WO2016073222A1

WO2016073222A1 - Fluorochemical compositions, methods, and articles

Info

Publication number: WO2016073222A1
Application number: PCT/US2015/057056
Authority: WO
Inventors: Leonardus Alfons Maria DOELEN; Dirk M. Coppens
Original assignee: 3M Innovative Properties Company
Priority date: 2014-11-03
Filing date: 2015-10-23
Publication date: 2016-05-12
Also published as: TW201632684A

Abstract

A fluorochemical treatment composition that includes: at least one fluorochemical compound in an amount of 1 wt-% to 5 wt-% solids based on the total weight of the fluorochemical treatment composition; at least one monoether alkyl glycol solvent present in an amount of 3 wt-% to 25 wt-%, based on the total weight of the fluorochemical treatment composition; at least one cationic surfactant; and water; wherein the treatment composition is dried at room temperature on a fibrous substrate to provide an increase in at least one of oil repellency or water repellency compared to the same fluorochemical treatment composition without the monoether alkyl glycol solvent and dried at room temperature.

Description

FLUOROCHEMICAL COMPOSITIONS, METHODS, AND ARTICLES

BACKGROUND

Repellent fluorochemical textile treatment compositions based on C4- fluorochemistry have been in use over the past few years. Many commercially available fluorochemical treatment compositions require complex chemistry, resulting in processing and production issues and high manufacturing costs. Many conventional aqueous fluorochemical treatment compositions require high temperature drying and/or curing of the textile to provide acceptable levels of oil and/or water repellency. There is a need for additional fluorochemical treatment compositions that can be dried at room temperature to provide textiles with high oil and/or water repellency.

SUMMARY

The present disclosure provides fluorochemical compositions that include one or more fluorinated (i.e., fluorochemical) compounds and one or more monoether alkyl glycol solvents. Such fluorochemical treatment compositions can be used to treat fibrous substrates, especially synthetic textiles such as polyester and polyamide, to impart one or more repellency characteristics (e.g., water repellency and/or oil repellency) to such substrate.

In one embodiment, the present disclosure provides a fluorochemical treatment composition that includes at least one fluorinated (i.e., fluorochemical) compound, at least one monoether alkyl glycol solvent, at least one cationic surfactant, and water. Any combination of fluorinated compounds and monoether alkyl glycol solvents described herein can be used in such treatment compositions.

In one embodiment, the present disclosure provides a fluorochemical treatment composition that includes: at least one fluorochemical compound in an amount of 1 wt-% to 5 wt-% solids, based on the total weight of the fluorochemical treatment composition; at least one monoether alkyl glycol solvent present in an amount of 3 wt-% to 25 wt-%, based on the total weight of the fluorochemical treatment composition; at least one cationic surfactant; and water. Fluorochemical treatment compositions of the present disclosure are capable of being dried at room temperature on a fibrous substrate to provide an increase in at least one of oil repellency or water repellency compared to the same fluorochemical treatment composition without the monoether alkyl glycol solvent and dried at room temperature.

In certain embodiments, fluorochemical treatment compositions of the present disclosure are dried at room temperature on a fibrous substrate in an amount sufficient to provide an oil repellency value of at least 2 on a scale of 0 to 8, a water repellency value of at least 80 on a scale of 0 to 100, or both.

In one embodiment, the present disclosure provides a method of imparting repellency to a fibrous substrate having one or more surfaces. The method includes applying a fluorochemical treatment composition as described herein onto one or more surfaces of the fibrous substrate, and drying the fluorochemical composition at room temperature.

In one embodiment, the present disclosure provides an article that includes a fibrous substrate having one or more surfaces and a fluorochemical treatment composition as described herein disposed on one or more surfaces of the fibrous substrate, and impregnated within the fibrous substrate.

In one embodiment, the present disclosure provides a method of improving the repellency performance of a fluorochemical treatment composition. The method includes: providing an initial composition that includes at least one fluorochemical compound, at least one cationic surfactant, and water; and combining the initial composition with at least one monoether alkyl glycol solvent to provide a fluorochemical treatment composition that includes the at least one fluorochemical compound in an amount of 1 wt-% to 5 wt-% solids, and the at least one monoether alkyl glycol solvent in an amount of 3 wt-% to 25 wt-%, based on the total weight of the fluorochemical treatment composition; wherein the treatment composition is dried at room temperature on a fibrous substrate to provide an increase in at least one of oil repellency or water repellency compared to the same fluorochemical treatment composition without the monoether alkyl glycol solvent and dried at room temperature.

The terms "comprises" and variations thereof do not have a limiting meaning where these terms appear in the description and claims. The words "preferred" and "preferably" refer to embodiments of the disclosure that may afford certain benefits, under certain circumstances. However, other embodiments may also be preferred, under the same or other circumstances. Furthermore, the recitation of one or more preferred embodiments does not imply that other embodiments are not useful, and is not intended to exclude other embodiments from the scope of the disclosure.

In this application, terms such as "a," "an," and "the" are not intended to refer to only a singular entity, but include the general class of which a specific example may be used for illustration. The terms "a," "an," and "the" are used interchangeably with the term "at least one." The phrases "at least one of and "comprises at least one of followed by a list refers to any one of the items in the list and any combination of two or more items in the list.

As used herein, the term "or" is generally employed in its usual sense including "and/or" unless the content clearly dictates otherwise.

The term "and/or" means one or all of the listed elements or a combination of any two or more of the listed elements.

Also herein, all numbers are assumed to be modified by the term "about." As used herein in connection with a measured quantity, the term "about" refers to that variation in the measured quantity as would be expected by the skilled artisan making the

measurement and exercising a level of care commensurate with the objective of the measurement and the precision of the measuring equipment used.

Also herein, the recitations of numerical ranges by endpoints include all numbers subsumed within that range as well as the endpoints (e.g., 1 to 5 includes 1, 1.5, 2, 2.75, 3, 3.80, 4, 5, etc.). And, the phrase "up to" a particular number includes that number (e.g., "up to 80 wt-%" includes 80 wt-%).

As used herein, the term "room temperature" refers to a temperature of about 15°C to about 30°C, or about 20°C to about 25°C, or about 22°C to about 25°C.

