Water- and oil-repellency imparting ester oligomers comprising perfluoroalkyl moieties

(Cross-reference of related applications) This application claims the benefit of US Provisional Application No. 60 / 942,701 filed June 8, 2007.

(Field of invention) The present invention relates to a fluorochemical composition comprising one or more compounds or oligomers having at least one fluorine-containing repeatable unit and at least one fluorine-containing terminal group. The present invention also relates to articles comprising a substrate and a fluorochemical composition which may be applied as a coating. These fluorochemical compositions impart oil repellency and water repellency to the base material. In another aspect, the invention relates to a process for imparting oil and water repellency properties to a substrate and an article.

It is well known in the art that certain fluorochemical compositions are used on fibers and fibrous substrates such as cloth, paper and leather to impart oil repellency and water repellency as well as stain and stain resistance. For example, "Organofluorine Chemicals and Their Industrial Applications" edited by Banks, Ellis Horwood. Ltd.), Chichester, UK, 1979, pp. 226-234. Such fluorochemical compositions include, for example, fluorochemical guanidine (US Pat. No. 4,540,497 (Chang et al.)), Cationic and non-cationic fluorochemicals (US Pat. No. 4,566,981 (Howells)). ), Composition containing fluorochemical carboxylic acid and epoxide-based cationic resin (US Pat. No. 4,426,466 (Schwartz)), Fluoroaliphatic carbodiimide (US Pat. No. 4,215,205 (Landucci)), Fluoro Aliper alcohol (US Pat. No. 4,468,527 (Patel)), fluorine-containing adduct polymer, copolymer and macromer (US Pat. No. 2,803,615, No. 3,068,187, No. 3,102,103, No. 3,341,497, No. 3,574,791) , 3,916,053, 4,529,658, 5,216,097, 5,276,175, 5,725,789, and 6,037,429), Fluorine-containing phosphate ester (US Patents 3,094,547, 5,414,102, and 5,424,474), Fluorochemical Urethane (US Patents 3,987,182, 3,987,227, 4,504,401, and 4,958,039), Fluorochemical Alofanate (US Patent 4,606,737), Fluorochemical Biuret (US Patent 4,668,406) ), Fluorochemical oxazolidinone (US Pat. No. 5,025,052), and Fluorochemical piperazine (US Pat. No. 5,451,622).

<p> There is a need for water / oil repellent treatments that provide improved ease of use and improved performance under desired conditions.</p>

<p> In one aspect, the invention relates to a chemical composition comprising at least one fluorine-containing repeatable unit and one or more oligomers having at least one fluorine-containing end group. These oligomers (a) One or more polyols and (b) One or more polyacyl compounds containing 17 or more carbon atoms (carboxylic acids, esters, acyl halides, etc.) and (c) Condensation reaction product of one or more monofunctional fluorine-containing compounds containing a functional group reactive with the hydroxyl group of the polyol (a) or the acyl group of the polyacyl compound (b). At least a portion of this polyol compound further comprises at least one fluorine-containing group selected from the group consisting of perfluoroalkyl, perfluoroheteroalkyl, and perfluoroheteroalkylene. In some embodiments, the compound or oligomer is a condensation reaction product of (a), (b) and (c) above and (d) one or more monofunctional, fluorine-free compounds. Including. Surprisingly, the oligomers of the invention have been found to provide superior performance compared to known shorter chain materials, especially dynamic water / oil repellency.</p><p> As used herein, the term "oligomer" is at least two or more and up to several, i.e. up to 10 on average but preferably up to 5 on average, repeatable (polymerized) or repeatable. It means a molecule containing a unit. Each repeating unit reacts with at least one polyol having an average of more than one, preferably two or more hydroxyl moieties and at least one polyacyl compound having an average of more than one, preferably two or more acyl moieties. At least one polyol compound containing an ester group derived from or derivable from, further selected from the group consisting of perfluoroalkyl, perfluoroalkylene, perfluorohetelloalkyl, and perfluoroheteroalkylene. Contains fluorine-containing parts. The oligomer is terminated with one or more perfluoroalkyl groups, one or more perfluoroheteroalkyl groups, or mixtures thereof.</p><p> A particular preferred embodiment of the fluorochemical composition of the present invention is a terminal and side branch R having 1-12 carbons, preferably 6 or less carbons, more preferably 3-5 carbons.^fContains compositions containing groups.</p><p> Another embodiment of the present invention relates to a coating composition comprising the fluorochemical oligomer of the present invention and a solvent. In this embodiment, the fluorochemical composition is dissolved or dispersed in a solvent. When applied to a substrate, the coating composition (which may be a solution or an emulsion) provides a uniform dispersion of the chemical composition on the substrate without changing the appearance of the substrate. provide. The present invention further relates to a method of imparting properties such as water repellency and oil repellency, stain release property and stain resistance to a substrate composed of one or more surfaces. (a) A step of applying the coating composition of the present invention on one or more surfaces of a substrate, wherein the coating composition is (i) At least one solvent and (ii) A step of application, including the fluorochemical composition of the present invention, and (b) Including the step of curing this coating composition.</p><p> The fluorochemical composition of the present invention can be applied to a wide variety of substrates as a coating, for example by topical application, to impart properties such as oil repellency, water repellency, stain release property, and stain resistance to the substrate. .. When the substrate coated with the fluorochemical composition of the present invention was tested, unexpectedly high dynamic water / oil repellency was observed.</p><p> When applied as a coating, the chemical compositions of the present invention can provide a uniform film. When applied as a coating, the chemical compositions of the present invention do not change the appearance of the substrate to which they are applied.</p><p> Definition Unless otherwise specified, the following terms used herein and in the claims have the meaning given below.</p><p> "Acyloxy" means radical-OC (O) R, where R is alkyl, alkenyl, and cycloalkyl, eg, acetoxy, 3,3,3-trifluoroacetoxy, propionyloxy, And similar.</p><p> "Alkenyl" means unsaturated aliphatic radicals.</p><p> "Alkoxy" means radical-OR, where R is an alkyl group, such as methoxy, ethoxy, propoxy, butoxy, and the like.</p><p> "Alkyl" means a linear saturated monovalent hydrocarbon radical or a branched saturated monovalent hydrocarbon radical, such as methyl, ethyl, 1-propyl, 2-propyl, pentyl, and the like. ..</p><p> "Alkylene" means a linear saturated divalent hydrocarbon radical or a branched saturated divalent hydrocarbon radical, such as methylene, ethylene, propylene, 2-methylpropylene, pentylene, hexylene, and the like. is there.</p><p> "Aralkylene" means the alkylene radicals defined above that have an attached aromatic group, such as benzyl, pyridylmethyl, 1-naphthylethyl, and the like.</p><p> "Curing chemical composition" means that the chemical composition is dry or that the solvent has evaporated from the chemical composition at high temperatures (eg, 50 ° C. or higher) for up to approximately 24 hours to a dry state. means.</p><p> A "fibrous substrate" is a material composed of synthetic or inorganic fibers such as woven fabrics, knits, non-woven fabrics, carpets and other fabrics such as laminates (PTFE and / or PU), as well as cotton and paper. , And a material composed of natural fibers such as leather.</p><p> "Fluorocarbon monoalcohol" means a compound having one hydroxyl group and a perfluoroalkyl or perfluorohetelloalkyl group, eg, C.₄F₉SO₂N (CH₃) CH₂CH₂OH, C₄F₉CH₂CH₂OH, C₂F₅O (C₂F₄O)₃CF₂CONHC₂H₄OH, C₃F₇O (C₃F₆O)_nCF (CF)₃) CONHC₂H₄OH, cC₆F₁₁CH₂OH, and similar.</p><p> "Hard substrate" means any rigid material that maintains its shape, such as glass, ceramics, concrete, natural stone, wood, metal, plastic, and the like.</p><p> "Heteroacyloxy" means that one or more heteroatoms (ie, oxygen, sulfur, and / or nitrogen) may be present in the R group and the total number of carbon atoms present may be up to 50. Except for, it has essentially the meaning given above for acyloxy, eg CH₃CH₂OCH₂CH₂C (O) O-, C₄H₉OCH₂CH₂OCH₂CH₂C (O) O-, CH₃O (CH₂CH₂O)_nCH₂CH₂C (O) O-, and similar.</p><p> A "heteroalkoxy" may have one or more heteroatoms (ie, oxygen, sulfur, and / or nitrogen) present in the alkyl chain and the total number of carbon atoms present may be up to 50. Except for that, it essentially has the implications given for alkoxy above, eg CH₃CH₂OCH₂CH₂O-, C₄H₉OCH₂CH₂OCH₂CH₂O-, CH₃O (CH₂CH₂O)_nH, and similar.</p><p> "Heteroalkyl" has essentially the meaning given above for alkyl, except that one or more heteroatoms (ie, oxygen, sulfur, and / or nitrogen) may be present in the alkyl chain. And these heteroatoms are separated from each other by at least one carbon, eg CH₃CH₂OCH₂CH₂-, CH₃CH₂OCH₂CH₂OCH (CH)₃) CH₂-, C₄F₉CH₂CH₂SCH₂CH₂-And similar.</p><p> "Heteroalkylene" has essentially the meaning given above for alkylene, except that one or more heteroatoms (ie, oxygen, sulfur, and / or nitrogen) may be present in the alkylene chain. And these heteroatoms are separated from each other by at least one carbon, eg-CH₂OCH₂O-, -CH₂CH₂OCH₂CH₂-, -CH₂CH₂N (CH₃) CH₂CH₂-, -CH₂CH₂SCH₂CH₂-And similar.</p><p> "Heteroaralkylene" means the alkylene radicals defined above, except that oxygen, sulfur, and / or nitrogen atoms linked in a chain can be present, eg, phenyleneoxymethyl, phenyleneoxyethyl, benzine. Phenoxymethyl, and the like.</p><p> "Halo" means fluoro, chloro, bromo, or iodine, preferably fluoro and chloro.</p><p> "Perfluoroalkyl" has the meaning given above for "alkyl", except that all or essentially all of the hydrogen atoms of the alkyl radical are replaced by fluorine atoms and the number of carbon atoms is 1 to about 12. In essence, such as perfluoropropyl, perfluorobutyl, perfluorooctyl, and the like.</p><p> "Perfluoroalkylene" has essentially the meaning given above for "alkylene", except that all or essentially all of the hydrogen atoms of the alkylene radical are replaced by fluorine atoms, eg, perfluoropropylene. , Perfluorobutylene, perfluorooctanoic acid, and the like.</p><p> "Perfluoroheteroalkyl" is given above for "heteroalkyl" except that all or essentially all hydrogen atoms of the heteroalkyl radical are replaced by fluorine atoms and the number of carbon atoms is 3 to about 100. In essence, for example, CF₃CF₂OCF₂CF₂-, CF₃CF₂O (CF)₂CF₂O)₃CF₂CF₂-Or C₃F₇O (CF (CF)₃) CF₂O)_mCF (CF)₃) CF₂-(In the formula, m is about 10-30), and the like.</p><p> "Perfluoroheteroalkylene" is given above for "heteroalkylene", except that all or essentially all hydrogen atoms of the heteroalkylene radical are replaced by fluorine atoms and the number of carbon atoms is 3 to about 100. In essence, for example, -CF₂OCF₂-, -CF₂O (CF)₂O)_n(CF₂CF₂O)_mCF₂-And similar.</p><p> "Perfluoroforming group" means an organic group in which all or essentially all of the hydrogen atoms bonded to carbon are replaced with fluorine atoms, for example, perfluoroalkyl, perfluoroheteroalkyl, and the like. ..</p><p> "Polyacyl compound" means a compound containing two or more acyl groups, or a derivative thereof, in which a carboxylic acid, an ester, or an acyl halide is bonded to a polyvalent organic group, for example, dimethyl adipate. , And similar ones.</p><p> "Polyproxide" means an organic compound or polymer having an average of at least about 2 primary or secondary hydroxyl groups per molecule, eg, ethylene glycol, propylene glycol, etc. 1,6-Hexanediol, and the like. The compound or polymer may be fluorinated, i.e., it may contain a fluorinated moiety in the main chain and / or added to a side branch.</p><p> By "porous" is meant capable of absorbing a liquid.</p>

