TW201609873A - Fluorinated compound, fluorinated polymer formed from same, curable composition comprising the fluorinated polymer, and cured product - Google Patents

Abstract

A fluorinated compound has the general formula (1): Rf-CONR-(CH2)a-SiR1X-(OSiR1X)b-(CH2)c-Y (1); wherein Rf is a fluoro-substituted group; R is H or a substituted or unsubstituted hydrocarbyl group; each R1 is an independently selected substituted or unsubstituted hydrocarbyl group; each X is independently R1 or an amine-containing group; Y is a terminal group selected from R and X; subscripts a and c are each are each independently selected from 0 and an integer from 1 to 10; and subscript b is an integer from 2 to 20; with the proviso that the fluorinated compound includes at least one amine-containing group. A fluorinated polymer comprises the reaction product of a Michael addition reaction of the fluorinated compound and a polyfunctional acrylate. A curable composition comprising the fluorinated polymer, a cured product formed from the curable composition, and a method of forming the cured product are also disclosed.

Description

a fluorinated compound, a fluorinated polymer formed therefrom, a curable composition comprising the fluorinated polymer, and a cured product

The present invention relates generally to fluorinated compounds, and more particularly to fluorinated compounds, fluorinated polymers formed from the fluorinated compounds, curable compositions comprising the fluorinated polymers, curable therefrom A cured product formed from the composition, and a method of forming the cured product from the curable composition.

Fluorinated compounds are known in the art and are used in a variety of applications and end uses. For example, fluorinated compounds are commonly used in curable compositions. The curable composition is applied to the substrate and cured to form a layer or coating on the substrate.

The layer formed from the curable composition comprising the fluorinated compound may have diverse and desirable physical properties depending on the components of the curable composition. These layers can be used to modify or modify the physical properties of the substrate or otherwise protect the substrate. For example, certain layers are commonly used to achieve stain and stain resistance, or to provide an easy to clean surface. Other layers are used to provide protection to the underlying substrate, such as providing water repellency and/or scratch resistance.

Ideally, the curable composition preferably has excellent physical properties such as storage stability. nature. These physical properties associated with the curable composition must be balanced with the desired properties of the resulting layer formed from the curable composition. For example, it is desirable that the layer have a high adhesion to the substrate while providing a scratch-resistant and easy-to-clean surface.

The present invention provides fluorinated compounds. The fluorinated compound has the formula (1): R _f -CONR-(CH ₂ ) _a -SiR ¹ X-(OSiR ¹ X) _b -(CH ₂ ) _c -Y (1); wherein R _f is a fluorine-substituted group; R is H or a substituted or unsubstituted hydrocarbon group; each R ¹ is an independently selected substituted or unsubstituted hydrocarbon group; each X is independently R ¹ or an amine group; Y is a terminal selected from the group consisting of R and X; subscripts a and c are each independently selected from 0 and an integer from 1 to 10; and the subscript b is an integer from 2 to 20; however, the fluorinated compound includes X or Y specifies at least one amine-containing group.

The invention also provides fluorinated polymers. The fluorinated polymer comprises the reaction product of a fluorinated compound and a Michael addition reaction of a polyfunctional acrylate.

Additionally, the present invention provides a curable composition comprising a fluorinated polymer and a polyfunctional acrylate. The invention further provides a cured product formed from a curable composition.

Finally, the invention provides a method of forming a cured product. The method comprises applying a curable composition to a substrate. The method further includes curing the curable composition on the substrate to form a cured product on the substrate.

The present invention provides fluorinated compounds. Fluorinated compounds are especially useful for forming, for example, A fluorinated polymer of a curable composition. In such embodiments, the fluorinated compound may alternatively be referred to as a fluorinated intermediate. The fluorinated compound, the fluorinated polymer, the curable composition, the cured product formed from the curable composition, and the method of forming the cured product are described below.

The fluorinated compound has the formula (1): R _f -CONR-(CH ₂ ) _a -SiR ¹ X-(OSiR ¹ X) _b -(CH ₂ ) _c -Y (1); wherein R _f is fluorine a substituted group; R is H or a substituted or unsubstituted hydrocarbon group; each R ¹ is an independently selected substituted or unsubstituted hydrocarbon group; each X is independently R ¹ or an amine group; Y is selected From the end groups of R and X; subscripts a and c are each an integer independently selected from 0 and 1 to 10; and the subscript b is an integer from 2 to 20; but the fluorinated compound includes X or Y At least one of the specified amine-containing groups.