Reference throughout this specification to "one embodiment," "an embodiment," or "certain embodiment," etc. means that a particular feature, configuration, composition, or characteristic described in connection with the embodiment is included in at least one embodiment of the invention. Thus, the appearances of such phrases in various places throughout this specification are not necessarily referring to the same embodiment of the invention. Furthermore, the particular features, configurations, compositions, or characteristics may be combined in any suitable manner in one or more embodiments.

The above summary of the present disclosure is not intended to describe each disclosed embodiment or every implementation of the present disclosure. The description that follows more particularly exemplifies illustrative embodiments. In several places throughout the application, guidance is provided through lists of examples, which examples can be used in various combinations. In each instance, the recited list serves only as a representative group and should not be interpreted as an exclusive list. DETAILED DESCRIPTION OF EXEMPLARY EMBODIMENTS

The present disclosure provides fluorochemical compositions that include one or more fluorinated (i.e., fluorochemical) compounds and one or more monoether alkyl glycol solvents. Such fluorochemical treatment compositions can be used to treat fibrous substrates, to impart one or more repellency characteristics (e.g., water repellency and/or oil repellency) to such fibrous substrate.

Monoether alkyl glycol solvents are particularly advantageous, as compared to other solvents, including other glycol ethers (e.g., diether alkyl glycols such as bis(2- methoxyethyl) ether or "Diglyme" and proglyme, or monoether aryl glycols such as 1- phenoxypropan-2-ol or DOWANOL PPH), due to their ability to provide fluorochemical treatment compositions that are dried at room temperature on a fibrous substrate to provide an increase in at least one of oil repellency or water repellency compared to the same fluorochemical treatment composition without the monoether alkyl glycol solvent and dried at room temperature.

Due to the presence of one or more monoether alkyl glycol solvents,

fluorochemical treatment compositions of the present disclosure are dried at room temperature on a fibrous substrate in an amount sufficient to provide an oil repellency value of at least 2 on a scale of 0 to 8, a water repellency value of at least 80 on a scale of O to 100, or both.

Fluorochemical treatment compositions of the present disclosure include water and can be in the form of an aqueous dispersion, suspension, emulsion, or solution. Typically, a fluorochemical treatment composition of the present disclosure includes water in an amount of at least 75 weight percent (wt-%), based on the total weight of the fluorochemical treatment composition. Typically, a fluorochemical treatment composition of the present disclosure includes water in an amount of up to 95 weight percent (wt-%), based on the total weight of the fluorochemical treatment composition.

One or more fluorinated compounds (i.e., fluorochemical compounds) can be emulsified, dissolved, suspended, or dispersed in water and a monoether alkyl glycol solvent to form fluorochemical treatment compositions suitable for treating a fibrous substrate. In certain embodiments, the compositions contain at least 1 wt-%, or at least 2 wt-%, non- volatile solids (based on the total weight of the components). In certain embodiments, the compositions contain no greater than 5 wt-%, or no greater than 3 wt-%, non- volatile solids (based on the total weight of the components).

When applied and dried, the fluorochemical compositions of the present disclosure impart oil and/or water repellency properties to a wide variety of fibrous substrates.

Certain preferred fluorochemical treatment compositions of the present disclosure impart good water repellency to a fibrous substrate, particularly polyester and polyamide fabrics, as demonstrated by at least an 80 spray rating, or at least a 90 spray rating, or a 100 spray rating (on a scale of 0 to 100, treated and tested according to the Spray Rating procedure in the Examples Section). Certain preferred fluorochemical treatment compositions of the present disclosure impart good oil repellency to a fibrous substrate, particularly polyester and polyamide fabrics, as demonstrated by at least a 2 oil repellency rating, or at least a 3 oil repellency rating, or at least a 4 oil repellency rating, or at least a 5 oil repellency rating, or at least 6 oil repellency rating (on a scale of 1 to 8, treated and tested according to the Oil Repellency procedure in the Examples Section).

Fluorochemical Compounds

Fluorochemical treatment compositions of the present disclosure include at least one fluorochemical compound. Herein, a fluorochemical composition can include one fluorochemical compound, or a mixture of different fluorinated compounds, as described herein.

Fluorinated compounds suitable for use in fluorochemical treatment compositions of the present disclosure include a wide variety of conventional fluorinated compounds that are useful for treatments of fibrous substrates. Suitable fluorinated compounds include fluorochemical esters and polyesters, fluorochemical urethanes and polyurethanes (including blocked urethanes and polyurethanes), fluorochemical poly(meth)acrylates, and mixtures thereof. In particular, preferred fluorinated compounds have terminal perfluorinated aliphatic groups with 4 to 6 carbon atoms, such as C4F9- and C₆Fi3- containing compounds.

In certain embodiments, the fluorochemical compound is selected from the group of a fluorochemical polyurethane, a fluorochemical (meth)acrylate copolymer (e.g., a C6- or a C4-acrylate), and mixtures thereof.

Suitable fluorochemical polyurethanes are described, for example, in International Publication No. WO 2013/162704 (Coppens et al.) and U.S. Pat. Nos. 7,750,093 (Elsbernd et al.) and 7,078,456 (Jariwala et al). Such fluorinated compounds include: (i) a fluorochemical oligomeric portion; (ii) a fluorine-free hydrocarbon moiety; and (iii) a di-, tri-, or polymeric isocyanate-derived linking group.

Other fluorinated compounds (i.e., fluorochemical compounds) include a fluorochemical (meth)acrylate copolymer (e.g., a C6- or a C4-acrylate). Herein, a

(meth)acrylate includes methacrylates as well as acrylates. Examples include copolymers made from fluorochemical (meth)acrylates and hydrocarbon (meth)acrylates (e.g., MeFBSEMA/ODMA), fluorochemicals based on C6-telomer fluorochemical acrylate chemistry (such as those available from Asahi Glass under the trade designation "AGE- 082"), and mixtures thereof.

Specific examples of fluorinated compounds are described in the Examples

Section: FC-1 to FC-7 (fluorinated (meth)acrylate urethanes, blocked with MEKO or unblocked), FC-8 (80/20 weight ratio of MeFBSEMA and ODMA copolymer), and FC-9 (Asahi Glass "AGE-082" C6-telomer fluorochemical acrylate chemistry).