The fluorochemical composition of the present invention is (a) One or more fluorinated polyols, (b) One or more polyacyl compounds containing 17 or more carbon atoms (carboxylic acids, esters, acyl halides, etc.) and (c) Condensation reaction product of one or more monofunctional fluorine-containing compounds containing a functional group reactive with the hydroxyl group of the polyol (a) or the acyl group of the polyacyl compound (b).

The fluorinated polyol compound further comprises at least one fluorine-containing group selected from the group consisting of perfluoroalkyl, perfluoroheteroalkyl, and perfluoroheteroalkylene. The ester oligomer may further comprise one or more non-fluorinated polyols. If desired, the reaction mixture of the fluorochemical oligomers of the invention may further comprise (a), (b) and (c) plus (d) one or more monofunctional, fluorine-free compounds. Adjust properties such as water / oil repellency and melting point.

This oligomer contains at least two repeatable or repeatable polymerization units. Each repeatable or repeating unit is a fluorine-containing group in one or more side branches or chains selected from the group consisting of perfluoroalkyl, perfluoroalkylene, perfluoroheteroalkyl, and perfluoroheteroalkylene, and between the polyol and the polyacyl compound. Contains ester groups formed from the reaction of. The oligomer is terminated with one or more perfluoroalkyl groups, one or more perfluoroheteroalkyl groups, or optionally one or more fluorine-free compounds or mixtures thereof.

It will be appreciated that the resulting ester molecule mixture preferably comprises ester molecules with varying numbers of repeating or repeatable units, such as two or more repeating units. This mixture of ester molecules containing various numbers of repeating units allows simple blending of the above components in the preparation of fluorochemical compositions.

The fluorochemical composition of the present invention comprises at least one diacyl compound (or a derivative thereof, for example, a dicarboxylic acid halide, a dicarboxylic acid, provided that at least a part of the polyol compound is composed of a side branch or a fluorine-containing group in a chain. Contains a mixture of ester molecules resulting from the reaction of an anhydride or dicarboxylic acid ester) with at least one fluorinated polyol and at least one fluorine-containing monoalcohol or fluorine-containing monocarboxylic acid (or derivative).

Therefore, the fluorochemical composition can include a single ester oligomer having a certain number of specific repeatable or repeatable units (one or more), or such compounds and / or various. It can contain a mixture of oligomers of several repeating units.

The ester compound and oligomer can be represented by the following formula (I).

R^fQ [OR²]_{o o}[OC (O) R¹C (O) OR²O]_n[C (O) R¹C (O)]_mT (I) During the ceremony o is a number from 0 to 1 (including 0 and 1) n is a number from 1 to 10 (including 1 and 10) m is a number from 0 to 1 (including 0 and 1) R^fIs a perfluoroalkyl group having 1 to 12, preferably 6 or less, most preferably 3 to 5 carbon atoms, or 1 to 6 perfluorocarbon chains present, preferably 1 It is a perfluoroheteroalkyl group having 3 to about 50 carbon atoms and having 4 to 4 carbon atoms. Q is a divalent linking group R¹Is a polyvalent organic group that is the same or different and is a residue of a polyacyl compound, which is a linear or branched or unsaturated group consisting of 15 to 20 carbon atoms, most preferably 16 carbon atoms. It is a chain alkylene group R²Is the same or different divalent organic group that is a residue of the polyol, and at least a part of it is replaced with one or more perfluoroalkyl groups, perfluoroheteroalkyl groups, perfluoroheteroalkylene groups, or a mixture thereof. Or it contains these, preferably 6 or less carbon atoms have fluorine atoms bonded to them, and T is the QR defined above^fOr, it is either a fluorine-free monovalent compound capable of reacting with a polyacyl compound or a polyol.

R above^fRegarding the group, R^fIt is preferable that the group has 6 or less carbon atoms. Shorter chain R^fThe groups are believed to reduce the tendency to cause in vivo accumulation, as described in US Pat. No. 5,688,884.

Suitable linking groups Q include the following structures in addition to covalent bonds: For the purposes of this list, each k is an independently integer from 0 to about 20 and R^1’Is an alkyl of hydrogen, phenyl, or 1 to about 4 carbon atoms, R^2’Is an alkyl of 1 to about 20 carbon atoms. Each structure is non-directional, i.e.-(CH₂)_kC (O) O-is -O (O) C (CH)₂)_k-Equivalent to.

<tables num="1"><img file="JP2010529263A_D0001.tif" /></tables>

It will be appreciated that in addition to a single compound, a mixture of oligomers corresponding to this general formula can be represented, and that o, m and n can be represented by non-integer numbers.

Suitable polyols for use in the preparation of fluorochemical compositions of the invention containing mixtures of polyol molecules include more than one average hydroxyl functional group (preferably about 2 to about 3 and about 2 as a diol). Examples thereof include organic polyols having (preferably one). Hydroxy groups can be primary or secondary, and primary hydroxyl groups are preferred because of their greater reactivity.

Suitable polyols include at least one aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aromatic, heterocyclic aromatic, or polymer portion. Preferred polyols are aliphatic or polymeric polyols that contain a hydroxyl group as the terminal group.

The polyol may contain at least one fluorine-containing group selected from the group consisting of perfluoroalkyl, perfluoroheteroalkyl, and perfluoroalkylene moieties. All perfluorocarbon chains containing these perfluoro moieties are preferably no more than 6 carbon atoms. The perfluoroalkyl moiety is preferable, and the perfluoroalkyl moiety having 6 or less carbon atoms is preferable. The perfluoroheteroalkyl moiety may have 3 to 50 carbon atoms. The perfluoroheteroalkylene group may have 3 to 50 carbon atoms. The perfluoroheteroalkyl and alkylene moieties are preferably perfluoropolyethers that do not have a perfluorocarbon chain of more than 6 carbon atoms.