R _f of the formula (1) is a group substituted by fluorine. Substitution by fluorine means that at least one portion, one segment, or one portion of R _f is substituted with fluorine. R _f can be partially or perfluorinated. Partially fluorinated means that _Rf can be monofluorinated or polyfluorinated rather than perfluorinated. For example, partially fluorinated covering monofluorinated, wherein only one substituted fluorine in R _f; and polyfluorinated, wherein the presence of two or more fluorine substituents in R _f. R _f is a price.

For example, _Rf can be an organic group or segment, a polyoxyl group or segment, or a combination thereof. An organic group as used herein is different from a polyoxyalkyl group in which a polyoxyalkyl group has a main chain comprising a siloxane chain (Si-O-Si), and the organic group has a carbon-based backbone and is absent A siloxane chain. R _f may include a decane bond and a carbon bond in the main chain.

When _Rf is a polyoxyalkyl group, the fluorine substitution is typically present in one or more hydrocarbyl substituents bonded to the oxime. In other words, the fluorine atom is usually not directly bonded to the ruthenium atom. For example, the ruthenium atoms of the polyoxyl group typically have two substituents in addition to the decane linkage, and such substituents may independently be fluorine-substituted. As a specific example, when R _f is a polyoxyalkyl group, R _f may include a group Si(CF ₃ ) ₂ O, wherein the CF ₃ group represents a fluorine substitution. Since R _{f does} not need to be perfluorinated, such a group of R _f may be, for example, Si(CFH ₂ )(CH ₃ )O, of which only one fluorine is substituted. If this particular group is present in _Rf , it is typically capped, for example trihydrocarbyl terminated, since _Rf is monovalent.

Alternatively, as set forth above, _Rf can be a fluorine-substituted organic group or moiety. In such embodiments, _Rf can be, for example, a fluorine-substituted alkyl group or a fluorine-substituted alkoxy group. The alkoxy groups can be independently repeated. R _f is the time when the fluorine substituted alkyl group, R _f typically comprise end groups having ₃ CF (if perfluorinated) of CF ₂ repeating group. When R _f is a fluorine-substituted alkoxy group, R _f includes one or more oxygen atoms, and may include an OCH ₂ group having a CF ₃ terminal group and a CF ₂ group.

In certain embodiments, R _f :(i) is partially fluorinated; (ii) comprises a perfluoropolyether segment; or (iii) both (i) and (ii) are combined. When R _f is (i) and (ii) and sometimes, R _f includes a substituent, moiety or group that is not perfluorinated, such that although R _f comprises a perfluorinated moiety, R as a monolithic group _{f is} not perfluorinated but is partially fluorinated.

When the R _f contains a perfluoropolyether segment, it may be present in a particular instance in R _f comprises the portion of _{- (CF 2) -, -} (CF (CF 3) CF 2 O) -, - (CF 2 CF (CF ₃ ) O)-, -(CF(CF ₃ )O)-, -(CF(CF ₃ )-CF ₂ )-, -(CF ₂ -CF(CF ₃ ))-, and -(CF(CF ₃ ) )-. These moieties may be present in any order in the perfluoropolyether segment of _Rf and may be in random or block form. Each portion may independently be present twice or more in the perfluoropolyether segment of _Rf . Typically, the perfluoropolyether segment of _Rf does not contain an oxygen-oxygen bond, wherein oxygen is typically present as a heteroatom between adjacent carbon atoms to form an ether linkage. The perfluoropolyether segment may be capped CF ₃ group.

In one particular embodiment, when R _f contains a perfluoropolyether segment, segment contains perfluoropolyether moiety has the following general formula (5) of _{:-( C 3 F 6 O) x} - (C 2 F 4 O _y -(CF ₂ ) _z - (5); wherein the subscripts x, y and z are each independently selected from 0 and an integer from 1 to 40, except that x, y and z are all not 0 at the same time. If both x and y are zero, then z is an integer from 1 to 40 and at least one other perfluoroether moiety is present in the perfluoropolyether segment. The subscripts y and z may be 0 and x is selected from an integer from 1 to 40, or the subscripts x and y are 0 and z is selected from an integer from 1 to 40; or, the subscripts x and z are 0 and y It is selected from an integer from 1 to 40. The subscript z may be 0 and x and y are each independently selected from an integer from 1 to 40, or the subscript y is 0 and x and z are each independently selected from an integer from 1 to 40; alternatively, the subscript x is 0. And y and z are each independently selected from an integer of from 1 to 40. Typically, x, y and z are each independently selected from an integer from 1 to 40. The portions indicated by the subscripts x and y may independently be branched or linear. For example, (C ₃ F ₆ O) may be independently represented by CF ₂ CF ₂ CF ₂ O, CF(CF ₃ )CF ₂ O or CF ₂ CF(CF ₃ )O.