Fluorinated compounds that are not suitable for use in treatment compositions of the present disclosure include those that are designed for application to hard surfaces (e.g., terracotta, granite, marble, concrete, etc.). Treatment compositions for such surfaces are typically anionic or nonionic compositions, such as that available as PM-5000 (anionic fluorochemical dispersion from 3M Company).

In certain embodiments, fluorochemical treatment compositions of the present disclosure include at least one fluorochemical compound in an amount of at least 1 wt-%, or at least 2 wt-% solids (i.e., the nonvolatile material), based on the total weight of the fluorochemical treatment composition. In certain embodiments, fluorochemical treatment compositions of the present disclosure include at least one fluorochemical compound in an amount of up to 5 wt-%, or up to 3 wt-% solids, based on the total weight of the fluorochemical treatment composition.

The amount of the at least one fluorochemical compound could include simply one fluorochemical compound or a mixture thereof. For example, this amount could include a mixture of different fluorochemical compounds, each of which is less than 1 wt-%, but the total amount is at least 1 wt-%.

Monoether Alkyl Glycol Solvents

Fluorochemical treatment compositions of the present disclosure include one or more monoether alkyl glycol solvents.

In certain embodiments, suitable monoether alkyl glycol solvents are those soluble in water in an amount of at least 3 wt-% at room temperature. In certain embodiments, monoether alkyl glycol solvents are those soluble in water in an amount of at least 5 wt-% at room temperature, or at least 10 wt-% at room temperature, or at least 15 wt-% at room temperature.

Monoether alkyl glycol solvents are particularly advantageous, as compared to other solvents such as alcohols, esters, amides, ketones, hydrocarbons,

hydrofluorocarbons, hydrofluoroethers, chlorohydrocarbons, chlorocarbons, glycols (e.g., ethylene glycol, propylene glycol, dipropylene glycols), and other glycol ethers (e.g., diether alkyl glycols such as bis(2-methoxyethyl) ether known as "Diglyme" and diether(dimethoxy dipropyleneglycol) known as "Proglyme DMM," or monoether aryl glycols such as l-phenoxypropan-2-ol or DOWANOL PPH), due to their ability to provide fluorochemical treatment compositions that are capable of being dried at room temperature on a fibrous substrate to provide an increase in at least one of oil repellency or water repellency compared to the same fluorochemical treatment composition without the monoether alkyl glycol solvent. Due to the presence of one or more monoether alkyl glycol solvents, fluorochemical treatment compositions of the present disclosure are dried at room temperature on a fibrous substrate in an amount sufficient to provide an oil repellency value of at least 2 on a scale of 0 to 8, a water repellency value of at least 80 on a scale of 0 to 100, or both. Exemplary monoether alkyl glycol solvents suitable for use in compositions of the present disclosure include dipropylene glycol n-butyl ether (available from Dow Chemical as DOWANOL DPnB), dipropylene glycol methyl ether (available from Dow Chemical as DOWANOL DPM), butyl diglycol (available from Dow Chemical as BDG), and tripropylene glycol methyl ether (available from Dow Chemical as DOWANOL TPM), ethylene glycol monopropyl ether (2-propoxyethanol, CH3CH2CH2OCH2CH2OH), ethylene glycol monoisopropyl ether (2-isopropoxyethanol, (CHs^CHOCEhCEhOH), ethylene glycol monobutyl ether (2-butoxyethanol, CH3CH2CH2CH2OCH2CH2OH), and diethylene glycol mono-n-butyl ether (2-(2-butoxyethoxy)ethanol,

CH3CH2CH2CH2OCH2CH2OCH2CH2OH). Mixtures of such solvents may be used in the compositions of the present disclosure.

In certain embodiments, the monoether alkyl glycol solvent is a mono-(Cl- C4)alkyl ether of mono-, di-, or tri-ethylene or propylene glycol.

In certain embodiments of the present disclosure, a fluorochemical treatment composition includes a monoether alkyl glycol solvent selected from the group of dipropylene glycol n-butyl ether, dipropylene glycol methyl ether, tripropylene glycol methyl ether, butyl diglycol, and mixtures thereof.

In certain embodiments, fluorochemical treatment compositions of the present disclosure include at least one monoether alkyl glycol solvent in an amount of at least 3 wt-%, or at least 4 wt-%, or at least 5 wt-%, based on the total weight of the

fluorochemical treatment composition. In certain embodiments, fluorochemical treatment compositions of the present disclosure include at least one monoether alkyl glycol solvent in an amount of up to 25 wt-%, or up to 20 wt-%, or up to 15 wt-%>, or up to 10 wt-%>, based on the total weight of the fluorochemical treatment composition. In a preferred embodiment, the amount of the at least one monoether alkyl glycol solvent (i.e., the total amount of monoether alkyl glycol solvents) in the fluorochemical treatment composition is at least equal to or higher than the amount of the at least one fluorochemical compound (i.e., the total amount of fluorochemical compounds).

The amount of the at least one monoether alkyl glycol solvent could include simply one monoether alkyl glycol solvent or a mixture thereof. For example, this amount could include a mixture of different monoether alkyl glycol solvents, each of which is less than 3 wt-%, but the total amount is at least 3 wt-%. Cationic Surfactants

Suitable cationic surfactants include mono- or bi-tail ammonium salts. Examples of useful cationic surfactants include dodecyl ammonium chloride, dodecyl ammonium bromide, dodecyl trimethyl ammonium bromide, dodecyl pyridinium chloride, dodecyl pyridinium bromide, hexadecyl trimethyl ammonium bromide, cationic quaternary amines, and combinations thereof. Other useful cationic surfactants include esterquat and amide quat surfactants as disclosed in International Publication No. WO 2013/162704 (Coppens et al.) and U.S. Pat. No. 7,807,614 (Llosas et al).

In certain embodiments, fluorochemical treatment compositions of the present disclosure include at least one surfactant in an amount of at least 0.01 wt-%, or at least 1 wt-%, based on the total weight of the fluorochemical treatment composition. In certain embodiments, fluorochemical treatment compositions of the present disclosure include at least one surfactant in an amount of up to 0.03 wt-%, or up to 0.5 wt-%, based on the total weight of the fluorochemical treatment composition.