Mixtures of fluorinated polyols and non-fluorinated polyols can be advantageously utilized in preparing the particular fluorochemical compositions of the present invention. For example, by including a non-fluorinated polyol, the melting temperature of the fluorochemical composition can be varied, making preparation at the processing temperatures commonly used in a given application more effective. An increase in cost effectiveness is also achieved by replacing some of the more expensive fluorinated polyols with less expensive non-fluorinated polyols. The choice of non-fluorinated polyol and amount used is determined by performance requirements such as melting temperature and water / oil repellency. When using non-fluorinated polyols, the typically useful range of ratios of non-fluorinated polyols to fluorinated polyols is from about 1: 1 to about 1: 100.

Therefore, the fluorochemical ester oligomers are preferably one or more fluorinated polyols, optionally one or more non-fluorinated polyols, one or more polyacyl compounds and one or more monofunctional fluorine-containing compounds. It may contain a condensation reaction product with a fluorine-free monofunctional compound that can react with a polyacyl compound or a polyol.

A typical example of a suitable fluorinated polyol composed of at least one fluorine-containing group is R.^fSO₂N (CH₂CH₂OH)₂, For example N-bis (2-hydroxyethyl) perfluorobutyl sulfonamide, R^fOC₆H₄SO₂N (CH₂CH₂OH)₂, R^fSO₂N (R') CH₂CH (OH) CH₂OH, for example C₆F₁₃SO₂N (C₃H₇) CH₂CH (OH) CH₂OH, R_fCH₂CON (CH₂CH₂OH)₂, R^fCON (CH₂CH₂OH)₂, CF₃CF₂(OCF₂CF₂)₃OCF₂CON (CH₃) CH₂CH (OH) CH₂OH, R_fOCH₂CH (OH) CH₂OH, for example C₄F₉OCH₂CH (OH) CH₂OH, R^fCH₂CH₂SC₃H₆OCH₂CH (OH) CH₂OH, R^fCH₂CH₂SC₃H₆CH (CH)₂OH)₂, R^fCH₂CH₂SCH₂CH (OH) CH₂OH, R^fCH₂CH₂SCH (CH)₂OH) CH₂CH₂OH, R^fCH₂CH₂CH₂SCH₂CH (OH) CH₂OH, for example C₅F₁₁(CH₂)₃SCH₂CH (OH) CH₂OH, R^fCH₂CH₂CH₂OCH₂CH (OH) CH₂OH, for example C₅F₁₁(CH₂)₃OCH₂CH (OH) CH₂OH, R^fCH₂CH₂CH₂OC₂H₄OCH₂CH (OH) CH₂OH, R^fCH₂CH₂(CH₃) OCH₂CH (OH) CH₂OH, R^f(CH₂)₄SC₃H₆CH (CH)₂OH) CH₂OH, R^f(CH₂)₄SCH₂CH (CH)₂OH)₂, R^f(CH₂)₄SC₃H₆OCH₂CH (OH) CH₂OH, R^fCH₂CH (C₄H₉) SCH₂CH (OH) CH₂OH, R^fCH₂OCH₂CH (OH) CH₂OH, R^fCH2CH (OH) CH₂SCH₂CH₂OH, R^fCH₂CH (OH) CH₂SCH₂CH₂OH, R^fCH₂CH (OH) CH₂OCH₂CH₂OH, R^fCH₂CH (OH) CH₂OH, R^fR''SCH (R'''OH) CH (R'''OH) SR''R^f, (R^fCH₂CH₂SCH₂CH₂SCH₂)₂C (CH₂OH)₂, ((CF₃)₂CFO (CF)₂)₂(CH₂)₂SCH₂)₂C (CH₂OH)₂, (R^fR''SCH₂)₂C (CH₂OH)₂, 1,4-bis (1-hydroxy-1,1-dihydroperfluoroethoxyethoxy) perfluoro-n-butane (HOCH)₂CF₂OC₂F₄O (CF)₂)₄OC₂F₄OCF₂CH₂OH), 1,4-bis (1-hydroxy-1,1-dihydroperfluoropropoxy) perfluoro-n-butane (HOCH)₂CF₂CF₂O (CF)₂)₄OCF₂CF₂CH₂Manufactured by ring-opening polymerization of fluorinated oxetane such as OH), POLY-3-FOX (from Omniva Solutions, Inc., Akron, Ohio) Fluorinated oxetane polyols, ring-opening addition polymerization of fluorinated organic group-substituted epoxides with compounds containing at least two hydroxyl groups, as described in US Pat. No. 4,508,916 (Newell et al.). Polyether alcohols prepared by, and perfluoropolyether diols, such as HOCH from FOMBLIN ZDOL (Ausimont).₂CF₂O (CF)₂O)_8~12(CF₂CF₂O)_8~12CF₂CH₂OH) is mentioned, and in the formula, R^fIs a perfluoroalkyl group having 1 to 6 carbon atoms, or a perfluoroheteroalkyl group having 3 to about 50 carbon atoms in which all existing perfluorocarbon chains have 6 or less carbon atoms, or It is a mixture of these R'is an alkyl of 1 to 4 carbon atoms, R'' is a branched or linear alkylene of 1 to 12 carbon atoms, and an alkylene thio-alkylene of 2 to 12 carbon atoms. , 2 to 12 carbon atoms of alkylene-oxyalkylene, or 2 to 12 carbon atoms of alkyleneiminoalkylene, and the nitrogen atom is a halogen or 1 to 6 carbon atoms as a third substituent. Contains alkyl, as well as R'''is a straight chain or branched chain alkylene of 1 to 12 carbon atoms or formula C_rH_2r(OC_SH_2s)_tIn the formula, r is 1 to 12, s is 2 to 6, and t is 1 to 40.

Preferred polyols composed of at least one fluorine-containing group include N-bis (2-hydroxyethyl) perfluorobutyl sulfonamide, POLY-3-FOX (Omnova Solutions, Inc.). (Omnova Solutions, Inc., from Akron, Ohio), a fluorinated oxetane polyol produced by ring-opening polymerization of fluorinated oxetane, described in US Pat. No. 4,508,916 (Newell et al.) Polyether alcohols, perfluoropolyetherdiols, such as those prepared by ring-opening addition polymerization of fluorinated organic group-substituted epoxides with compounds containing at least two hydroxyl groups, such as FOMBLIN . ZDOL (HOCH from Ausimont)₂CF₂O (CF)₂O)_8~12(CF₂CF₂O)_8~12CF₂CH₂OH), 1,4-bis (1-hydroxy-1,1-dihydroperfluoroethoxyethoxy) perfluoro-n-butane (HOCH)₂CF₂OC₂F₄O (CF)₂)₄OC₂F₄OCF₂CH₂OH) and 1,4-bis (1-hydroxy-1,1-dihydroperfluoropropoxy) perfluoro-n-butane (HOCH)₂CF₂CF₂O (CF)₂)₄OCF₂CF₂CH₂OH).

For more preferred polyols composed of at least one fluorine-containing group, N-bis (2-hydroxyethyl) perfluorobutyl sulfonamide, 1,4-bis (1-hydroxy-1,1-dihydroperfluoropropoxy) perfluoro-n-butane (HOCH)₂CF₂CF₂O (CF)₂)₄OCF₂CF₂CH₂OH).

Representative examples of suitable, non-polymeric, non-fluorinated polyols include alkylene glycols, polyhydroxyalkanes, and other polyhydroxy compounds. The alkylene glycol includes, for example, 1,2-ethanediol, 1,2-propanediol, 3-chloro-1,2-propanediol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 2-methyl-1,3-propanediol, 2,2-Dimethyl-1,3-propanediol (neopentyl glycol), 2-ethyl-1,3-propanediol, 2,2-diethyl-1,3-propanediol, 1,5-pentanediol, 2-ethyl-1,3-pentanediol, 2,2,4-trimethyl-1,3-pentanediol, 3-methyl-1,5-pentanediol, 1,2-, 1,5-, and 1,6-hexanediol, 2-Ethyl-1,6-hexanediol, bis (hydroxymethyl) cyclohexane, 1,8-octanediol, bicyclo-octanediol, 1,10-decanediol, tricyclo-decanediol, norbornanediol, and 1,18- Dihydroxyoctadecane can be mentioned. Polyhydroxyalkanes include, for example, glycerin, trimethylolethane, trimethylolpropane, Included are 2-ethyl-2- (hydroxymethyl) -1,3-propanediol, 1,2,6-hexanetriol, pentaerythritol, quinitol, mannitol, and sorbitol. Other polyhydroxy compounds include, for example, polyols, which include, for example, di (ethylene glycol), tri (ethylene glycol), tetra (ethylene glycol), tetramethylene glycol, dipropylene glycol, diisopropylene glycol. , Tripropylene glycol, bis (hydroxymethyl) propionic acid, N, N-bis (2-hydroxyethyl) -3-aminopropyltriethoxysilane, bicin, 1,11- (3,6-dioxaundecane) diol, 1,14- (3,6,9,12-tetraoxatetradecane) diol, 1,8- (3,6-dioxa-2,5,8-trimethyloctane) diol, 1,14- (5,10-dioxatetradecane) diol, castor oil, 2-Butin-1,4-diol, N, N-bis (hydroxyethyl) benzamide, 4,4'-bis (hydroxymethyl) diphenylsulfone, 1,4-benzenedimethanol, 1,3-bis (2-) Hydroxyethioxy) Benzene, 1,2-dihydroxybenzene, resorcinol, 1,4-dihydroxybenzene, 3,5-, 2,6-, 2,5-, and 2,4-dihydroxybenzoic acid, 1,6- , 2,6-, 2,5-, and 2,7-Dihydroxynaphthalene, 2,2'-and 4,4'-biphenol, 1,8-dihydroxybiphenyl, 2,4-Dihydroxy-6-methyl-pyrimidine, 4,6-dihydroxypyrimidine, 3,6-dihydroxypyridazine, bisphenol A, 4,4'-ethylidene bisphenol, 4,4'-isopropyrimidine (2,6-) Dimethylphenol), Bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane (bisphenol C), Examples include 1,4-bis (2-hydroxyethyl) piperazine, bis (4-hydroxyphenyl) ether, as well as other aliphatic, heteroaliphatic, saturated alicyclics, aromatics, saturated heteroalicyclics, And heteroaromatic polyols and the like, and mixtures thereof.

