-2-methyl-2H-isothiazol-3-one (CIT or CMIT) ;

· Mixture of 5-chloro-2-methyl-2H-isothiazol-3-one (CMIT) and 2-methyl-2H-isothiazol-3-one (MIT) (Mixture of CMIT/MIT) ;

· 1, 2-benzisothiazol-3 (2H) -one (BIT) ;

· Hexa-2, 4-dienoic acid (trivial name “sorbic acid” ) and its salts, e.g., calcium sorbate, sodium sorbate; potassium (E, E) -hexa-2, 4-dienoate (Potassium Sorbate) ;

· Lactic acid and its salts; L- (+) -lactic acid; especially sodium lactate;

· Benzoic acid and salts of benzoic acid, e.g., sodium benzoate, ammonium benzoate, calcium benzoate, magnesium benzoate, MEA-benzoate, potassium benzoate;

· Salicylic acid and its salts, e.g., calcium salicylate, magnesium salicylate, MEA salicylate, so-dium salicylate, potassium salicylate, TEA salicylate;

· Benzalkonium chloride, benzalkonium bromide, benzalkonium saccharinate;

· Didecyldimethylammonium chloride (DDAC) ;

· N- (3-aminopropyl) -N-dodecylpropane-1, 3-diamine (Diamine) ;

· Peracetic acid; and

· Hydrogen peroxide.

The cleaning compositions according to the invention may comprise the at least one antimicrobial agent or preservative in an amount of 0.0001 to 10%, based on the total weight of the composi-tions.

Preferably, the cleaning compositions according to the invention may comprise 2-phenoxyethanol in an amount of 2 ppm to 5%, preferably 0.1%to 2%, or 4, 4’ -dichloro 2-hydroxydiphenyl ether (DCPP) in an amount of 0.001%to 3%, preferably 0.002%to 1%, more preferably 0.01%to 0.6%, based on the total weight of the compositions.

Preferably, the cleaning compositions according to the invention may comprise 4, 4’ -dichloro-2-hydroxydiphenylether, preferably in an amount of 0.001 to 3%, preferably 0.002 to 1%, more preferably 0.01 to 0.6%, based on the total weight of the compositions.

The cleaning compositions according to the invention may also comprise water and/or additional organic solvents, e.g., ethanol or propylene glycol, and/or fillers such as sodium sulfate.

Further optional ingredients may include, but are not limited to, viscosity modifiers, cationic sur-factants, foam boosting or foam reducing agents, perfumes, dyes, optical brighteners, and dye transfer inhibiting agents.

In another aspect, the present invention provides a method of preserving an aqueous cleaning composition comprising the alkoxylated iso-nonanol as described herein against microbial con-tamination or growth, which includes adding 2-phenoxyethanol in the cleaning composition.

In another aspect, the present invention provides a method of cleansing a fabric or a hard surface, which includes an antimicrobial treatment of the fabric or the hard surface with a cleaning com-position comprising the alkoxylated iso-nonanol as described herein and 4, 4’ -dichloro-2-hy-droxydiphenylether.

Aspects of the present invention will be more fully illustrated by the following examples, which are set forth to illustrate certain aspects of the present invention and are not to be construed as limiting thereof.

Various types of cleaning formulations are known in the art. Any conventional formulations may be applied with including the alkoxylated iso-nonanol nonionic surfactant according to the present invention. The alkoxylated iso-nonanol nonionic surfactant according to the present invention may be used in those formulations in addition to or in place of a conventional nonionic surfactant typi-cally comprised in cleaning formulations.

When the alkoxylated iso-nonanol is used in a cleaning composition as non-ionic surfactant, the alkoxylated iso-nonanol is present in the composition in an amount varying in the range of 0.5%to 40%, preferably 1%to 30%, preferably 2%to 20%based on the total weight of the composition.

According to the present invention, the alkoxylated iso-nonanol is particularly useful as a non-ionic surfactant in textile pre-treatment formulations such as textile auxiliary compositions. Partic-ularly, the alkoxylate iso-nonanol has a degree of propoxylation in the range of 1.1 to 7, preferably in the range of 1.5 to 7, more preferably in the range of 2 to 5, for example 2, 3, 4, 5, and has a degree of ethoxylation in the range of 3 to 10, preferably in the range 3 to 9, more preferably in the range of 5 to 9, for example 5, 6, 7, 8, 9. Particularly, the most suitable alkoxylated iso-nonanol in a composition for being used in textile production process, is obtained by alkoxylation of a mixture of isomeric nonanols having a degree of branching in the range of 1.1 to 1.5, preferably in the range of 1.1 to 1.4.

The textile auxiliary compositions for textile manufacturing comprising the alkoxylated iso-nonanol may lead to more desirable dynamic foaming property, wetting property and improved scouring performance.

The textile auxiliary compositions are widely used in textile industry for treating fibers, yarns or textiles, for example before dyeing, bleaching, printing, and/or finishing, to remove soluble and insoluble impurities, which may be natural, added and adventitious impurities, for example, oils, waxes, fats, vegetable matter, as well as dirt. Particularly, the textile auxiliary composition can be a scouring composition or a detergent composition used in textile manufacture process.

The textile auxiliary compositions are generally in form of aqueous solution of a surfactant, and optionally comprise one or more further components such as desizing agent, oxidant, alkali agent, bleaching agent, fluorescent whitening agent, stabilizer, defoaming agent and organic solvent.

According to the present invention, the alkoxylated iso-nonanol of the present invention may be used in the textile auxiliary compositions as the sole surfactant or in combination with one or more other surfactant.

The other surfactant may be cationic, anionic, nonionic, amphoteric surfactant or a combination thereof. Particularly, the surfactant may be anionic, nonionic or a combination thereof. Conven-tional nonionic surfactants useful for the scouring/detergent formulations are for example adducts of C_8-20-aliphatic alcohol with alkylene oxide such as ethylene oxide and/or propylene oxide, ad-ducts of C_6-20-alkyl phenols with alkylene oxide such as ethylene oxide and/or propylene oxide, and alkyl polyglycosides such as C_8-18-alkyl polyglycosides. Conventional anionic surfactants use-ful for the scouring/detergent formulations are for example alkyl ether phosphonates, alkyl sul-fates, alkyl ether sulfates, linear alkylsulfonic acid salts alkylnaphthalenesulfonic acids.

The desizing agent may be for example enzyme such as malt enzyme and pancreatic enzyme, acid such as sulfuric acid and hydrochloric acid, or sodium hydroxide.