Optional Cosolvents and Additives

In certain embodiments, mixtures of water-insoluble solvents with water-soluble solvents can be employed in treatment compositions of the present disclosure. Suitable water-soluble (i.e., those soluble in water in an amount of at least 3 wt-% at room temperature) solvents include, for example, mono- or di-alcohols, lower ketones, polyglycol esters, and polyglycol ethers, or mixtures of such solvents. Suitable water- insoluble (i.e., those soluble in water in an amount of less than 3 wt-% at room

temperature) solvents are esters, ethers, and higher ketones.

Additionally, the compositions of the invention may also include other fluorinated or non-fluorinated repellent materials, softeners, anti-static, anti-dust mite or antimicrobial additives.

Articles and Methods

The amount of the fluorochemical composition applied to a fibrous substrate in accordance with this disclosure is chosen so that sufficiently high or desirable water and/or oil repellencies are imparted to the substrate surface, said amount usually being such that 0.01% to 5% by weight, preferably 0.05% to 2% by weight, of the fluorinated compound is present on the treated substrate. The amount which is sufficient to impart desired repellency can be determined empirically and can be increased as necessary or desired.

Another embodiment of the present invention is an article having a dried treatment derived from the fluorochemical composition of the present disclosure and optionally a co- solvent. After application and drying of the treatment composition, the article exhibits durable oil and/or water repellency. The treatment compositions of the present invention can be applied to a wide variety of fibrous substrates. Fibrous substrates include woven, knit, and nonwoven fabrics, textiles, carpets, and paper.

Fibrous substrates are capable of imbibing a liquid and are therefore porous.

Preferred substrates are textiles such as cotton, wool, polyester, polyamide, and blends thereof. Particularly preferred substrates are synthetic substrates. Such substrates are particularly subject to staining and soiling, but also benefit greatly from the

fluorochemical compositions of the present invention because the treatment composition can penetrate into the fibrous or porous substrate surface and spread over the internal surfaces of the substrate. Preferred fibrous substrates that can be treated with the treatment composition of the present invention are nonwoven, knits, and woven fabrics, carpet, drapery material, upholstery, clothing, and essentially any textile. The fibrous substrate can be in the form of a yarn, toe, web, or roving, or in the form of fabricated textiles such as carpets, woven and nonwoven fabrics, etc.

To impart one or more repellency characteristics to a fibrous substrate, having one or more surfaces, (a) the treatment composition is applied onto one or more surfaces of the substrate and (b) the treatment composition is dried at room temperature.

The treatment compositions comprising the fluorochemical composition can be applied to a treatable substrate by standard methods such as, for example, spraying, padding, foaming, dipping, roll coating, brushing, or exhaustion followed by room temperature drying of the treated substrate to remove any remaining water or co-solvent. When treating flat substrates of appropriate size, knife-coating or bar-coating may be used. If desired, the fluorochemical composition can be co-applied with conventional fiber treating agents, for example, spin finishes or fiber lubricants. ILLUSTRATIVE EMBODIMENTS

Embodiment 1 is a fluorochemical treatment composition comprising:

at least one fluorochemical compound in an amount of 1 wt-% to 5 wt-% solids, based on the total weight of the fluorochemical treatment composition;

at least one monoether alkyl glycol solvent present in an amount of 3 wt-% to 25 wt-%, based on the total weight of the fluorochemical treatment composition;

at least one cationic surfactant; and

water;

wherein the treatment composition is dried at room temperature on a fibrous substrate to provide an increase in at least one of oil repellency or water repellency compared to the same fluorochemical treatment composition without the monoether alkyl glycol solvent and dried at room temperature.

Embodiment 2 is the fluorochemical treatment composition of embodiment 1 wherein the treatment composition is dried at room temperature on a fibrous substrate in an amount sufficient to provide at least one of an oil repellency value of at least 2 (or at least 3, or at least 4, or at least 5) on a scale of 0 to 8, a water repellency value of at least 80 (or at least 90, or 100) on a scale of 0 to 100, or both.

Embodiment 3 is the fluorochemical treatment composition of embodiment 1 or 2 wherein the at least one monoether alkyl glycol solvent is present in an amount of 5 wt-% to 15 wt-%, based on the total weight of the fluorochemical treatment composition.

Embodiment 4 is the fluorochemical treatment composition of any one of embodiments 1 through 3 wherein the at least one fluorochemical compound is present in an amount of 2 wt-% to 3 wt-% solids, based on the total weight of the fluorochemical composition.

Embodiment 5 is the fluorochemical treatment composition of any one of embodiments 1 through 4 wherein the amount of the at least one monoether alkyl glycol solvent in the fluorochemical treatment composition is at least equal to or higher than the amount of the at least one fluorochemical compound.

Embodiment 6 is the fluorochemical treatment composition of any one of embodiments 1 through 5 wherein water is present in an amount of 75 wt-% to 95 wt-%, based on the total weight of the fluorochemical composition. Embodiment 7 is the fluorochemical treatment composition of any one of embodiments 1 through 6 wherein the at least one monoether alkyl glycol solvent is soluble in water in an amount of at least 3 wt-% (or at least 5 wt-%, or at least 10 wt-%, or at least 15 wt-%) at room temperature.

Embodiment 8 is the fluorochemical treatment composition of any one of embodiments 1 through 7 wherein the at least one monoether alkyl glycol solvent is a mono-(Cl-C4)alkyl ether of mono-, di-, or tri-ethylene or propylene glycol.

Embodiment 9 is the fluorochemical treatment composition of embodiment 8 wherein the at least one monoether alkyl glycol solvent is selected from the group of dipropylene glycol n-butyl ether, dipropylene glycol methyl ether, tripropylene glycol methyl ether, butyl diglycol, and mixtures thereof.

Embodiment 10 is the fluorochemical treatment composition of any one of embodiments 1 through 9 wherein the at least one fluorochemical compound is selected from the group of a fluorochemical polyurethane, a fluorochemical (meth)acrylate copolymer, and a mixture thereof.

Embodiment 11 is the fluorochemical treatment composition of embodiment 10 wherein the at least one fluorochemical compound is a fluorochemical polyurethane comprising: (i) a fluorochemical oligomeric portion; (ii) a fluorine-free hydrocarbon moiety; and (iii) a di-, tri-, or polymeric isocyanate-derived linking group.