Typical examples of useful polymers and non-fluorinated polyols are polyoxyethylene, polyoxypropylene, and ethylene oxide-terminated polypropylene glycols and triols, of which about 100 to about 1000 for this diol, or about about 1000 for triol. Polytetramethylene glycols of various molecular weights, polydialkylsiloxane diols of various molecular weights, hydroxy-terminated polyesters and hydroxy-terminated polylactones (eg, polycaprolactones), equivalent to 70-about 700 equivalents, with a molecular weight of about 200-about 2000. Polyols), hydroxy-terminated polyalkadiene (eg, hydroxyl-terminated polybutadiene), and the like. If desired, a mixture of polymer polyols can be used.

A useful commercially available polymer, non-fluorinated polyol, has a number average molecular weight (M) of about 200 to about 2000._n) Range of Carbo Wax (Trademark) Poly (Ethylene Glycol) Materials (from Union Carbide Corp.), PPG-425 (from Lyondell Chemicals) and other poly (propylene glycol) ) Materials, block copolymers of poly (ethylene glycol) and poly (propylene glycol), such as PLURONIC L31 (from BASF Corporation), Bisphenol A ethoxylate, Bisphenol Bisphenol A propyloxylate, Bisphenol A propoxylate / ethoxylate (from Sigma-Aldrich), POLYMEG 650 and 1000 (Quaker Oats) Company (Quaker Oats From Company) and polytetramethylene ether glycols such as TERATHANE (trademark) polyol (from DuPont), poly bd (trademark) materials (from Elf Atochem), etc. Hydroxy-terminal polybutadiene resin, "PeP" series of polyoxyalkylene tetrols with secondary hydroxyl groups (from Wyandotte Chemicals Corporation), such as "PeP" 450, 550, and 650, TONE ) (Trademarks) M of the range of about 200 to about 2000, such as 0201, 0210, 0301, and 0310 (from Union Carbide)._nPolycaprolactone polyol (PARAPLEX) (trademark) U-148 (from Rohm and Haas), aliphatic polyesterdiol, MULTRON (trademark) poly (ethylene adipate) polyol (Mobay) Polyester polyols such as (from Mobay Chemical Co.), M_nPolycarbonate diols such as DURACARB 120 (PPG Industries Inc.), which is a hexanediol carbonate having = 900, and similar, and mixtures thereof.

Preferred non-fluorinated polyols include 1,2-ethanediol, 1,2- and 1,3-propanediol, 1,3- and 1,4-butanediol, neopentyl glycol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,2-, 1,5-, and 1,6-hexane Diol, bis (hydroxymethyl) cyclohexane, 1,8-octanediol, 1,10-decanediol, di (ethylene glycol), tri (ethylene glycol), tetra (ethylene glycol), di (propylene glycol), di (iso) Propylene glycol), tri (propylene glycol), poly (ethylene glycol) diol (number average molecular weight of about 200 to about 1500), poly (di (ethylene glycol) phthalate) diol (for example, number average molecular weight of about 350 or about 575). (With), poly (propylene glycol) diol (number average molecular weight of about 200 to about 500), PLURONIC L31 (BASF (BASF) From Corporation), block copolymers of poly (ethylene glycol) and poly (propylene glycol), polycaprolactone diols (number average molecular weight of about 200 to about 600), resorcinol, hydroquinone, 1,6-, 2,5 -, 2,6-, and 2,7-dihydroxynaphthalene, Included are 4,4'-biphenols, bisphenol A, bis (4-hydroxyphenyl) methane, and the like, as well as mixtures thereof.

More preferred non-fluorinated polyols include 1,2-ethanediol, 1,2- and 1,3-propanediol, 1,4-butanediol, neopentyl glycol, 1,2- and 1,6-hexanediol. , Di (ethylene glycol), Tri (ethylene glycol), poly (di (ethylene glycol) phthalate) diols (eg, having a number average molecular weight of about 350 or about 575), poly (ethylene glycol) diols (eg, number averages of about 200, 300, 400) Polypropylene glycol (for example, having a number average molecular weight of about 425), dimer diol, polycaprolactone diol (for example, having a number average molecular weight of about 530), 3,5-dihydroxybenzene, bisphenol A , Resorcinol, hydroquinone, and mixtures thereof.

Polyaclic compounds and derivatives thereof (eg, dicarboxylic acid halides, dicarboxylic acid anhydrides, and dicarboxylic acid esters) suitable for use in the preparation of fluorochemical compositions are at least one aliphatic, heteroaliphatic (ie,). , Containing heteroatoms in the chain, such as nitrogen, oxygen, or sulfur), saturated alicyclic, saturated heteroaliphatic, or polymer moieties. Preferably, the polyacyl compound is aliphatic in its native state.

Acyl derivatives are sometimes preferred over acids for a variety of reasons. For example, acyl halides provide both relatively high reaction rates and reactions that tend to reach completion. The resulting HCl is volatile and can be removed by other removal means, such as under vacuum or by washing with water.

When polybasic acids are used, catalysts such as p-toluenesulfonic acid or trifluoromethanesulfonic acid can be used, as well as minimizing the degradation of the fluorochemical composition obtained under conditions of use. To do so, it can be selected to be removable or deactivated after the reaction is complete (eg, for reactions with bases such as triethylamine, CaO, etc.).

Representative examples of suitable dicarboxylic acids and dicarboxylic acid derivatives include the following acids and their corresponding esters, halides, and anhydrides, octadecanedic acids (ie, R).¹Is 16), icosane diacid (ie, R)¹Is 18) and docosanedioic acid (ie, R¹Is 20), most preferably 16 carbon atoms.

When the fluorochemical composition of the present invention is used as a topical treatment, aliphatic dicarboxylic acids (and derivatives thereof) are preferable.

A fluorochemical monofunctional compound useful for preparing the fluorochemical compositions of the present invention comprising a mixture of ester molecules includes at least one R.^fExamples include those containing a group. R^fThe group can contain a straight chain, a branched chain, a cyclic fluorinated alkylene group, or a combination thereof. R^fThe group optionally contains one or more heteroatoms (ie, oxygen, sulfur, and / or nitrogen) in the carbon-carbon chain to form a carbon-heteroatom-carbon chain (ie, a heteroalkylene group). it can. A fully fluorinated group is generally preferred, but hydrogen or chlorine atoms can also be present as substituents if any one or less atoms are present for every two carbon atoms. Either R^fThe group further preferably contains at least about 40% by weight of fluorine, more preferably at least about 50% by weight of fluorine. The terminal portion of this group is usually all fluorinated and preferably contains at least 3 fluorine atoms, eg CF.₃O-, CF₃CF₂-, CF₃CF₂CF₂-, (CF₃)₂N-, (CF₃)₂CF-, SF₅CF₂-Can be mentioned. Perfluoroaliphatic group (ie, formula C_nF_{2n + 1}-) (In the formula, n is 1 to 6 (including 1 and 6)) is preferable. Further, the fluorochemical monofunctional compound preferably has a melting point above room temperature. Oligomers derived from solid or crystalline fluorochemical monofunctional compounds at room temperature have been found to exhibit higher contact angle performance than compounds with lower melting points.

Useful fluorine-containing monofunctional compounds also include compounds of formula II: R^fQ'(II) During the ceremony R^fIs a perfluoroalkyl group having 1 to 12 carbon atoms, or a perfluoroheteroalkyl group having 3 to about 50 carbon atoms in which all existing perfluorocarbon chains have 6 or less carbon atoms. Yes, Q'is the moiety containing a functional group that is reactive with the terminal acyl group (of the polyacyl compound) or the hydroxyl group (of the polyol).

Compound R_fQ'reacts with polyol or acyl compound to end portion R^fSupplying Q- can be understood by referring to Equation I.

R^fQ'is the following fluorine-containing monoalcohol,

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And the like, and mixtures thereof, may be included in the formula, R.^fIs a perfluoroalkyl group having 1 to 12 carbon atoms, or a perfluoroheteroalkyl group having 3 to about 50 carbon atoms in which all existing perfluorocarbon chains have 6 or less carbon atoms. .. If desired, similar thiols can be utilized without the use of such alcohols.