The oxidant may be for example alkali metal bromate such as sodium bromate, peroxide such as hydrogen peroxide and peroxydisulfuric acid, and alkali metal hypochlorite such as sodium hypo-chlorite.

The alkali agent may be for example sodium carbonate or hydrates thereof, sodium hydrogencar-bonate nathorium silicate, Borax, ammonium hydroxide and sodium dihydrogen phosphate.

The bleaching agent may be for example oxidative bleach including chlorine bleach such as bleached powder, sodium hyperchlorite, sodium chlorite andisocyanuric trichloride, and peroxide bleach such as peroxide such as hydrogen peroxide, sodium peroxide, sodium perborate, potas-sium permanganate and peracetic acid, and reducing bleach such as sulfur dioxide, sodium hy-drogen sulfite, and sodium dithionite or hydrates thereof.

The fluorescent whitening agent, also called optical brighteners, may be for example triazine-stilbenes (di-, tetra-or hexa-sulfonated) , coumarins, imidazolines, diazoles, triazoles, benzoxa-zolines, biphenyl-stilbenes.

The stabilizer may be for example silicate such as sodium silicate, polycarboxylic acid, polyphos-phate such as sodium tripolyphosphate, aminocarboxylic acid such as ethylenediaminetetraacetic acid (EDTA) , organo-phosphonic acids hydroxycarboxylic acid, and sodium salt of carboxymethyl cellulose (CMC) .

The defoaming agent may be for example non-silicone defoamer such as mineral oil, polypropyl-ene glycol, kerosene and polyether, and silicon defoamer such as silicone oil, polyether modified silicone oil and silica gel/silicon mixture.

The organic solvent may be for example petroleum gasoline, aromatics such as benzen, chlorin-ated hydrocarbons such as trichloroethylene, tetrachloroethylene and carbon tetrachloride, In some embodiments, the alkoxylated iso-nonanol is particularly useful as a surfactant for cotton scouring/detergent formulations.

When the alkoxylated iso-nonanol is used in a texile auxiliary composition such as scouring and/or detergent composition for textile manufacturing, the alkoxylated iso-nonanol is present in the com-position in an amount varying in the range of 10%to 90%, preferably 30%to 80%, preferably 50%to 70%based on the total weight of the composition.

In another aspect, the alkoxylated iso-nonanol of the present invention can be also used as co-surfactant in an emulsion polymerization process for various monomer systems including, for ex-ample acrylate, styrene acrylate, vinyl-acetate acrylate, vinyl acetate ethylene. The alkoxylated iso-nonanol of the present invention used in an emulsion polymerization can lead to higher sta-bility and improved tinting strength.

In still another aspect, the alkoxylated iso-nonanol of the present invention can be also suitably used in an agrochemical formulation, for example, when being blended with fatty acid methyl ester to prepare for example a tank mix adjuvant, the alkoxylated iso-nonanol of the present in-vention leads to low foaming and better emulsion stability.

Embodiments

Various embodiments (Embodiments 1 to 10) are listed below. It will be understood that the em-bodiments listed below may be combined with all aspects and other embodiments in accordance with the scope of the invention.

Embodiment 1: An alkoxylated iso-nonanol represented by the formula:

RO- (PO) _n- (EO) _m -H (I)

Wherein

PO is propyleneoxy and EO is ethyleneoxy, and

n is a number in the range of 0.9 to 7,

m is a number in the range of 3 to 17.

Embodiment 2: The alkoxylated iso-nonanol according to Embodiment 1 obtained by alkoxylation of a mixture of isomeric nonanols having a degree of branching in the range of 1.1 to 1.5, prefer-ably in the range of 1.1 to 1.4.

Embodiment 3: A composition comprising the alkoxylated iso-nonanol as defined according to Embodiment 1 or 2, wherein the composition is laundry detergent composition, industrial and institutional cleaning composition, fabric and home care composition, cosmetic or personal care composition, oil field-composition, inks, electro plating composition, cementitious composition, lacquers or paints, textile auxiliary composition, emulsion polymerization composition, or agro-chemical composition.

Embodiment 4: The composition according to Embodiment 3, wherein the alkoxylated iso-nonanol is present in the composition in an amount varying in the range of 0.5%to 90%, preferably 1%to 80%, based on the total weight of the composition.

Embodiment 5: The composition according to Embodiments 3 to 4, which further comprises from 1%to 70%by weight of a surfactant system.

Embodiment 6: The composition according to any one of Embodiments 3 to 5 is a laundry deter-gent composition, industrial and institutional cleaning composition, or fabric and home care com-position, wherein the alkoxylated iso-nonanol has a degree of propoxylation in the range of 1.1 to 7, preferably in the range of 1.5 to 7, and has a degree of ethoxylation in the range of 3 to 14, preferably 3 to 10, more preferably in the range of 3 to 9.

Embodiment 7: The composition according to any one of Embodiments 3 to 5 is a textile auxiliary composition, wherein the alkoxylated iso-nonanol has a degree of propoxylation in the range of 1.1 to 7, preferably in the range of 1.5 to 7, more preferably in the range of 2 to 5, and has a degree of ethoxylation in the range of 3 to 10, preferably in the range of 3 to 9, more preferably in the range of 5 to 9.

Embodiment 8: The composition according to any one of Embodiments 1 to 7, which comprises 2-phenoxyethanol, preferably in an amount of 2 ppm to 5%, more preferably 0.1 to 2%by weight, based on the total weight of the composition.

Embodiment 9: The composition according to any one of Embodiments 1 to 8, which comprises 4, 4’ -dichloro-2-hydroxydiphenylether, preferably in an amount of 0.001 to 3%, preferably 0.002 to 1%, more preferably 0.01 to 0.6%, based on the total weight of the composition.

Embodiment 10: The composition according to any one of Embodiments 1 to 9, which comprises at least one enzyme, preferably at least one enzyme selected from the group consisting of prote-ases, amylases, lipases, cellulases, hemicellulases, mannanases, xylanases, DNases, dis-persins, pectinases, oxidoreductases, and cutinases.

Embodiment 11: Use of an alkoxylated iso-nonanol as defined in Embodiment 1 or 2 in a compo-sition, wherein the composition is laundry detergent composition, industrial and institutional clean-ing composition, fabric and home care composition, cosmetic or personal care composition, oil field-composition, inks, electro plating composition, cementitious composition, lacquers or paints, textile auxiliary composition, emulsion polymerization composition, or agrochemical composition.