Embodiment 12 is the fluorochemical treatment composition of any one of embodiments 1 through 11 wherein the at least one cationic surfactant is present in an amount of 0.01 wt-% to 1 wt-%, preferably 0.03 wt-% to 0.5 wt-%, based on the total weight of the fluorochemical treatment composition.

Embodiment 13 is the fluorochemical treatment composition of any one of embodiments 1 through 12 further comprising one or more additional fluorinated or non- fluorinated repellent materials, softeners, anti-static additives, anti-dust mite additives, or anti-microbial additives.

Embodiment 14 is a method of imparting repellency to a fibrous substrate having one or more surfaces, the method comprising: applying the fluorochemical treatment composition of any one of embodiments 1 through 13 onto one or more surfaces of the fibrous substrate; and drying the fluorochemical treatment composition at room

temperature. Embodiment 15 is the method of embodiment 14 wherein applying the

fluorochemical treatment composition onto the one or more surfaces of the fibrous substrate comprises applying the fluorochemical treatment composition in an amount sufficient to provide an oil repellency value of at least 2 on a scale of 0 to 8, a water repellency value of at least 80 on a scale of 0 to 100, or both.

Embodiment 16 is an article comprising a fibrous substrate having one or more surfaces treated according to the method of embodiment 14 or 15.

Embodiment 17 is a method of improving the repellency performance of a fluorochemical treatment composition, the method comprising:

providing an initial composition comprising:

at least one fluorochemical compound;

at least one cationic surfactant; and

water;

combining the initial composition with at least one monoether alkyl glycol solvent to provide a fluorochemical treatment composition comprising the at least one

fluorochemical compound in an amount of 1 wt-% to 5 wt-% solids, and the at least one monoether alkyl glycol solvent in an amount of 3 wt-% to 25 wt-%, based on the total weight of the fluorochemical treatment composition;

Embodiment 18 is the method of embodiment 17 wherein the treatment composition is dried at room temperature on a fibrous substrate in an amount sufficient to provide an oil repellency value of at least 2 (or at least 3, or at least 4, or at least 5) on a scale of 0 to 8, a water repellency value of at least 80 (or at least 90, or at least 100) on a scale of 0 to 100, or both.

Embodiment 19 is the method of embodiment 17 or 18 wherein the at least one monoether alkyl glycol solvent is present in an amount of 5 wt-% to 10 wt-%, based on the total weight of the fluorochemical treatment composition. Embodiment 20 is the method of any one of embodiments 17 through 19 wherein the at least one fluorochemical compound is present in an amount of 2 wt-% to 3 wt-% solids, based on the total weight of the fluorochemical composition.

Embodiment 21 is the method of any one of embodiments 17 through 20 wherein water is present in an amount of 75 wt-% to 95 wt-%, based on the total weight of the fluorochemical composition.

Embodiment 22 is the method of any one of embodiments 17 through 21 wherein the at least one monoether alkyl glycol solvent is soluble in water in an amount of at least 3 wt-%) (or at least 5 wt-%, or at least 10 wt-%, or at least 15 wt-% or at least 20 wt-% or at least 25 wt-%) at room temperature.

Embodiment 23 is the method of any one of embodiments 17 through 22 wherein the at least one monoether alkyl glycol solvent is a mono-(Cl-C4)alkyl ether of mono-, di- , or tri-ethylene or propylene glycol.

Embodiment 24 is the method of embodiment 23 wherein the at least one monoether alkyl glycol solvent is selected from the group of dipropylene glycol n-butyl ether, dipropylene glycol methyl ether, tripropylene glycol methyl ether, butyl diglycol, and mixtures thereof.

Embodiment 25 is the method of any one of embodiments 17 through 24 wherein the at least one fluorochemical compound is selected from the group of a fluorochemical polyurethane, a fluorochemical (meth)acrylate copolymer, or a mixture thereof.

Embodiment 26 is the method of embodiment 25 wherein the at least one fluorochemical compound is a fluorochemical polyurethane comprising: (i) a

fluorochemical oligomeric portion; (ii) a fluorine-free hydrocarbon moiety; and (iii) a di-, tri-, or polymeric isocyanate-derived linking group.

Embodiment 27 is the method of any one of embodiments 17 through 26 wherein the amount of the monoether alkyl glycol solvent in the fluorochemical treatment composition is at least equal to or higher than the amount of the fluorochemical compound.

Embodiment 28 is the method of any one of embodiments 17 through 27 wherein the at least one cationic surfactant is present in an amount of 0.01 wt-% to 1 wt-%, based on the total weight of the fluorochemical treatment composition. Embodiment 29 is the method of any one of embodiments 17 through 28 further comprising one or more additional fluorinated or non-fluorinated repellent materials, softeners, anti-static additives, anti-dust mite additives, or anti-microbial additives.

EXAMPLES

Objects and advantages of this disclosure are further illustrated by the following examples, but the particular materials and amounts thereof recited in these examples, as as other conditions and details, should not be construed to unduly limit this disclosure.

Materials utilized for the examples are shown in Table 1.

Table 1 : Materials List

Material Description Source

PROGLYDE DMM Di(propylene glycol) dimethyl ether, mixture of Dow Chemical,

isomers. PROGLYDE DMM is a trade designation Netherlands of Dow Chemical.

PM Acetate l-Methoxy-2-propanol acetate ; CAS No. 108-65-6 Dow Chemical,

Netherlands

V-59 2,2'-Azobis(2-methylbutyronitrile). Solvent soluble Wako Pure Chemical azo initiator. V-59 is a trade designation of Wako Industries Ltd., Germany Pure Chemical Industries

VGH-70 Dipalmitoylethyldimethyl ammonium chloride. AkzoNobel, Netherlands

VGH-70 is a trade designation of Akzo Nobel

2 -Merc aptoethanol Chain transfer agent Sigma- Aldrich, Belgium

Ethylacetate Solvent Sigma- Aldrich, Belgium

DBTDL Dibutyltin dilaurate Sigma- Aldrich, Belgium

Ethoquad C-12 Cationic surfactant. Ethoquad C-12 is a trade AkzoNobel, Netherlands designation of Akzo Nobel

Tergitol 15-S-30 Nonionic surfactant. Tergitol 15-S-30 is a trade Dow Chemical,

designation of Dow Chemical. Netherlands

Tergitol TMN-6 Nonionic surfactant. Tergitol THM-6 is a trade Dow Chemical,

designation of Dow Chemical. Netherlands

V-50 2,2'-Azobis(2- Wako Pure Chemical methylpropionamidine)dihydrochloride. V-50 is a Industries Ltd., Germany trade designation of Wako Pure Chemical

Industries.