Preferred fluorine-containing monoalcohols include 2- (N-Methylperfluorobutane sulfonamide) ethanol, 2- (N-ethylperfluorobutane sulfonamide) ethanol, 2- (N-Methylperfluorobutane sulfonamide) propanol, N-Methyl-N- (4-Hydroxybutyl) Perfluorohexanesulfonamide, 1,1,2,2-Tetrahydroperfluorooctanol, 1,1-dihydroperfluorooctanol, C₆F₁₃CF (CF)₃) CO₂C₂H₄CH (CH)₃) OH, nC₆F₁₃CF (CF)₃) CON (H) CH₂CH₂OH, C₄F₉OC₂F₄OCF₂CH₂OCH₂CH₂OH, C₃F₇CON (H) CH₂CH₂OH, 1,1,2,2,3,3-hexahydroperfluorodecanol, C₃F₇O (CF (CF)₃) CF₂O)_1~36CF (CF)₃) CH₂OH, CF₃O (CF)₂CF₂O)_1~36CF₂CH₂OH, C₄F₉-SO₂NMeC₂H₄OH and the like, and mixtures thereof.

Other useful fluorine-containing compounds include functional oligomers such as those described as components in paragraph [00010] of U.S. Patent Application Publication No. 2007/004895, which is incorporated herein by reference in its entirety. Fluoroacrylates and fluorinated polyethers such as those described in formulas (I) and (III) of US Pat. No. 7,214,736 (which is incorporated herein by reference in its entirety). Medium, T_kIs a reactive group capable of reacting with an acyl group or a hydroxyl group.

Fluorochemical monofunctional compound, R^fQ'may contain a derivative of a fluorine-containing monocarboxylic acid (ester, acid halide, etc.), and the fluorine-containing carboxylic acid includes Eq. (1) R.^f(CH₂)_n(X)_p(CH₂)_mC (O) OH (in the formula, R^fIs as defined above, n and m are independently integers from 0 to 14 (preferably 0 to 8, more preferably 0 to 4), and X is divalent oxygen or sulfur. p is an integer of 0 or 1), and equation (2) R^fQR'C (O) OH (in the formula, R^fIs as defined above, where R'has 1 to about 12 carbon atoms (preferably 1 to 8 carbon atoms, more preferably 1 to about 4 carbon atoms). Divalent alkyl (straight or branched) or cycloalkyl radicals, and divalent linking group Q are -SO₂N (R'')-or -CON (R'')-, where R'' is 1 to about 12 carbon atoms (preferably 1 to 8 carbon atoms, more preferably 1 to about 4 carbon atoms. Those having a monovalent alkyl (straight or branched), cycloalkyl, or aryl radical having a carbon atom) can be mentioned.

Perfluorobutyric acid (C) is a typical example of a useful derivative of fluorine-containing monocarboxylic acid.₃F₇C (O) OH), perfluoroisobutyric acid ((CF)₃)₂CFC (O) OH), hydroperfluorobutyric acid (C₃F₆HC (O) OH), perfluoropentanoic acid (C)₄F₉C (O) OH), hydroperfluoropentanoic acid (C)₄F₈HC (O) OH), perfluorohexanoic acid (C)₅F₁₁C (O) OH), hydroperfluorohexanoic acid (C)₅F₁₀HC (O) OH), perfluorocyclohexanylcarboxylic acid (C)₆F₁₁C (O) OH), perfluoroheptanic acid (C)₆F₁₃C (O) OH), perfluoro (3-ethoxypropionic acid), Perfluoro (3-propoxypropionic acid), perfluoro (3-butoxypropionic acid), perfluoro (3-pentoxypropionic acid), R^f[OCF (CF)₃) CF₂]_1~6OCF (CF)₃) C (O) OH (in the formula, R^fIs a perfluoroalkyl group of 1 to 12 carbon atoms), 4- (4-perfluoroisopropoxyperfluorobutyl) butyric acid, 4- (bis (perfluoroisopropyl) fluoromethoxy) perfluorobutyric acid, 12- (2-Perfluoroisopropoxyperfluoroethyl) dodecanoic acid, 6- (2-Perfluorocyclobutoxyperfluoroethyl) caproic acid, 4- (bis (perfluoroisopropyl) fluoromethoxy) perfluorobutyric acid, 4- (2-bis (perfluoroisopropyl) fluoromethoxyperfluoroethyl) butyric acid, 2- (N- (ethyl) perfluorobutane sulfonamide) acetic acid, and Included are 2- (N- (methyl) perfluorobutane sulfonamide) acetic acid, and the like, and mixtures thereof.

Preferred fluorine-containing monocarboxylic acids include Included are 2- (N- (ethyl) perfluorobutane sulfonamide) acetic acid, 2- (N- (methyl) perfluorobutane sulfonamide) acetic acid, and the like, and mixtures thereof.

With respect to the above list, the terminal hydroxyl or carboxyl group is replaced with a terminal acyl group (of the polyacyl compound) or another functional group that is reactive with the hydroxyl group (of the polyol) to form the linking group Q of formula I. It will be understood that it may be.

If desired, a non-fluorinated monofunctional compound such as a monoalcohol or monocarboxylic acid can be added as part of the total monoalcohol or monocarboxylic acid content (eg, in addition to the fluorine-containing monoalcohol or monocarboxylic acid). , Up to about 50 mol% of the total amount) can be used.

The most preferred ester oligomers are one or more fluorinated polyols, an excess of one or more diacyl compounds (compared to polyols), and a fluorinated monoalcohol sufficient to react with the terminal acyl group. Contains condensation reaction products. Such most preferred oligomers correspond to Formula III.

R^fQ [C (O) R³C (O) OR⁴O]_n[C (O) R³C (O)]_mQR^f (III) During the ceremony n is a number from 1 to 10 (including 1 and 10) m is 1 R^fHas a perfluoroalkyl group having 1 to 12 carbon atoms, preferably 6 or less carbon atoms, or all existing perfluorocarbon chains having 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms 3 It is a perfluoroheteroalkyl group having 1 to about 50 carbon atoms. Q is a divalent linking group as described above, May be the same or different R³Is a linear alkylene with 15 to 20 carbon atoms, R⁴Is a polyvalent organic group that is a residue of the polyol, which is 1 to 14 carbon atoms, preferably 1 to 8 carbon atoms, more preferably 1 to 4 carbon atoms, most. It is preferably a linear or branched alkylene, cycloalkylene, arylene or heteroalkylene group of two carbon atoms, with at least a portion of R.⁴The group is substituted with or contains a single perfluoroalkyl group, a perfluoroheteroalkyl group, a perfluoroheteroalkylene group, or a mixture thereof.

The fluorochemical composition further comprises a reaction product of a polymerizable compound comprising one or more polymerizable groups and at least one reactive group reactive with a hydroxyl group or an acyl group. The polymerizable group may be incorporated into the fluorochemical ester oligomer by a reactive functional group as described above. Examples of useful polymerizable groups include, but are not limited to, acrylates, methacrylates, vinyls, allyls, and glycidyls. Typical useful compounds having a polymerizable group include hydroxyethyl acrylate, hydroxyethyl methacrylate, pentaerythriol triacrylate, allyl alcohol, glycidol, C.₂H₅(CH₃) C = NOH, CH₂= CHO (CH₂)₄OH and glycidyl methacrylate are mentioned.

The fluorochemical compositions of the present invention comprising a mixture of ester molecules are obtained by simply blending a polyol, a monofunctional compound, a polyacyl compound and optionally (d) one or more polymerizable compounds. Can be manufactured. As will be appreciated by those skilled in the art, the order of blending or process ordering is non-limiting and can be improved to produce the desired fluorochemical composition. In synthesis, for example, polyacyl compounds, polyols, and fluorine-containing monofunctional compounds (R)_fQ'), and optionally (d) one or more polymerizable compounds, and a solvent are filled into a dry reaction vessel immediately continuously or as a pre-prepared mixture. Once a homogeneous mixture or solution is obtained, a catalyst is typically added and the reaction mixture is heated. The temperature is usually determined by the boiling point of the solvent and the boiling point of the by-product. By-products such as water or alcohol are usually removed by azeotropic distillation.

Fluorine-containing monofunctional compound (R)^fWhen preparing the fluorine-containing ester oligomer of the above formula I using Q'), the molar weight of the obtained polyester was controlled by changing the molar ratio of the monofunctional compound and / or the polyol to the polyacyl compound. The properties can be adjusted as desired.

Depending on the reaction conditions (eg, the reaction temperature and / or the polyacyl compound used), a catalyst concentration of up to about 0.5% by weight of the mixture of polyacyl compound / polyol / monofunctional compound may be used, but typically about. 0.00005 wt% to about 0.5 wt% is required, preferably from about 0.02 wt% to about 0.1 wt%. Suitable catalysts include acid and base esterification catalysts such as those known in the art. Useful catalysts include para-toluenesulfonic acid and CF₃SO₃H is mentioned. If an acid catalyst is used, the acid catalyst is preferably removed from the oligomer or neutralized after oligomerization. It has been found that the presence of catalyst can adversely affect contact angle performance.

Mixtures of polyols and / or mixtures of monofunctional compounds can be used in place of single polyols and / or single monofunctional compounds. For example, polyols with polymerizable groups and R^fA polyol mixture containing a polyol having a group can be used. Similarly, a mixture of monofunctional compounds containing a monofunctional compound having a polymerizable group and a fluorine-containing monofunctional compound can be used.