Embodiment 12: An alkoxylated iso-nonanol represented by the formula (II) :

RO- (PO) _n- (EO) _m- (PO) _k-H (II)

wherein

PO is propyleneoxy and EO is ethyleneoxy, and

n is a number in the range of 0.9 to 7, preferably in the range of 1.1 to 5,

m is a number in the range of 3 to 17, preferably in the range of 3 to 14;

k is a number in the range of 0 to 5, preferably in the range of 0.5 to 3;

preferably, the alkoxylated iso-nonanol is obtained by alkoxylation of a mixture of isomeric nonanols having a degree of branching in the range of 1.1 to 1.5, preferably in the range of 1.1 to 1.4.

Embodiment 13: A composition comprising the alkoxylated iso-nonanol as defined according to Embodiment 12, wherein the composition is laundry detergent composition, industrial and institu-tional cleaning composition, fabric and home care composition, cosmetic or personal care com-position, oil field-composition, inks, electro plating composition, cementitious composition, lac-quers or paints, textile auxiliary composition, emulsion polymerization composition, or agrochem-ical composition.

Embodiment 14: The composition according to Embodiment 12 is a dishwashing composition, wherein the alkoxylated iso-nonanol is represented by the formula (II) RO- (PO) _n- (EO) _m- (PO) _k-H (II) , and n is a number in the range 1.1 to 3, m is a number in the range of 3 to 10, and k is a number in the range of 0.5 to 2.

Embodiment 15: Use of an alkoxylated iso-nonanol as defined in Embodiment 12 in a composition, wherein the composition is laundry detergent composition, industrial and institutional cleaning composition, fabric and home care composition, cosmetic or personal care composition, oil field-composition, inks, electro plating composition, cementitious composition, lacquers or paints, tex-tile auxiliary composition, emulsion polymerization composition, or agrochemical composition.

Examples

I. Chemicals and Examples:

Iso-nonanols for preparing the examples is commercially available from BASF.

INA-1.1PO-3EO: alkoxylated iso-nonanol containing 1.1 PO and 3EO per molecule.

INA-1.1PO-5EO: alkoxylated iso-nonanol containing 1.1 PO and 5EO per molecule.

INA-1.5PO-3EO: alkoxylated iso-nonanol containing 1.5 PO and 3EO per molecule.

INA-1.5PO-5EO: alkoxylated iso-nonanol containing 1.5 PO and 5EO per molecule.

INA-1.9PO-3EO: alkoxylated iso-nonanol containing 1.9PO and 3EO per molecule.

INA-1.9PO-5EO: alkoxylated iso-nonanol containing 1.9PO and 5EO per molecule.

INA-1.9PO-7EO: alkoxylated iso-nonanol containing 1.9PO and 7EO per molecule.

INA-3PO-3EO: alkoxylated iso-nonanol containing 3PO and 3EO per molecule.

INA-3PO-5EO: alkoxylated iso-nonanol containing 3PO and 5EO per molecule.

INA-3PO-7EO: alkoxylated iso-nonanol containing 3PO and 7EO per molecule.

INA-5PO-3EO: alkoxylated iso-nonanol containing 5PO and 3EO per molecule.

INA-5PO-5EO: alkoxylated iso-nonanol containing 5PO and 5EO per molecule.

INA-5PO-7EO: alkoxylated iso-nonanol containing 5PO and 7EO per molecule.

INA-7PO-7EO: alkoxylated iso-nonanol containing 7PO and 5EO per molecule.

INA-3EO: Ethoxylated iso-nonanol containing 3EO per molecule.

INA-5EO: Ethoxylated iso-nonanol containing 5EO per molecule.

INA-7EO: Ethoxylated iso-nonanol containing 7EO per molecule.

Commercial chemicals:

Natural C12/14 alcohol ethoxylates

C12/14 (EO) 7: C₁₂C₁₄ fatty alcohol ethoxylates with 7 moles of ethylene oxide, commercially avail-able from BASF

C12/14 (EO) 9: C₁₂C₁₄ fatty alcohol ethoxylates with 9 moles of ethylene oxide, available from BASF

LAS: Linear alkylbenzene sulfonates, commercially available from BASF

LABSA: Linear alkyl benzene sulphonic acid, commercially available from BASF, and

AES: Alcohol ethoxysulphates commercially available from BASF

C12/14 (EO) 2 (PO) 4: C₁₂C₁₄ fatty alcohol alkoxylates with 2 moles of ethylene oxide and 4 moles of propylene oxide.

II. Preparations

Examples:

INA-1.1PO-3EO was prepared in accordance with the following process:

1037 g of iso-nonanol (from BASF) and 3.3 g of catalyst KOH (88%, solid) were charged into a 5L pressure reactor. 3.5 bar of nitrogen was charged and then discharged to a pressure of 0.3 bar, and the same charging-discharging process was repeated. Under a stirring speed of 150 rpm and a temperature of 115℃, a vacuum of 200 mbar was applied for 15 min and then 80 mbar for 30min.

After the water content is less than 1,000ppm, 3.5 bar of nitrogen was charged into the pressure reactor and discharged to a pressure to 0.3 bar and the same charging-discharging process was repeated three times. Then, 0.5 bar of nitrogen was charged into the pressure reactor, which was set with a stirring speed of 400 rpm and heated to a temperature of 130 ℃. 514g of propylene oxide (PO) was charged into the pressure reactor at an PO flow rate of 250 g/h, with using the heat of reaction to reach the alkoxylation temperature in the range of 130 ℃ to 140 ℃. After the PO charging was finished, the reaction system was kept at 140 ℃ for 2 h. Then, 950 g of ethylene oxide (EO) was charged into the pressure reactor at an EO flow rate of 450 g/h, with using the heat of reaction to reach the alkoxylation temperature in the range of 160 ℃ to 180 ℃. After the EO charging was finished, the reaction system was kept at 170 ℃ for 1 h. After analysis and identification, the reactor is cooled down to 60℃. Afterwards, 3.1 g of acetic acid was added into the reactor and stirred for 15 minutes to obtained neutralized product, which was then discharged at a temperature below 60℃ into a bottle.

Other alkoxylated iso-nonanol nonionic surfactants were prepared by the same process, except that the iso-nonanol, ethylene oxide (EO) , propylene oxide (PO) and KOH were charged in amounts summarized in Table A below.

Table A.

III. Test Methods and Results

Degree of branching measurement and calculation

Apparatus: GC-FID

Measurement Method:

The retention time of each isomer has been identified by GC-FID. The iso-index is calculated with sum of branching number multiply with proportion. For example, the branching number for Nona-nol-1 is 1, for 2-Ethyl-2-methylhexanol-1 is 2 and for 2, 3, 4-Trimethylhexanol-1 is 3, according to the branching methyl group number. The proportion is tested via GC-FID. The lower the ISO index, the greater the linearity of the molecules in the respective fraction.