PES (Dark Grey) Dark grey polyester fabric

PES (Grey) Grey polyester fabric

PA (White) White polyamide fabric

PA (Grey) Grey polyamide fabric

PES/CO Polyester cotton

Test Methods

Oil Repellency (OR)

The oil repellency of a treated substrate was measured by the American

Association of Textile Chemists and Colorists (AATCC) Standard Test Method No 118- 1983, which is based on the resistance of a treated substrate to penetration by oils of varying surface tensions (see U.S. Patent No. 5,910,557). Ratings from 1 to 8 were assigned, with higher values indicating better oil repellency. Spray Rating (SR

The spray rating of a treated substrate is a value indicative of the dynamic

repellency of the treated substrate to water that impinges on the treated substrate. The repellency is measured by Test Method 22-1996, published in the 2001 Technical Manual of the American Association of Textile Chemists and Colorists (AATCC), and is expressed in terms of a 'spray rating' of the tested substrate. The spray rating was obtained by spraying 250 milliliters (ml) water on the substrate from a height of 15 centimeters (cm). The wetting pattern was visually rated using a 0 to 100 scale, where 0 means complete wetting and 100 means no wetting at all.

Fluorinated Compounds

Fluorinated compounds FC-1 to FC-4

Fluorinated compounds FC-1 to FC-4 as given in Table 2 were prepared according to the general procedure outlined below for the synthesis of fluorinated compound FC-1 as follows:

Fluorinated oligomer C4-MA12: In a first step a fluorinated oligomer was prepared. In a three necked flask fitted with a stirrer, heating mantle, thermometer, and cooler, were placed 1000 grams (g) (2.4 equivalent) of MeFBSEMA (C4-MA), 15.3 g (0.2 equivalent) 2-mercaptoethanol, and 338.4 g ethylacetate. The mixture was heated to 40°C under nitrogen and degassed with vacuum. To this flask was added 2.55 g V-59 initiator and the mixture was heated to about 75°C for 3 hours. A second aliquot of 2.55 g V-59 initiator was then added to the flask and heating was continued under nitrogen for 16 hours. A third charge of 2.55 g V-59 was then added and the reaction continued for 8 hours. A clear, viscous solution of oligomeric fluorochemical alcohol was obtained at 75% solids. This fluorochemical oligomer, made from a C4-fluorinated methacrylate comprised, on average, 12 methacrylate (MA) groups per 1 alcohol group and was labeled C4-MA12. The fluorinated oligomers used to prepare fluorinated compounds FC-2 to FC- 4 (as well as FC-5 to FC-7) were prepared in the same way and identified in Table 2 as Cx-MAy or Cx-Ay wherein MA and A represent methacrylate and acrylate units respectively, x refers to the number of perfluorinated carbon atoms present in the monomer and y refers to the number of (meth)acrylate units in the oligomer.

Urethane Reaction: In a second step, a fluorinated (meth)acrylate urethane was prepared. Therefore, a three necked flask fitted with a stirrer, heating mantle, thermometer, and cooler was loaded with 1353.7 g (0.2 equivalent) fluorinated oligomer C4-MA12, 53 g (0.2 equivalent) SA, and 1537 g ethylacetate. About 100 g ethylacetate were distilled off, and the flask was cooled to about 40°C under nitrogen. To this flask were then added 136 g (1 equivalent) PAPI and 2.5 g DBTDL and the mixture was heated to 80°C under nitrogen for 8 hours. To this mixture was then added 49.2 g (0.6 equivalent) MEKO and the reaction continued for 2 hours. A clear solution was obtained.

Emulsification: In a next step, the fluorinated acrylate urethane was emulsified. In a three necked flask were placed 3125.3 g of the clear solution obtained after the urethane reaction and ethylacetate (40% solids). The solution was heated to about 70°C. In a second 3-necked flask were placed 2730 g deionized water, 354 g propyleneglycol, and 125 g VGH-70 to make a cationic dispersion. This mixture was heated to about 70°C. The hot water phase was then added to the hot ethylacetate phase and mixed vigorously for about 30 minutes, until a stable pre-emulsion was formed. This hot pre-emulsion was then passed twice through a heated Manton-Gaulin homogenizer (Lab 60, APV Belgium, Diegem, Belgium) at 300 bar and about 67°C. A thick liquid was obtained. Ethylacetate was stripped from the emulsion at about 50-60°C and reduced pressure of about 30 mm Hg to obtain an aqueous dispersion at about 30% solids. The dispersion was filtered through a 100 micron polypropylene filter bag to yield FC-1. The average particle size was about 90-110 nanometers (nm).

Fluorinated Compound FC-5

Fluorinated compound FC-5 as given in Table 2 was prepared according to the same procedure, but without the addition of MEKO (an isocyanate blocking agent).

Fluorinated Compounds FC-6 and FC-7

Fluorinated compounds FC-6 and FC-7 as given in Table 2 were prepared according to the same procedure, but without the addition of MEKO.

Table 2

FC-6 PAPI SA IPA C4-MA12 / 1/0.2/0.6/0.2

FC-7 PAPI SA Ethanol C4-MA12 / 1/0.2/0.6/0.2

Fluorinated Compound FC-8

Fluorinated compound FC-8 MeFBSEMA/ODMA 80/20 was prepared as follows: 32 g MeFBSEMA and 8 g ODMA were mixed and heated to 60°C, to this mixture a 60°C blend of 105 g water, 1.1 g Ethoquad C-12, 1.2 g Tergitol 15-S30, and 2.4 g Tergitol TMN-6 was added.

The blend of all these components was stirred vigorously to form a pre-emulsion. This pre-emulsion was then sonicated for 6 minutes with a Branson Sonifier, at maximum setting, to form a stable emulsion of the monomers. This monomer dispersion was then poured in a reaction flask, purged with Nitrogen, and 0.4 g V-50 (Wako) initiator was added. The polymerization was done for 16 hours at 75°C. After the polymerization reaction, a stable fluoropolymer dispersion with 29.5% solids was obtained.