The fluorochemical compositions of the present invention can be prepared by using the procedures and transesterification procedures and transesterification reactions known to those skilled in the art. For example, in a fluorochemical composition, (a) a fluorine-containing monofunctional compound is reacted with a polyol and a diacyl compound (or derivative) at the same time, and (b) the polyol is first reacted with a polyacyl compound (or derivative), and then (C) First, the fluorine-containing monofunctional compound is reacted with the diacyl compound (or derivative), or the fluorine-containing monofunctional compound is reacted with the polyol. It can be prepared by doing either of the following and then reacting the resulting mixture with the remaining reactants.

The reaction is sufficient to maintain the reactants in solution or in melt (using commonly used solvents and / or equipment), usually under atmospheric pressure and in solution or melt. At temperature, it can be done. For example, melting temperatures in the range of about 90 ° C to about 240 ° C (preferably about 100 ° C to about 210 ° C, more preferably about 110 ° C to about 170 ° C) can be typically utilized. If present, the removal of the solvent or by-product HCl can be carried out under reduced pressure, for example using a vacuum corresponding to about 67 kPa (500 torr) or less. Removal of esterification by-products by distillation is with toluene or fluorination such as NOVEC HFE-7100 or HFE-7200 (from 3M Company). It may be affected by the choice of a suitable solvent such as ether.

When water is a by-product, water-immiscible hydrocarbon solvents such as heptane or toluene, fluorinated ethers, or perfluorocarbons are preferred. Perfluorocarbons are preferred when the by-product is a lower alcohol.

The fluorochemical composition of the present invention containing a mixture of ester oligomers can be produced according to a step-by-step synthesis method in addition to the batch method. In the synthesis, the polyacyl compound and the polyol are dissolved together under dry conditions, preferably in a solvent, then the resulting solution is heated as described above for 0.5 to 2 hours in the presence of a catalyst. , Preferably for 1 hour.

The resulting ester oligomer may then be further reacted with one or more of the above monofunctional compounds. A monofunctional compound may be added to the reaction mixture, which reacts with the remaining or significant portion of the remaining hydroxyl or acyl groups. The above temperatures, drying conditions, and mixing are continued for 0.5 to 2 hours, preferably 1 hour. Thereby, the terminal fluorine-containing group may be bonded to the hydroxyl or acyl functional ester oligomer and the compound. These oligomers and compounds are optionally further polymerized by reacting any of the hydroxyl or acyl groups remaining in the resulting mixture with the one or more reactive polymerizable group-containing compounds. Can be functionalized. Therefore, the polymerizable compound is added to the reaction mixture using the same conditions as for the preceding addition.

A polymerizable group-containing compound can be added to react with a hydroxyl group or an acyl group under the above conditions in any of the above steps. For example, as described above, the polymerizable group-containing compound can be added to the polyol as a mixture. Alternatively, the polymerizable group-containing compound may be (a) after the reaction of the polyol with the polyacyl compound, (b) as a mixture with the monoalcohol, and (c) after the reaction of the polyol and the monofunctional compound with the polyacyl compound. , Can be added. When the polymerizable group-containing compound is a monoalcohol, it is preferably added as a mixture with a fluorine-containing monoalcohol. When the polymerizable group-containing compound is a diol, it is preferably added as a mixture with polycol.

When the chemical composition of the present invention contains an ester oligomer having one or more carboxylic acid groups, the solubility or dispersibility of the composition in water is further increased by producing a salt of the carboxylic acid group. .. Basic salt-forming compounds such as tertiary amines, quaternary ammonium hydroxides, and inorganic bases include sodium hydroxide, potassium hydroxide, cesium hydroxide, lithium hydroxide, calcium hydroxide, magnesium hydroxide. , Zinc hydroxide, and barium hydroxide, but are not limited to these, and are used in suitable amounts (ie, in amounts to maintain pH greater than about 6). be able to. These basic salt-forming compounds are preferably added to the aqueous phase to form incorporated side branches and / or terminal carboxylic acid base salts on the ester oligomer, but may optionally be added during the preparation of the ester oligomer. Can be done. Examples of useful amine salt-producing compounds include ammonia, trimethylamine, triethylamine, tripropylamine, triisopropylamine, tributylamine, triethanolamine, diethanolamine, methyldiethanolamine, morpholine, N-methylmorpholine, dimethylethanolamine, and these. Can be selected from the group consisting of a mixture of, but is not limited to these. Preferred salt-producing compounds include those selected from the group consisting of ammonia, trimethylamine, dimethylethanolamine, methyldiethanolamine, triethylamine, tripropylamine, and triisopropylamine, which have a chemical composition prepared from them. This is because the compound is not excessively hydrophilic during coating and curing. All of the diols, alcohols, and silane compounds are polyacyl compounds, as certain salts formed by the reaction of salt-forming compounds such as potassium hydroxide in combination with carboxylic acid groups can cause undesired reactions with acyl groups. It is preferable to add the salt-forming compound to the aqueous phase after reacting with the acyl group of.

If desired for a particular application, in addition to the above reactants, a small amount of one or more polymeric chain extenders or non-polymeric chain extenders (eg, diamines) are used in the preparation of the fluorochemical composition. be able to.

The coating composition of the present invention comprises an aqueous suspension, an aqueous emulsion, or an aqueous solution, or an organic solvent (or organic solvent / water) solution, an organic suspension, or an organic emulsion, which are the fluorochemicals of the present invention. Contains the composition. When applied as a coating material, the fluorochemical coating composition imparts oil repellency and water repellency, and / or stain release and stain resistance to a wide variety of any substrate.

The fluorochemical composition of the present invention is dissolved, suspended or dispersed in various solvents to form a coating composition suitable for use when coating the chemical composition of the present invention on a substrate. Can be done. Aqueous suspensions, emulsions, or solutions are usually preferred and can contain from about 0.1% to about 50% by weight of non-volatile solids (based on the total weight of the ingredients). Depending on the substrate to which the composition is applied, water is a preferred solvent as it does not cause environmental problems and is safe and non-toxic and acceptable.

Another embodiment of the present invention is an article composed of a substrate having one or more surfaces, the cured coating obtained from the coating composition of the present invention on one or more surfaces of the substrate. There is a membrane. After application and curing of the coating composition, the article exhibits high hydraulic and hexadecane dynamic contact angles, oil repellency and water repellency, and / or stain release and stain resistance.

The coating composition of the present invention can be applied to a wide variety of substrates including, but not limited to, fibrous substrates, leather substrates, and hard substrates. Illustrative examples of fibrous substrates include woven fabrics, knit fabrics, and non-woven fabrics (eg, cotton, flax, wool, silk, polyester, nylon, and blends of such fibers. Nylon or polyester bonded to natural, synthetic, and / or natural / synthetic blends), laminates (eg, stretched polytetrafluoroethylene (PTFE) as used for GORE® films. Fabric), cloth, carpet, and paper. Examples of hard substrates include, but are not limited to, glass, ceramics, masonry, concrete, natural stone, artificial stone, metal, wood, plastic, and painted surfaces. The substrate can have a flat or curved surface and may be inherently particulate or fibrous. Preferred substrates are fibrous or capable of absorbing liquids and are therefore porous. Such substrates are particularly susceptible to stains and stains, but are also very susceptible to the fluorochemical compositions of the present invention, which are the substrates in which the coating composition is fibrous or porous. This is because it can penetrate into the surface and spread to the inner surface of the substrate.

Typical examples of substrates that can be coated with this coating composition are lenses used in ophthalmic eyeglasses, sunglasses, optical equipment, lighting equipment, watch crystals, and the like, plastic window glazing. ), Signs, modified surfaces such as wallpaper and vinyl flooring, composites such as FORMICA branded sheeting or laminated flooring (eg, PERGO branded flooring). Or laminated substrates, ceramic tiles and fixtures (sinks, showers, toilets), natural and artificial stones, decorative stones and paving stones, cement and stone, sideways and motorways, particles that make up grout or applied grout. Finished surfaces, wooden furniture surfaces (desktops, table tops), cabinet surfaces, wooden flooring, decking and fence materials, leather, paper, fiberglass fabrics and other fiber-containing fabrics, cloths, carpets, drapes, Examples include upholstery materials, clothing, and the like.

The coating film prepared from this coating composition can make the metal surface stain resistant and can preserve the optical properties of the metal surface, such as those on decorative metal pieces and mirrors, for a longer period of time. This coating composition can make the wooden surface more resistant to food and drink stains, while helping to maintain a glossy appearance. In addition, this coating composition can be applied as airplane wings, boat hulls, fishing lines, medical surfaces, and siding materials for food peeling, melt peeling, sticky peeling applications, and the like. Can be used for things. Decorative stones include, for example, marble, granite, limestone, slate, and the like.