The degree of branching of the inventive examples is calculated as below table.

The results of the degree of branching of the Examples in Table B.

Examples:

Table B:

Test of Emulsifying ability

Test condition: 2g/L of alkoxylated iso-nonanol in deionized water at 23℃

Oil types: anti-wear hydraulic oil L-HM 46# (UK CULL)

Test method:

1) 20ml oil and 20ml surfactant solution@2g/L into the 100ml graduated cylinder;

2) after inverting for 1min, then record time water phase separates out to 10ml.

Test of Wetting performance

The tests are implemented according to EN1772: 2000. The different concentrations (0.5g/L, 1g/L and 2g/L of surfactants were prepared by adding the surfactant into 2g/L soda ash solution. 150 ml surfactant solution was added into a 200ml beaker and stirred evenly. The temperature was adjusted at 23 ℃. A piece of cotton canvas was placed on a clean wire ring and carefully posi-tioned on the liquid surface of the beaker. The stopwatch was started simultaneously and the time when the canvas ring became wet was recorded. The test continued when the canvas ring just being remained submerged and the time was recorded.

Table 1. Test data of Emulsifying abibility and wetting performance

Longer time means better emulsification performance.

less time means the better wetting performance.

Hard surface cleaning performance test:

1) Preparation of metal plates: washing the metal plates by water, then degreasing by 100%ethanol, weighing (M0) .

2) Preparation of the soiled metal plates: 0.3 g ～ 0.4 g of soil (motor oil SAE 5W-30 (ExxonMobil US) ) was applied on the plates (stainless steel 304) and spreaded by dropper; dried at 150℃±2℃ for 15 mins. Then the metal plates are Cooled down at room temperature and weighed (M1) .

3) Preparation of cleaning solution formulation:

2g/L product (alkoxylated iso-nonanol) content with 20g/L NaOH (SCRC) .

4) Test procedure: 600ml cleaning solution was prepared at 40℃±2℃; the soiled metal plates were soaked into the cleaning solution for 6 min, swing cleaning was carried out for 15s; swing cleaning for 15s in tap water at 40℃±2℃. Then the plates were dried at 105℃±2℃ for 1 hours, and then weighed (M2) .

Oil removal ratio:

Table 2. Test Results of hard surface cleaning performance

Higher value means better oil removal performance.

Alkoxylated iso-nonanol in laundry detergent formulations and performance tests

Formulation Viscosity:

The formulations were checked for the viscosity by a viscometer (DV2T LVT from Brookfield) at 25 ℃ with spindle 63 at 60 rpm.

Foaming Formation &Stability (Ross Miles) :

550 ml detergent solution (2g/L detergent) was prepared in hard water (Ca/Mg 3: 2, 250 ppm calculated as CaCO₃) to test foaming formation and stability by Ross Miles method. Firstly, 50 ml detergent solution was pre-charged into the volumetric cylinder and then the rest 500 ml detergent solution was poured into the cylinder from the top via a glass bulb. The foam volume was recorded after 30s and 5min.

Emulsification:

2%surfactant solution was formulated with dye as indicator for phase separation observation. Then mix 15 ml oil/fat and 15 ml surfactant solution in 50 ml cylinder and shake the cylinder up and down for 60 s. Record the time when water phase separates out to 5 ml.

Laundry Test:

A laundering process was simulated in lab using a Tergotometer (RHLQ-IV from RIDCI) which includes 16 barrels with respective rotor blades as washing units. The washing units were oper-ated at the same stirring speed of 120 rotation per minute (rpm) and each contains 1L water. Unless otherwise specified, 8-12 pieces of stained fabrics (square pieces of 6 cm x 6 cm, min 3 pieces for each stain) were immersed into water in each barrel, to which the detergent formulation were added, the washing cycle being carried out at 30 ℃ for 20 min. After the washing, the sam-ples were removed from the washing units, drained and rinsed twice in 10 L tap water for 30 seconds, followed by drying at ambient temperature overnight.

Measurement for whiteness change:

The fabrics were measured photometrically before and after the laundering process, by determin-ing reflectance values (in %) representing the degrees of whiteness with a sphere reflectance spectrometer (SF 500 type with a wavelength range of 360 to 700nm, optical geometry d/8°, from Datacolor, USA) with a UV cut-off filter, at a wavelength of 457 nm. Reflectance change (ΔR) represents the whiteness change of a fabric before and after the laundering and is used to eval-uate soil/stain removal performance of each detergent formulation in following Examples. Higher value of ΔR means higher cleaning performance.

Following fabrics were used for tests in the Examples:

JB 01: cotton stained with carbon black/oil, standard soiled fabric according to GB-T13174-2008, available from China research institute of daily chemical industry;

JB 02: cotton stained with pigment/protein, standard soiled fabric according to GB-T13174-2008, available from China research institute of daily chemical industry;

JB 03: cotton stained with pigment/sebum, standard soiled fabric according to GB-T13174-2008; available from China research institute of daily chemical industry;

WFK 10D: cotton stained with pigment/sebum, from WFK Testgewebe GmbH, Germany;

WFK 30D: polyester stained with pigment/sebum, from WFK Testgewebe GmbH, Germany;

C-S-61: cotton stained with beef fat, coloured with Sudan red, from Center For Testmaterials, Netherland;

P-S-61: polyester stained with beef fat, coloured with Sudan red, from Center For Testmaterials, Netherland;

C-S-62: cotton stained with lard, colored with Sudan red, from Center For Testmaterials, Nether-land; and

P-S-62: polyester stained with lard, colored with Sudan red, from Center For Testmaterials, Neth-erland.

Test results

Emulsification of nonionic surfactants

Table 3.

a. all results are seconds when 5 ml water phase separates out.

Longer time means higher emulsifying ability and higher emulsion stability.

Formulations and performances:

The amounts shown for the ingredients in following Tables refer to weight percentages unless specified otherwise. Percentages are usually based on total weight, unless specified otherwise.

Group A: regular liquid laundry detergent Formulations (pH=8)

Table A-1. Composition of the formulations

Table A-2. Performance

a. all tests were done in 250 ppm water (Ca/Mg 3: 2) with 2.0 g/L detergent;

b. JB01, JB02, JB03, WFK 10D, WFK 30D;

c. C-S-61, P-S-61, C-S-62, P-S-62

The formulation with alkoxylated iso-nonanols of the present invention exhibit enhanced proper-ties in terms of cleaning performance on sebum and tough stains.