Fluorinated Compound FC-9

Fluorinated compound FC-9 was a cationic textile repellent comprising 20% fluorinated compound, commercially available from Asahi Glass, under the trade designation AGE-082.

Formulation and Treatment Procedure

Treatment Dispersions Comprising Fluorinated Compounds

Cationic treatment dispersions were prepared by first mixing the monoether alkyl glycol solvent with water and subsequently adding the emulsified fluorinated compound in amounts to obtain the desired concentration as indicated in the examples. Treatment Procedure via "Padding" Process

The treatments were applied onto the textile substrates, by immersing the substrates in the treatment dispersion and agitating until the substrate was saturated. The saturated substrate was then run through a padder/roller to remove excess of the dispersion and to obtain 100% Wet Pick Up (WPU) (100% WPU means that after this process the substrate absorbed 100% of its own weight of the treatment dispersion before drying). Drying was done at room temperature for a time as indicated in the examples.

Examples

Examples 1 to 5 and Reference Example Ref-1

In Examples 1 to 5 white PA and grey PES were treated by padding (see

"Treatment Procedure") with a cationic dispersion comprising 2.5 % solids FC-1 and various amounts of DPnB as given in Table 3. In Reference Example Ref-l the fabrics were treated with the same cationic dispersion comprising 2.5% solids FC-1, but without the addition of DPnB. The treated fabrics were hang dried at room temperature (RT) overnight. After drying, the fabrics were tested for their oil repellency (OR) and dynamic water repellency (SR) according to the general procedure outlined above. The results are listed in Table 3 ("comp" refers to a comparative example). Table 3

Examples 6 to 10 and Reference Example Ref-2

In Examples 6 to 10 white PA and grey PES were treated by padding with a cationic dispersion comprising 5% DPnB and various amounts of FC-1 as indicated in Table 4. In Reference Example Ref-2 the fabrics were treated with a 5% dispersion of DPnB in water, without addition of FC-1. The treated fabrics were hang dried at RT overnight. After drying, the fabrics were tested for their oil repellency (OR) and dynamic water repellency (SR) according to the general procedure outlined above. The results are listed in Table 4 ("comp" refers to a comparative example).

Table 4

Examples 11 to 26 and Reference Examples Ref-3 to Ref 6

In Examples 11 to 22 grey PA and dark grey PES were treated by padding (see "Treatment Procedure") with a cationic dispersion comprising 2.5% of different fluorinated compounds and different monoether alkyl glycol solvents in amounts as given in Table 5. In Examples 23 to 26 grey PA and dark grey PES were treated by padding with a cationic dispersion comprising AGE-082 comprising 2% fluorinated compound (referred to as FC-9) and different monoglycol ethers in amounts as given in Table 5. In Reference Examples Ref-3 to Ref-6, the fabrics were treated with a cationic dispersion comprising the same amount of fluorochemical compound as in the respective examples, but without addition of monoether alkyl glycol solvents. The treated fabrics were hang dried at RT for 48 hours. After drying, the fabrics were tested for their oil repellency (OR) and dynamic water repellency (SR) according to the general procedure outlined above. The results are listed in Table 5.

Table 5

Ex FC- Monoether solvent PA (grey) PES (dark grey) compound % OR SR OR SR

1 1 FC-1 DPnB 5 5 90 5.5 100

12 FC-1 DPM 15 6 100 5.5 100

13 FC-1 BDG 15 6 100 6 100 14 FC-1 TPM 10 5.5 100 5.5 100

Ref-3 FC-1 / / 0 50 0 50

15 FC-6 DPnB 5 6 90 5.5 100

16 FC-6 DPM 15 6 100 5.5 100

17 FC-6 BDG 15 6 100 5.5 100

18 FC-6 TPM 10 6 100 5 100

Ref-4 FC-6 / / 0 50 0 50

19 FC-8 DPnB 5 4 80 3 90

20 FC-8 DPM 15 4 80 3.5 90

21 FC-8 BDG 15 4.5 100 4 100

22 FC-8 TPM 10 5 80 3.5 90

Ref-5 FC-8 / / 0 0 0 0

23 FC-9 DPnB 5 6 80 6 90

24 FC-9 DPM 15 6 90 6 90

25 FC-9 BDG 15 6 100 6 100

26 FC-9 TPM 10 6 90 6 100

Ref-6 FC-9 / / 4 50 4 70

Examples 27 to 30 and Reference Examples Ref -7 to Ref-10

In Examples 27 to 30 white PA and grey PES were treated by padding (see "Treatment Procedure") with a cationic dispersion comprising 5% DPnB and 2.5% of various fluorinated compounds as indicated in Table 6. In Reference Examples Ref-7 to Ref-10 the fabrics were treated with a cationic dispersion comprising 2.5% of the fluorinated compound, but without addition of DPnB. The treated fabrics were hang dried at RT overnight. After drying, the fabrics were tested for their oil repellency (OR) and dynamic water repellency (SR) according to the general procedure outlined above. The results are listed in Table 6.

Table 6

30* FC-1 5 6 100 6 100

Ref-10** FC-1 0 0 50 0 50

Note : * : repeat of Examp le 11

** : repeat of Reference Example Ref-3

Example 31 and Comparative examples C-l to C-18

Example 31 is a repeat of Example 11. In Comparative Examples C-l to C-18, grey PA and dark grey PES were treated by padding (see "Treatment Procedure") with a cationic dispersion comprising 2.5% fluorinated compound FC-1 and different solvents, other than monoether alkyl glycols, in amounts as given in Table 7. The treated fabrics were hang dried at RT for 48 hours. After drying, the fabrics were tested for their oil repellency (OR) and dynamic water repellency (SR) according to the general procedure outlined above. The results are listed in Table 7 ("C-#" refers to a comparative example)

Table 7

C-12 Diglyme 15 3.5 70 2 70

C-13 IPA 5 0 70 0 50

C-14 IPA 10 0 70 0 50

C-15 IPA 15 0 70 0 50

C-16 t-butylalcohol 5 0 70 0 50

C-17 t-butylalcohol 10 0 70 0 50

C-18 t-butylalcohol 15 0 70 0 50

Example 32 and Reference Example Ref-11

In Example 32 a PES/CO substrate was treated by padding (see "Treatment Procedure") with a cationic dispersion comprising 2.5% solids FC-1 and 5 % DPnB. In Reference Example Ref-11 the fabric was treated with a cationic dispersion comprising 2.5% solids FC-1, without the addition of DPnB. The treated fabric was hang dried at RT overnight. After drying, the fabric was tested for its oil repellency (OR) and dynamic water repellency (SR) according to the general procedure outlined above. The results are listed in Table 8.