Preferred substrates that can be coated with the coating compositions of the present invention are fibrous materials such as non-woven fabrics, knits, and woven fabrics, laminates, carpets, drape fabrics, upholstery materials, garments, and essentially any fabric. It is a base material. In order to impart water / oil repellency and / or stain resistance to a substrate having one or more surfaces, (a) the coating composition of the present invention is applied on one or more surfaces of the substrate. (b) The coating composition is cured (ie, dried) at ambient temperature or preferably at high temperature. The use of high temperatures is particularly advantageous for curing fibrous substrates coated with the fluorochemical compositions of the present invention, as it achieves the best water / oil repellency. High temperatures of about 50 ° C to about 175 ° C are preferred, and typically more preferred are about 100 ° C to about 170 ° C.

The coating composition dries the treated substrate by standard methods such as spraying, padding, dipping, roll coating, brushing, or dyeing (optionally, to remove any remaining water or solvent). It can be applied to a processable substrate. The processable substrate is a sheet, fiber (such form or aggregated form, eg, weaving, toe, web, roving), woven or non-woven fabric in the form of a molded or blow-molded article. It can be fabric, film, etc. When coating a flat substrate of appropriate size, knife coating or bar coating may be used to ensure a uniform coating of the substrate. If desired, the fluorochemical composition can be applied together with conventional fiber treatment agents such as, for example, spin finishes or fiber lubricants. Such a topical treatment process can include the use of pure fluorochemical compositions without additional solvents, which is preferred from an environmental point of view regarding the use of organic solvent solutions of fluorochemical compositions.

The coating composition can be applied in an amount suitable to achieve the desired water / oil repellency for a particular application. This amount can be determined empirically and can be adjusted as needed or desired to achieve water / oil repellency without jeopardizing the properties of the processable substrate.

The coating composition can be applied to the substrate in any desired thickness. Coatings as thick as a few micrometers can provide very low surface energy, stain resistance, and stain release. However, thicker coatings (eg, up to about 20 micrometers or more) can also be used. Thicker coatings can be obtained by applying a single thicker layer of coating composition containing a relatively high concentration of the chemical composition of the invention to the substrate. Thicker coatings can also be obtained by applying a continuous layer of coating composition containing a relatively low concentration of the fluorochemical composition of the invention to the substrate. The latter can be done by applying a layer of the coating composition to the substrate and allowing it to dry, followed by the application of successive layers. The continuous layer of the coating can then be applied to the dry layer. This procedure can be repeated until the desired coating thickness is achieved.

To form a polymer melt blend by melt processing, the fluorochemical composition is thoroughly mixed with, for example, pelletized or powdered polymers and then, for example, mold molding, melt blowing, melt spinning, or melting. It can be melted by a known method such as extrusion molding. The fluorochemical composition can be mixed directly with the polymer or can be mixed with the polymer in the form of a "masterbatch" (concentrate) of the fluorochemical composition within the polymer. If desired, the organic solution of the fluorochemical composition can be mixed with the powdery or pelletized polymer, followed by drying (to remove the solvent) and subsequent melt processing. Alternatively, the fluorochemical composition can be injected into a stream of molten polymer to form a blend, which is immediately followed by, for example, extrusion molding into fibers or films or molding into articles.

After the melting process, an annealing step can be performed to improve the water / oil repellency properties. In addition to or instead of such an annealing step, a melt-processed mixture (eg, in the form of film or fiber) can be embossed between two heated rolls, one of these rolls. Or both can be patterned. The annealing step is typically carried out below the melting temperature of the polymer (for example, in the case of polyamide, at about 150 ° C to about 220 ° C for about 30 seconds to about 5 minutes).

The fluorochemical composition is made into a thermoplastic or thermosetting polymer in an amount sufficient to achieve the desired water / oil repellency for a particular application (or, alternative, to other treatable substrate materials. Can be added. This amount can be determined empirically and adjusted as needed or desired to achieve water / oil repellency without jeopardizing the properties of the polymer (or other treatable substrate). be able to. Generally, the fluorochemical composition is about 0.1% to about 10% by weight (preferably about 0.5% to about 4% by weight, more preferably about 4% by weight, based on the weight of the polymer (or other treatable substrate). It can be added in an amount in the range of about 0.75% by weight to about 2.5% by weight).

The molded article can be produced from the water / oil repellent composition of the present invention, and such a structure is found to be useful in any application requiring a certain degree of water / oil repellency. .. For example, the compositions of the present invention can be used to make films and mold or blown articles, as well as woven, knit, and non-woven fabrics (eg, microfibers and seascore fibers). It can be used to prepare melt-blown or melt-spun fibers such as. Such films, mold-molded or injection-molded articles, fibers, and fabrics exhibit water / oil repellency (and stain resistance) under various environmental conditions and can be used for various purposes.

For example, molded articles containing the compositions of the present invention can be prepared by standard methods (eg, by high temperature injection molding), eg, automobile headlamp covers, lenses (such as spectacle lenses), electronic. It is particularly useful as a case or circuit board for a device (eg, a computer), a screen for a display device, a window (eg, an airplane window), and the like. The film containing the composition of the present invention can be produced by any film production method generally adopted in the art. Such films can be non-porous or porous (the latter includes mechanically perforated films), and the presence and extent of perforations are selected according to the desired performance characteristics. This film can be used, for example, as a photographic film, a transparent film for use in overhead projectors, a tape backing material, a coating substrate, and the like.

Fibers containing the compositions of the present invention can be used, for example, in medical fabrics, medical and industrial clothing, fabrics for use in the manufacture of fabrics, home interiors such as rugs or carpets, papermaking tools, and chemical processes. It can be used to make woven, knitted, or non-woven fabrics that can be used to make filter media such as filters or breathing masks. Nonwoven webs or fabrics can be prepared by the steps used in the manufacture of either melt blown or spunbonded webs. For example, by Wente, "Superfine Thermoplastic Fibers" (Industrial &amp; Engineering Chemistry (Indus.) Eng'g Chem., Vol. 48, p. 1342, 1956), or by Wente et al., "Manufacture of Superfine Organic Fibers" (Naval Research Laboratories) A process similar to that described in Report) No. 4364, 1954) can be used. Multilayer structures made from non-woven fabrics have a wide range of industrial and commercial utility, such as medical fabrics. The construction of the constituent layers of such a multilayer structure can be varied depending on the properties of the desired end use, and the structure is incorporated herein by reference in US Pat. No. 5,145,727 (Potts). ) Etc.) and many useful combinations, such as those described in No. 5,149,576 (Potts et al.), Can include two or more layers of melt blown and spunbonded webs. In a multilayer structure, the fluorochemical composition can be used alone in one or more layers, or in combination with other additives in one or more layers. Alternatively, the fluorochemical composition and other additives can be separated from each other independently in one or more layers. For example, in a spunbond / melt blow / spunbond (SMS) three-layer structure, other additives (eg, for example, to impart both antistatic and water / oil repellency to the entire structure. Antistatic agents) can be used in one or both spunbond layers and fluorochemical compositions can be used in melt blown layers.

The fluorochemical polymer composition that imparts water / oil repellency can also be found to be useful as an additive to the coating film. Such coatings can be water and oil repellent as well as scratch resistant (and stain resistant) and can be used in the photographic industry or as a protective coating for engineering or magnetic recording media.

If desired, the water and oil repellent compositions of the present invention may further contain one or more additives, which are commonly used in the art, such as dyes. , Pigments, antioxidants, UV stabilizers, flame retardants, surfactants, plasticizers, tackifiers, fillers, and mixtures thereof. In particular, performance enhancers (eg, polymers such as polybutylene) can be used to impart water / oil repellency, for example in the application of melt additive polyolefins.