Group B: concentrated liquid laundry detergent formulations (pH=8)

Table B-1. Composition of the formulations

Table B-2. Performance

a. all tests were done in 250 ppm water (Ca/Mg 3: 2) with 0.8 g/L detergent;

The formulation B-5 was formulated with addition of 3%ethanol as solvent to lower the viscosity. However, ethanol as a volatile solvent is not safe during transportation and production. It will also not contribute to cleaning or other detergent performance at all.

Without any organic solvent like ethanol in the formulations, high viscosity was found.

It was found the alkoxylated iso-nonanol according to the present invention can control the for-mulation viscosity, in particular, as observed for the formulations B-1, B-2, and B-4.

The alkoxylated iso-nonanol according to the present invention can also control the foaming, in particular, as observed for the formulations B-3 to B-4.

Group C: powder laundry detergent formulations (pH=12, 1%aqueous solution)

Table C-1. Composition of the formulations

Table C-2. Detergency

a. all tests were done in 250 ppm water (Ca/Mg 3: 2) with 2.0 g/L detergent;

b. C-S-61, P-S-61, C-S-62, P-S-62

It was found the formulations comprising alkoxylated iso-nonanols according to the present in-vention shows better cleaning against tough stains than natural C_12/14 ethoxylates in powder de-tergent.

Alkoxylated iso-nonanol in auto dishwashing (ADW) formulations and performance tests

Requirements for Rinse Aids

Rinse performance: All items must show no/low spotting and filming.

Excellent Drying of all Materials: All items including plastic need to be dry.

Defoaming Action: Foam formation caused by soil components must be suppressed; Due to wa-ter recycling, rinse aid is going with fresh water through the individual steps back to pre-wash.

Single surfactant test methods:

Measurement Method:

Foaming Formation &Stability (Ross Miles Foam Test)

550 ml surfactant solution (1g/L single surfactant) was prepared in DI water to test foaming for-mation and stability by Ross Miles method. Firstly, 50 ml surfactant solution was pre-charged into the volumetric cylinder and then the rest 500 ml surfactant solution was poured into the cylinder from the top via a glass bulb. The foam volume was recorded after 30s and 5min.

Quick dry performance on melamine &ceramic plate:

100g solution comprising 10%by weight single surfactant rinse aid dishwasher was prepared and was diluted to 1: 1000, then heated the prepared solution to 80 ℃. The next step was immersing a black melamine or ceramic plate into the solution for 30 seconds then the plate was taken out, the formation of water film was checked on the surface and the drying time was recorded.

Performance of defoaming against protein:

The protein soil was prepared based on below composition in table xx. Then, the soil was manu-ally homogeneous mixing. The next step was testing in the machine (Winterhalter GS 501, wash temperature 60℃, rinse temperature 80℃) . The tank contents were prepared based on below composition in Table 4.

The test machine was started, the protein soil was manually added and stirred well then, the single surfactant was manually added and stirred well, the next step was running 1 cycle and then the defoaming effect was immediately observed and recorded.

Table 4. Composition of protein soil:

Table 5. Composition of tank contents:

Results

Table 6. Ross-miles foam performance of different single surfactant

All the alkoxylated iso-nonanol samples show good low-foaming behavior.

Table 7. Quick drying performance of different single surfactant on the Melamine plate

The alkoxylated iso-nonanols of the present invention show outstanding quick drying performance behavior on melamine material with shorter drying time.

Table 8. Quick drying performance of different single surfactant on the Ceramic plate

All the alkoxylated iso-nonanol samples show outstanding quick drying performance behavior on melamine material with shorter drying time.

Table 9. Defoaming behavior against protein soil

● Excellent: only 30%or less foam formed compared to the blank sample

● Good: 30%to 60%foam formed compared to the blank sample

● Ordinary: 60%to 90%foam formed compared to the blank sample

The alkoxylated iso-nonanol of the present invention show good defoaming against protein soil.

Rinse aid dishwasher performance

Test Formulations:

Table 10. Group A: rinse aid formulations (pH=3, Cloud point 40℃)

Foaming Formation &Stability (Ross Miles method) :

550 ml surfactant solution (1g/L rinse aid formulation) was prepared in tap water to test foaming formation and stability by Ross Miles method. Firstly, 50 ml surfactant solution was pre-charged into the volumetric cylinder and then the rest 500 ml surfactant solution was poured into the cyl-inder from the top via a glass bulb. The foam volume was recorded after 30s and 5min.

Quick dry performance on melamine &ceramic plates:

100g of rinse aid formulation was prepared and was diluted to 1: 1000 then was heated the pre-pared solution to 80 ℃. The next step was immersing a black melamine or ceramic plate into the solution for 30 seconds then the plate was taken out. The formation of water film was checked on the surface and the drying time was recorded.

Performance of defoaming against protein:

The protein soil was prepared according to below composition in Table 11. Then, the protein soil was manually homogeneous mixed. The next step was testing in the machine (Winterhalter GS 501, wash temperature 60 ℃, rinsing temperature 80 ℃) . The tank contents were prepared based on below composition in Table 12.

The test machine was started, while the protein soil was manually added and stirred well. Then the single surfactant was manually added and stirred well. The next step was running 5 cycles and the defoaming effect was observed and recorded.

Table 11. Composition of protein soil:

Table 12. Composition of tank contents:

Test Data

Table 13. Test data for Ross-miles foam performance

All the formulations based alkoxylated iso-nonanol show good defoaming effect.

Table 14. Quick drying performance of formulations on the Melamine plate

All the formulations comprising alkoxylated iso-nonanol of the present invention show outstanding quick drying performance behavior on melamine material with shorter drying time.

Table 15. Quick drying performance of different single surfactant on the Ceramic plate

The formulations comprising alkoxylated iso-nonanol show excellent fast drying performance on ceramic plate with shorter drying time.

Table 16. Foam control against Protein soil of iNA alkoxylates in full rinse aid formulations (Evaluation based on visual observation)

● Excellent: only 30%or less foam formed compared to the blank sample

● Good: 30%to 60%foam formed compared to the blank sample

● Ordinary: 60%to 90%foam formed compared to the blank sample

Formulations comprising alkoxylated iso-nonanol show good behavior against protein soil.

Alkoxylated iso-nonanol in textile auxiliary formulations for textile manufacturing

Wetting power under neutral pH condition

The wetting test preparation was shown in Table 17. The measurement was carried out according to GB/T 11983-2008 under neutral pH condition. The standard gray cotton disc should be store in dryer at 50℃ for more than 48h. 500ml surfactant aqueous solution were prepared with con-centration of 1g/L. The time from the disc immersed in solution to begin to sink was recorded. Ten times average was taken as the wetting time. The results are summarized in Table 18 below.