Table 8

The complete disclosures of the patents, patent documents, and publications cited herein are incorporated by reference in their entirety as if each were individually incorporated. Various modifications and alterations to this disclosure will become apparent to those skilled in the art without departing from the scope and spirit of this disclosure. It should be understood that this disclosure is not intended to be unduly limited by the illustrative embodiments and examples set forth herein and that such examples and embodiments are presented by way of example only with the scope of the disclosure intended to be limited only by the claims set forth herein as follows.

Claims

WHAT IS CLAIMED IS:

A fiuorochemical treatment composition comprising:

at least one fiuorochemical compound in an amount of 1 wt-% to 5 wt-% solids, based on the total weight of the fiuorochemical treatment composition;

at least one monoether alkyl glycol solvent present in an amount of 3 wt-% to 25 wt-%, based on the total weight of the fiuorochemical treatment composition;

at least one cationic surfactant; and

water;

wherein the treatment composition is dried at room temperature on a fibrous substrate to provide an increase in at least one of oil repellency or water repellency compared to the same fiuorochemical treatment composition without the monoether alkyl glycol solvent and dried at room temperature.

The fiuorochemical treatment composition of claim 1 wherein the treatment composition is dried at room temperature on a fibrous substrate in an amount sufficient to provide an oil repellency value of at least 2 on a scale of 0 to 8, a water repellency value of at least 80 on a scale of 0 to 100, or both.

The fiuorochemical treatment composition of claim 1 wherein the at least one monoether alkyl glycol solvent is present in an amount of 5 wt-% to 15 wt-%, based on the total weight of the fiuorochemical treatment composition.

The fiuorochemical treatment composition of claim 1 wherein the at least one fiuorochemical compound is present in an amount of 2 wt-% to 3 wt-% solids, based on the total weight of the fiuorochemical composition.

The fiuorochemical treatment composition of claim 1 wherein water is present in an amount of 75 wt-% to 95 wt-%, based on the total weight of the fiuorochemical composition.

6. The fluorochemical treatment composition of claim 1 wherein the at least one monoether alkyl glycol solvent is soluble in water in an amount of at least 3 wt-% at room temperature.

7. The fluorochemical treatment composition of claim 1 wherein the at least one

monoether alkyl glycol solvent is a mono-(Cl-C4)alkyl ether of mono-, di-, or tri- ethylene or propylene glycol.

8. The fluorochemical treatment composition of claim 7 wherein the at least one

monoether alkyl glycol solvent is selected from the group of dipropylene glycol n- butyl ether, dipropylene glycol methyl ether, tripropylene glycol methyl ether, butyl diglycol, and mixtures thereof.

9. The fluorochemical treatment composition of claim 1 wherein the at least one

fluorochemical compound is selected from the group of a fluorochemical

polyurethane, a fluorochemical (meth)acrylate copolymer, and a mixture thereof.

10. The fluorochemical treatment composition of claim 9 wherein the at least one

fluorochemical compound is a fluorochemical polyurethane comprising: (i) a fluorochemical oligomeric portion; (ii) a fluorine-free hydrocarbon moiety; and (iii) a di-, tri-, or polymeric isocyanate-derived linking group.

11. The fluorochemical treatment composition of any one of embodiments 1 through 4 wherein the amount of the at least one monoether alkyl glycol solvent in the fluorochemical treatment composition is at least equal to or higher than the amount of the at least one fluorochemical compound.

12. The fluorochemical treatment composition of claim 1 further comprising one or more additional fluorinated or non-fluorinated repellent materials, softeners, anti-static additives, anti-dust mite additives, or anti-microbial additives.

13. A method of imparting repellency to a fibrous substrate having one or more surfaces, the method comprising: applying the fluorochemical treatment composition of claim 1 onto one or more surfaces of the fibrous substrate; and

drying the fluorochemical treatment composition at room temperature. 14. The method of claim 13 wherein applying the fluorochemical treatment composition onto the one or more surfaces of the fibrous substrate comprises applying the fluorochemical treatment composition in an amount sufficient to provide an oil repellency value of at least 2 on a scale of 0 to 8, a water repellency value of at least 80 on a scale of 0 to 100, or both.

15. An article comprising a fibrous substrate having one or more surfaces treated

according to the method of claim 13.

16. A method of improving the repellency performance of a fluorochemical treatment composition, the method comprising:

providing an initial composition comprising:

at least one fluorochemical compound;

at least one cationic surfactant; and

water;

combining the initial composition with at least one monoether alkyl glycol solvent to provide a fluorochemical treatment composition comprising the at least one fluorochemical compound in an amount of 1 wt-% to 5 wt-% solids, and the at least one monoether alkyl glycol solvent in an amount of 3 wt-% to 25 wt-%, based on the total weight of the fluorochemical treatment composition;

wherein the treatment composition is dried at room temperature on a fibrous substrate to provide an increase in at least one of oil repellency or water repellency compared to the same fluorochemical treatment composition without the monoether alkyl glycol solvent and dried at room temperature. 17. The method of claim 16 wherein the treatment composition is dried at room

temperature on a fibrous substrate in an amount sufficient to provide an oil repellency value of at least 2 on a scale of 0 to 8, a water repellency value of at least 80 on a scale of O to 100, or both.

18. The method of claim 16 wherein the at least one monoether alkyl glycol solvent is present in an amount of 5 wt-% to 10 wt-%, based on the total weight of the fluorochemical treatment composition.

19. The method of claim 16 wherein the at least one monoether alkyl glycol solvent is soluble in water in an amount of at least 3 wt-% at room temperature.

20. The method of claim 16 wherein the at least one monoether alkyl glycol solvent is a mono-(Cl-C4)alkyl ether of mono-, di-, or tri-ethylene or propylene glycol.