<p> The objects and advantages of the present invention are further exemplified by the following examples, but the specific materials listed in these examples and their amounts, as well as other conditions and details, excessively limit the present invention. Should not be interpreted as doing. In the examples,% by weight and parts by weight are shown, which are based on the weight of the entire composition unless otherwise indicated.</p><p> material ODDA-octadecanedioic acid, HO (O) C (CH)₂)₁₆From C (O) OH, Cognis Corporation (Cincinnati, Ohio).</p><p> TDDA-Tetradecanedioic acid, HO (O) C (CH)₂)₁₂From C (O) OH, Cathay Industrial Biotech Ltd (Powell, Ohio).</p><p> FBSEE-C₄F₉SO₂N (C₂H₄OH)₂, Equal molar amount of C₄F₉SO₂NH₂C₈F₁₇SO₂NH₂Substitute for, and C₄F₉SO₂NH₂However, an equimolar amount of perfluorobutane sulfonyl fluoride (PBSF) was added to NH.₃It can be prepared as described in Example 8 of US Pat. No. 3,787,351 (Olson), except that it can be prepared by reacting with.</p><p> MeFBSE-C₄F₉SO₂N (CH₃) CH₂CH₂React PBSF with methylamine and ethylenechlorohydrin using procedures as described in Example 1 of US Pat. No. 2,803,656 (Ahlbrecht et al.) With OH, equivalent 357. This makes it possible to manufacture in two stages.</p><p> C6 Telomer-FLOWET EA 600 from Clariant Corporation.</p><p> C4 Telomer-1H, 1H, 2H, 2H-nonafluoro-1-hexanol from TCI America (Portland, Oregon).</p><p> SA-stearyl alcohol (octadecanol).</p><p> ETHOQUAD C12-dodecyltrimethylammonium chloride (H)₂75% in O), from Akzo-Nobel.</p><p> From ARMOCURE VGH-70, Akzo-Nobel.</p><p> TERGITOL 15-S-30-C_12~16From Alkyl Polyoxyethylene (30 EO) Surfactant, Rohm &amp; Haas.</p><p> From TERGITOL TMN-6-trimethylnonane polyoxyethylene (6 EO) surfactant, Rohm &amp; Haas.</p><p> MIBK-methyl isobutyl ketone, 4-methyl-2-pentanone.</p><p> Test method Spray score (spray) The spray rating of the treated substrate is a value indicating dynamic water repellency against water colliding with the treated substrate. Water repellency was measured and tested by test method 22-1996 published in the 2001 Technical Manual of the American Association of Textile Chemists and Colorists (AATCC). It was expressed by the "spray score" of the base material. Spray scores were obtained by spraying 250 mL of water onto the substrate from a height of 15 cm. Wet patterns were visually graded using a scale from 0 to 100, where 0 means complete wetness and 100 means no wetness at all.</p><p> Oil repellent (OR) The oil repellency of the substrate was measured by the American Association of Textile Chemists and Colorists (AATCC) standard test method Nos. 118-1983. The test was based on the resistance of the treated substrate to oil penetration of different surface tensions. Treated substrates that are resistant only to NUJOL® mineral oil (lowest permeability of test oils) are given a rating of 1, whereas heptane (highest of test solutions). A score of 8 was given to the treated substrate that is resistant to (permeability). Other intermediate values were determined using other pure oils or oil mixtures as shown in the table below.</p><p><tables num="3"><img file="JP2010529263A_D0003.tif" /></tables></p><p> Bundesmann exam To evaluate dynamic water repellency, the permeability of raindrops to the treated substrate was measured using the Bundesliga test method (DIN 53888). In this test, the treated substrate is exposed to simulated rainfall, during which the backside of the substrate is rubbed. The appearance of the exposed surface of the upper part is visually inspected after 1 minute, 5 minutes and 10 minutes and given a score between 1 (the surface is completely wet) and 5 (no water remains on the surface). It was. In general, the Bundesliga test was performed only if the initial spray score on the sample was 95 or higher.</p><p> Cleaning procedure Using the procedure described below, a treated substrate sample represented as 5 L (5 washes) in the examples below was prepared.</p><p> Almost square 400 cm of treated substrate²~ About 900cm²230g sample of sheet of ballast sample (8100cm with almost square border)²Placed in the washing machine with 226.8 g (8 ounces) of dough (1.9 g), which is the shape of the sheet. Commercially available detergent (46 g from SAPTON Brand Detergent, Henkel (Germany)) was added and the washing machine was filled with warm water (40 ° C ± 3 ° C) to a high water level. Substrate and ballast loads were washed 5 times using a 12 minute normal wash cycle, followed by 5 rinse cycles and centrifugation. Samples were not dried during the repeat cycle, but were dried after the final cycle.</p><p> (Example 1) In a round bottom reaction flask equipped with a stir bar, heater, and Dean Stark trap, ODDA (30 g, 0.095 mol), FBSEE (27.5 g, 0.071 mol), MeFBSE (17.01 g, 0.048 mol), toluene (100 g) and Methanesulfonic acid (1 g) was added. The resulting mixture was refluxed at 115 ° C. for 15 hours. When collecting the desired amount of water (3 g), the temperature was lowered to 80 ° C. Then K₂CO₃(2-3 g) was added and the mixture was stirred for an additional 30 minutes. FTIR analysis showed that there were no hydroxyl peaks. The mixture was then hot filtered and the solvent removed by rotary evaporation.</p><p> (Examples 2 to 5, 7) Other polyester compositions were prepared and tested using a procedure similar to Example 1 except that they had the components and ratios as shown in Tables 1 and 2.</p><p> (Example 6) ODDA (10.47 g, 0.033 mol), FBSEE (9.625 g, 0.025 mol), MeFBSE (2.975 g, 0.008 mol), C4MH spacer oligomeric alcohol in a round bottom reaction flask equipped with a stir bar, heater, and Dean Stark trap. (20.37 g, 0.008 mol) (same substance as SPOL 2, prepared as described in US Pat. No. 2007/0004895 (A1) (published January 4, 2007)), toluene (150 g) And methanesulfonic acid (1 g) were added. The resulting mixture was refluxed at 115 ° C. for 15 hours. When collecting the desired amount of water (3 g), the temperature was lowered to 80 ° C. Then K₂CO₃(2-3 g) was added and the mixture was stirred for an additional 30 minutes. FTIR analysis showed that there were no hydroxyl peaks. The mixture was then hot filtered and the solvent removed by rotary evaporation.</p><p> Comparative example C1 C14-polyester was produced using the same molar ratios as in Example 1 except that ODDA replaced TTDA.</p><p> Emulsion preparation and application The following C18 polyester emulsions (Examples 1-7): MIBK (50 g) was added to the resulting polymer solid (20 g) and the mixture was heated to 65 ° C. In a separate beaker, ETHOQUAD C12 (0.53 g), TERGITOL 15-S-30 (0.6 g) and TMN-6 (1.2 g) were added to water (100 g). The mixture was stirred and heated to 65 ° C. The polymer in MIBK was slowly added to this stirred solution. The mixture was then sonicated for 4 minutes and the solvent was removed by rotary evaporation. The emulsion was applied on polyester and nylon test fabrics via a 0.6% SOF (solid content on fiber) pad application and subsequently cured at 160 ° C for 1.5 minutes.</p><p> C18 polyester emulsification below (Example 8): The surfactants used were ARMOCURE VGH-70 (0.85g), TMN-6 (0.9g) and co-solvent dipropylene glycol monomethyl ether (7.5). Emulsions were prepared using the same procedure except that g).</p><p> The following C14 polyester emulsification (Comparative Example C1): Emulsions were prepared using the same procedure, except that co-solvent dipropylene glycol monomethyl ether (7.5 g) was added to the aqueous phase.</p><p> Performance results Initial performance results were obtained after 24 hours of adjustment at 21.1 ° C (70 ° F) and 60% RH. Durability was measured after washing the initial treated fabric at 40 ° C 5 times as described above. Performance results are provided in Table 1 (nylon fabric) and Table 2 (polyester fabric).</p><p><tables num="4"><img file="JP2010529263A_D0004.tif" /></tables></p><p><tables num="5"><img file="JP2010529263A_D0005.tif" /></tables></p><p> The following performance comparisons were made by applying the emulsion pad on 100% cotton fabric. The solid content (SOF) of the dough was set to be 0.9%. From the results, it is clear that C18-polyester (Example 8) exhibits higher dynamic water repellency than the comparative C14-polyester (Comparative Example C1).</p><p><tables num="6"><img file="JP2010529263A_D0006.tif" /></tables></p><p> (Examples 9 and 10) Examples 9 and 10 illustrate the use of the present invention on a laminate substrate. The 2.5% SIB load of the C18 embodiment of the present invention was applied to the indicated laminate.</p><p> The oligomer composition was prepared as follows. In a round bottom reaction flask equipped with a stir bar, heater, and Dean Stark trap, ODDA (30 g, 0.095 mol), FBSEE (27.5 g, 0.071 mol), MeFBSE (17.01 g, 0.048 mol), heptane (100 g) and Methanesulfonic acid (1 g) was added. The resulting mixture was refluxed at 100 ° C. for 5 hours. When collecting the desired amount of water (3 g), the temperature was lowered to 80 ° C. Triethylamine (1.10 g) was then added and the mixture was stirred for an additional 30 minutes. Heptane was then removed by distillation. Dissolve the remaining polyester solid sample (40 grams) in 80 grams of methyl isobutyl ketone (MIBK) in a three-necked 500 mL round-bottom flask. The mixture was heated to 65 ° C. Separately, in 200 grams of deionized water, 1.71 grams of VGH-70 (70% solids), 2.1 g of TERGITOL TMN-6 (90% solids) and 15 g of dipropylene glycol monomethyl. Ether was added. The water mixture was heated to 65 ° C. then the polyester mixture was added slowly with rapid stirring. After mixing for 15 minutes, the contents of the flask were passed through the homogenizer twice under a pressure of 17.2 MPa (2500 psig). MIBK was lost by vacuum distillation at 35 ° C from the resulting emulsion. The obtained emulsion had a solid content of 18.5%.</p><p> In Example 9, the substrate is 35 g / partially infiltrated with a monolithic urethane coating obtained from WL Gore and Associates, Inc. (Elkton, Maryland). m²86g / m bound to stretched PTFE (80% perforated) membrane²It was a two-layer laminate of woven nylon fabric.</p><p> In Example 10, the substrate is 35 g / partially infiltrated with a monolithic urethane coating obtained from WL Gore and Associates, Inc. (Elkton, Maryland). m²78g / m bound to stretched PTFE (80% perforated) membrane²It is a two-layer laminated body of woven polyester fabric.</p><p> The following performance was obtained.</p><p><tables num="7"><img file="JP2010529263A_D0007.tif" /></tables></p><p> Various improvements and modifications of the present invention will be apparent to those skilled in the art without departing from the scope and gist of the present invention.</p>