Table 17. Preparation chemicals for wetting test

Table 18. Wetting Power as Measured at 23℃.

The alkoxylated iso-nonanols of the present invention show improved wetting performance with shorter wetting time.

Foaming Behavior Under Neutral pH Condition

The foam volume was measured after 600ml of surfactant solution was flowed from certain height onto the liquid surface of the same solution cyclically and continuously. 1L sample solution with 1g/L concentration was prepared (shown in Table 19) . The equipment and samples were pre-heated according to the requirement of test, if necessary. The equipment was pre-washing. 600ml surfactant sample solution was poured into the equipment slowly to avoid foaming and to balance the test temperature. Then The pump was turned on and foam volume per 30 sec was recorded. The pump at 9min was stopped and the foam volumes per 30sec until 16min were recorded. The samples for foaming test were shown in Table 20.

Table 19. Samples for Dynamic Foaming Test

Table 20. Dynamic Foaming as Measured at 23℃

● Vol (ml) means foam volume

As can be seen from Table 20, the alkoxylated iso-nonanols of the present invention show lower foaming property.

Scouring Performance Test

Scouring performance was tested by treating cotton fabric. In order to study scouring performance on the cotton fabric, the experiment was carried out in which cotton fabric were treated with dif-ferent chemical formulations under same condition.

A piece of cotton woven fabric 5～15g without pre-treatment was weighted, the liquor ratio is cal-culated according to this fabric, as 1: 10. The liquor weight was used as the basis for the chemicals used in the process. The chemicals were directly added into the liquor into the beaker. The closed dye beakers are placed on the revolving disc and heated by infrared radiators under constant rotation. Scouring temperature was 95℃ running for 45mins. The dye beakers are cooled by air which is fed through a water-cooled heat exchanger. The fabric was taken out for further rinsing with water at 80℃ followed with rinsing with water at 50℃ for 10 min and rinsing with cold water twice. The fabric was Dried with line dry.

The specific operations are shown in the following Table 21.

Table 21. The chemical recipes used for scouring test in cotton pretreatment

The wicking test/capillary effect testing is the key test methods for evaluating the performance of fabric after scouring. The standard test methods as AATCC 198. To prepare fabric samples, the fabric was cut into warp 22.4cm and weft 2cm. The humidity of fabric samples was balanced at room temperature more than 24 hours. The samples were hung on the machine and the tension clamp was hung on the bottom of fabric. The wetted level was quickly recorded at 5min and 30min. The fabric was taken down and the average height was measured. The test results are shown in Table 22.

Table 22. Wicking /capillary testing

The formulations comprising the alkoxylated iso-nonanols of the present invention show better scouring performance with higher wicking height.

Institution Laundry Cleaning Performance Test

Inventive Examples

INA-5PO-5EO: alkoxylated iso-nonanol containing 5PO and 5EO per molecule

INA-5PO-7EO: alkoxylated iso-nonanol containing 5PO and 7EO per molecule

INA-1.9PO-5EO: alkoxylated iso-nonanol containing 1.9PO and 5EO per molecule

Comparative Examples

INA-5EO: Ethoxylated iso-nonanol containing 5EO per molecule

INA-7EO: Ethoxylated iso-nonanol containing 7EO per molecule

Group A Test as detergent: Commercial detergents are specially formulated to cope with the high demands of a professional laundry set up, like a care laundry room, it’s aim to achieve textile cleanliness by removing the tough levels of soiling effectively in a professional environment. The formulation of detergent mainly contains anionic surfactant, non-ionic surfactant and additives such as solvent and preservatives.

Group B Test as laundry booster: laundry boosters are additives that pair up with detergent to make it more effective and enhance your laundry detergent's cleaning power. It produces excel-lent performance by effectively emulsifying fatty/oily soils. Non-ionic surfactant is the main com-ponent for emulsification.

Ingredients used in the test formulations and the fabric used in the tests:

LAS: Linear alkylbenzene sulfonates 55%solid content (e.g. Disponil LDBS 55 from BASF)

IPA: Isopropanol CAS: 67-63-0 come from Sinopharm chemical Reagent Co., Ltd.

WFK 20B: polyester/cotton 65/35 stained with pigment/olive, from WFK Testgewebe GmbH, Ger-many;

WFK20C: polyester/cotton 65/35 stained with pigment/lanolin, from WFK Testgewebe GmbH, Germany;

WFK30B: polyester 100%stained with pigment/olive, from WFK Testgewebe GmbH, Germany;

WFK30C: polyester 100%stained with pigment/lanolin, from WFK Testgewebe GmbH, Germany;

Test methods:

Wash process:

A laundering process was simulated in lab using a Tergotometer (RHLQ-IV from RIDCI) which includes 16 barrels with respective rotor blades as washing units. The washing units were oper-ated at the same stirring speed of 120 rotation per minute (rpm) and each contains 1L water. Unless otherwise specified, 8-12 pieces of stained fabrics (square pieces of 6 cm x 6 cm, min 3 pieces for each stain) were immersed into water in each barrel, to which the detergent formulation were added with 0-500ppm, the washing cycle being carried out at 70 ℃ or 50 ℃ for 10 min. After the washing, the samples were removed from the washing units, drained and rinsed twice in 10 L tap water for 30 seconds, followed by drying at ambient temperature overnight.

Measurement for whiteness change:

The fabrics were measured photometrically before and after the laundering process, by determin-ing reflectance values (in %) representing the degrees of whiteness with a sphere reflectance spectrometer (SF 500 type with a wavelength range of 360 to 700nm, optical geometry d/8°, from Datacolor, USA) with a UV cut-off filter, at a wacelength of 457 nm. Refkectance change (ΔR) represents the whiteness change of a fabric before and after the laundering and is used to eval-uate soil/stain removal performance of each detergent formulation in following Examples. Higher value of ΔR means higher cleaning performance.

Group A: Formulation of detergent performance comparison

Liquid Commercial laundry detergent formulations are prepared containing the inventive nonionic surfactants of alkoxylated iso-nonanol and LAS. The formulations are prepared by first preparing a premix, containing surfactants, solvents, and water up to 90%. This pre-mix is prepared by adding all components to the appropriate amount of water and stirring at room temperature. At last water is added up to 100%.

Compositions are shown in Table 23.

Detergent performance comparison of group A under 70 ℃, results are shown in Table 24

a. all tests were done in 250 ppm water with 2.5 g/L detergent and 0.2g/L NaOH

Under 70 ℃ washing condition, compared to ethoxylated iso-nonanol (INA-5EO) surfactant, the detergent formulation comprising the inventive example INA-5PO-5EO shows significant improve-ment of washed textile whiteness for fabric. Among various fatty/oily soils, the alkoxylated iso-nonanol comprising both propoxylate and ethoxylate segments leads to improve cleaning perfor-mance.

Performance comparison of group A under 50 ℃, results are shown in Table 25

Under 50 ℃ washing condition, similar trends as washing at 70 ℃, the detergent performance is slightly better than washing at 70 ℃, which means INA-5PO-5EO is more suitable for low tem-perature washing which is help customer to save the heating energy.

Group B: Formulation of laundry booster performance comparison

Liquid Commercial laundry booster formulations are prepared containing the inventive nonionic surfactants of alkoxylated iso-nonanol. The formulations are prepared by first preparing a premix, containing surfactants, solvents, and water up to 90%. This pre-mix is prepared by adding all components to the appropriate amount of water and stirring at room temperature. At last water is added up to 100%.

Compositions are shown in Table 26

Laundry booster performance comparison of Group B under 65 ℃, results are shown in Table 27

b. all tests were done in 0 ppm water with 1.25 g/L detergent and 0.2g/L NaOH

The laundry booster performance of the inventive examples is much better than the comparative examples. The inventive examples alkoxylated iso-nonanol containing both propoxylation and ethoxylation segments show significant improvement in terms of laundry boost performance.

Use of alkoxylated iso-nonanol in auto dishwashing formulation

Inventive Example:

INA-3PO-3EO-2PO: alkoxylated iso-nonanol containing 3PO and 3EO and 2PO per molecule

INA-3PO-3EO-2PO was prepared in accordance with the following process:

671 g of iso-nonanol (from BASF, the same iso-nonanol for preparing the other inventive exam-ples having C₉-branching degree of 1.17) and 1.6 g of catalyst KOH (88%, solid) were charged into a 5L pressure reactor. 3.5 bar of nitrogen was charged and then discharged to a pressure of 0.3 bar, and the same charging-discharging process was repeated. Under a stirring speed of 150 rpm and a temperature of 115℃, a vacuum of 200 mbar was applied for 15 min and then 80 mbar for 30min.

After the water content is less than 1,000 ppm, 3.5 bar of nitrogen was charged into the pressure reactor and discharged to a pressure to 0.3 bar and the same charging-discharging process was repeated three times. Then, 0.5 bar of nitrogen was charged into the pressure reactor, which was set with a stirring speed of 400 rpm and heated to a temperature of 130 ℃. 810g of propylene oxide (PO) was charged into the pressure reactor at an PO flow rate of 250 g/h, with using the heat of reaction to reach the alkoxylation temperature in the range of 130 ℃ to 140 ℃. After the PO charging was finished, the reaction system was kept at 140 ℃ for 2 h. Then, 614g of ethylene oxide (EO) was charged into the pressure reactor at an EO flow rate of 450 g/h, with using the heat of reaction to reach the alkoxylation temperature in the range of 160 ℃ to 180 ℃. After the EO charging was finished, the reaction system was kept at 170 ℃ for 20min. Then temperature is lowered to 130C. 405g of propylene oxide (PO) was charged into the pressure reactor at an PO flow rate of 250 g/h, with using the heat of reaction to reach the alkoxylation temperature in the range of 130 ℃ to 140 ℃. After the PO charging was finished, the reaction system was kept at 140 ℃ for 2 h. After analysis and identification, the reactor is cooled down to 60℃. Afterwards, acetic acid was added into the reactor and stirred for 15 minutes to obtained neutralized product, which was then discharged at a temperature below 60℃ into a bottle.

Rinse aid performance test in auto dish washing formulation

Function and where to apply Rinse aid: Rinse aid is a surfactant formulation, with this formulation dispensed during the final rinse cycle of commercial auto dish wash process, can lower the sur-face tension of water, makes it easier for rinsing dishes in the dishwasher. rinse aid helps prevent water spots from forming on, for example, glasses, plates and cutlery. It also helps dishes dry faster.

2 in 1 Quick dry rinse aid agent: quick dry rinse aid is specially formulated with wetting agents to help water sheet off plates, crockery, glassware and cutlery. In quick dry rinse aid formulation, usually there would be 2 main components, 1 for improve the wetting, 1 for reducing foaming, in this invention, there would be possible to combine 2 components into a single ingredient, which balances the fast wetting and low foaming behavior.

Test methods:

Foaming Formation &Stability (Ross Miles) , usually used for single surfactant screening: 550 ml surfactant solution (1g/L single surfactant) was prepared in DI water to test foaming for-mation and stability by Ross Miles method. Firstly, 50 ml surfactant solution was pre-charged into the volumetric cylinder and then the rest 500 ml detergent solution was poured into the cylinder from the top via a glass bulb. The foam volume was recorded after 30s and 5min.

Performance of defoaming against protein (BASF method) , usually used for formulation as ma-chine foam:

The protein soil was prepared based on below composition in the Table 28. Then, above soil was manually homogeneous mixing. The next step is testing in the machine (wash temperature 60℃, rinse temperature 80℃) . The tank contents were prepared based on below composition in Table 29.

Start the test machine, manually adding protein soil and stirring well then manually adding single surfactant and stirring well, the next step is running 1 cycle immediately take the picture. At last, take the photo of after draining.

Table 28. Composition of protein soil:

Following test materials were used for tests in the Examples:

Wheat powder: available from Fulinmen wheat flour

Skimmed milk powder: available from Devondale instant skim milk powder

Whole egg powder: available from Qin wei Biotechnology Co., Ltd;

Table 29. Composition of tank contents:

Evaluation :

● Excellent: only 30%or less foam formed compared to the blank sample

● Good: 30%to 60%foam formed compared to the blank sample

● Ordinary: 60%to 90%foam formed compared to the blank sample

Performance of defoaming against manual dishwashing liquid (BASF method) usually used for formulation as machine foam:

The composition of tank content was prepared based on below composition in the table as below. Then apply 0.1g market dishwashing liquid onto 1 ceramic plate and start washing cycle wash. Repeat this procedure 10 times. At last visual check the foam level. Thought these pictures, we can clearly see the different foam-control for different rinse aids.

MDW soil: available White Cat manual dishwash liquid

Evaluation:

● Excellent: only 30%or less foam formed compared to the blank sample

● Good: 30%to 60%foam formed compared to the blank sample

● Ordinary: 60%to 90%foam formed compared to the blank sample

Quick dry performance on melamine &ceramic (Immerse plate, BASF method) :

Prepare 100g of contains 10%single surfactant rinse aid prototype and dilute to 1: 1000 then heat the prepared solution to 80 ℃. The next step is immersing a black melamine or ceramic plate into the solution for 30 seconds then take out the plate, check formation of water film on the surface and record drying time.

Example:

Table 30. Quick drying performance of different single surfactant on the plate of Melamine surface:

The results show that the inventive alkoxylated iso-nonanol containing propoxylation, ethoxylation and propoxylation segments (three segments) show significantly improved performance on Mel-amine surface.

Table 31. Quick drying performance on the plate of Ceramic surface:

The results show that the inventive alkoxylated iso-nonanol containing propoxylate, ethoxylate and propoxylate segments show significantly improved performance on ceramic surface.

Table 32. Ross-miles foaming performance under 23 ℃

Conclusion: compared to INA ethoxylated surfactant, alkoxylation blocked INA lower the foam-ing. PO number end-capped with 0.5 to 1.5, preferably 1 PO.

Table 33. Foam control against Protein soil in full rinse aid application

The inventive example alkoxylated iso-nonanol containing propoxylate, ethoxylate and propox-ylate (three units) segments lead to low foaming.

Table 34. Foam control against manual dishwashing liquid in full rinse aid application

The inventive example alkoxylated iso-nonanol containing propoxylation, ethoxylation and propoxylation (three units) segments lead to low foaming.

Claims

An alkoxylated iso-nonanol represented by the formula:
RO- (PO) _n- (EO) _m -H (I)

Wherein

R is a linear or branched C₉-alkyl, preferably R is a C₉-alkyl originating from iso-nonanol,

PO is propyleneoxy and EO is ethyleneoxy, and

n is a number in the range of 0.9 to 7, preferably 1.1 to 5,

m is a number in the range of 3 to 17, preferably 3 to 14.
The alkoxylated iso-nonanol according to claim 1 obtained by alkoxylation of a mixture of isomeric nonanols having a degree of branching in the range of 1.1 to 1.5, preferably in the range of 1.1 to 1.4.
A composition comprising the alkoxylated iso-nonanol as defined according to claim 1 or 2, wherein the composition is laundry detergent composition, industrial and institutional clean-ing composition, fabric and home care composition, cosmetic or personal care composition, oil field-composition, inks, electro plating composition, cementitious composition, lacquers or paints, textile auxiliary composition, emulsion polymerization composition, or agrochem-ical composition.
The composition according to claim 3, wherein the alkoxylated iso-nonanol is present in the composition in an amount varying in the range of 0.5%to 90%, preferably 1%to 80%, based on the total weight of the composition.
The composition according to claim 3 to 4, which further comprises from 1%to 70%by weight of a surfactant system.
The composition according to any one of claims 3 to 5 is a laundry detergent composition, industrial and institutional cleaning composition, or a fabric and home care composition, wherein the alkoxylated iso-nonanol has a degree of propoxylation in the range of 1.1 to 7, preferably in the range of 1.5 to 7, and has a degree of ethoxylation in the range of 3 to 14, preferably 3 to 10, more preferably in the range of 3 to 9.
The composition according to any one of claims 3 to 5 is a textile auxiliary composition, wherein the alkoxylated iso-nonanol has a degree of propoxylation in the range of 1.1 to 7, preferably in the range of 1.5 to 7, more preferably in the range of 2 to 5, and has a degree of ethoxylation in the range of 3 to 10, preferably in the range of 3 to 9, more preferably in the range of 5 to 9.
The composition according to any one of claims 1 to 7, which comprises 2-phenoxyethanol, preferably in an amount of 2 ppm to 5%, more preferably 0.1 to 2%by weight, based on the total weight of the composition.
The composition according to any one of claims 1 to 8, which comprises 4, 4’-dichloro-2-hydroxydiphenylether, preferably in an amount of 0.001 to 3%, preferably 0.002 to 1%, more preferably 0.01 to 0.6%, based on the total weight of the composition.
The composition according to any one of claims 1 to 9, which comprises at least one en-zyme, preferably at least one enzyme selected from the group consisting of proteases, am-ylases, lipases, cellulases, hemicellulases, mannanases, xylanases, DNases, dispersins, pectinases, oxidoreductases, and cutinases.
Use of an alkoxylated iso-nonanol as defined in claim 1 or 2 in a composition, wherein the composition is laundry detergent composition, industrial and institutional cleansing compo-sition, fabric and home care composition, cosmetic or personal care composition, oil field-composition, inks, electro plating composition, cementitious composition, lacquers or paints, textile auxiliary composition, emulsion polymerization composition, or agrochemical com-position.
An alkoxylated iso-nonanol represented by the formula (II) :
RO- (PO) _n- (EO) _m- (PO) _k-H (II)

wherein

R is a linear or branched C₉-alkyl, preferably R is a C₉-alkyl originating from iso-nonanol,

PO is propyleneoxy and EO is ethyleneoxy, and

n is a number in the range of 0.9 to 7, preferably in the range of 1.1 to 5,

m is a number in the range of 3 to 17, preferably in the range of 3 to 14;

k is a number in the range of 0 to 5, preferably in the range of 0.5 to 3;

preferably, the alkoxylated iso-nonanol is obtained by alkoxylation of a mixture of isomeric nonanols having a degree of branching in the range of 1.1 to 1.5, preferably in the range of 1.1 to 1.4.
A composition comprising the alkoxylated iso-nonanol as defined according to claim 12, wherein the composition is laundry detergent composition, industrial and institutional clean-ing composition, fabric and home care composition, cosmetic or personal care composition, oil field-composition, inks, electro-plating composition, cementitious composition, lacquers or paints, textile auxiliary composition, emulsion polymerization composition, or agrochem-ical composition.
The composition according to claim 12 is a dishwashing composition, wherein the alkox-ylated iso-nonanol is represented by the formula (II) RO- (PO) _n- (EO) _m- (PO) _k-H (II) , and n is a number in the range 1.1 to 3, m is a number in the range of 3 to 10, and k is a number in the range of 0.5 to 2.
Use of an alkoxylated iso-nonanol as defined in claim 12 in a composition, wherein the composition is laundry detergent composition, industrial and institutional cleaning composi-tion, fabric and home care composition, cosmetic or personal care composition, oil field-composition, inks, electro plating composition, cementitious composition, lacquers or paints, textile auxiliary composition, emulsion polymerization composition, or agrochemical com-position.