Specific examples of R _f include any polyfluoropolyether segment suitable for polyfluoropolyether decane disclosed in U.S. Application Publication No. US 2014/0272111 A1, the entire disclosure of which is incorporated by reference in its entirety. In this article.

R is H or a substituted or unsubstituted hydrocarbon group. When R is a substituted or unsubstituted hydrocarbon group, R is typically a C ₁ -C ₂₂ hydrocarbon group which may be straight chain, branched and/or cyclic. The cyclic hydrocarbon group encompasses an aryl group as well as a saturated or unsaturated cyclic group. "Substituted" means that one or more hydrogen atoms may be replaced by an atom other than hydrogen (eg, a halogen atom such as chlorine, fluorine, bromine or iodine); or by oxygen, sulfur or nitrogen. Typically, R is a C ₁ -C ₄ alkyl group.

Each X is independently R ¹ or an amine-containing group. When X is an amine-containing group, the nitrogen of the amine group may be primary, secondary or tertiary. When one or more X of the fluorinated compound is an amine-containing group, each X may be independently selected from such amine-containing groups. In various embodiments, the amine-containing group is first order such that the nitrogen atom containing the amine group is bonded to two hydrogen atoms (-NH ₂ ), that is, the amine-containing group can be an amine group. The amine group-containing group may be bonded to a carbon atom of a main chain of the fluorinated compound or a ruthenium atom of a main chain of the fluorinated compound. The nitrogen atom containing an amine group may be directly bonded to the carbon and/or ruthenium in the main chain of the fluorinated compound, or the nitrogen atom may be bonded to the carbon in the main chain of the fluorinated compound via a divalent bond group and/or Alternatively, the divalent linking group may be a hydrocarbon group, a hetero group or an organoheterylene linkage. For example, in such embodiments, the amine-containing group can be selected from the group consisting of 2-aminoethyl, 3-aminopropyl, 3-(2-aminoethyl)aminopropyl, and/or 6-amine. Base group.

In certain embodiments of the fluorinated compound, R is H such that the fluorinated compound has the formula (2): R _f -CONH-(CH ₂ ) _a -SiR ¹ X-(OSiR ¹ X) _b -(CH ₂ ) _c -Y (2); wherein R _f , R ¹ , X, Y and the subscripts a, b and c have been defined as above.

In this or other embodiments, X is R ¹ and Y is an amine-containing group such that the fluorinated compound has the general formula (3): R _f -CONH-(CH ₂ ) _a -SiR ¹ ₂ - (OSiR ¹ ₂ ) _b -(CH ₂ ) _c -NHR (3); wherein R _f , R, R ¹ and the subscripts a, b and c are as defined above.

In this or other embodiments, the subscripts a and c are each 0 such that the fluorinated compound has the formula (4): R _f -CONH-SiR ¹ ₂ -(OSiR ¹ ₂ ) _b -NHR (4); Wherein R _f , R, R ¹ and the subscript b have been defined as above.

Fluorinated compounds can be prepared via a variety of synthetic routes. For example, a fluorinated compound can be prepared by reacting a carboxylate compound and a polyoxydiamine compound. The carboxylic acid ester compound typically has the formula (6): R _f -COOR ¹ (6); wherein R _f and R ¹ have been defined as above. The polyoxydiamine compound typically has the formula (7): RHN-(CH ₂ ) _a -SiR ¹ X-(OSiR ¹ X) _b -(CH ₂ ) _c -Y (7); wherein R ¹ , R, X and subscript b have been defined as above.

To increase the reactivity of the polyoxydiamine compound and reduce steric hindrance, each R is typically H. R ^{1 of the} carboxylate compound is typically a methyl group. In these embodiments, the carboxylic acid ester compound can be referred to as a methyl ester compound. Like the fluorinated compound, the polyoxaoxydiamine compounds subscripts a and c are typically each zero.

The carboxylate compound and the polyoxydiamine compound are typically 10:1 to 1:10; or 5:1 to 1:5; or 2:1 to 1: of the carboxylate compound to the polyoxydiamine compound; 2 molar ratio to react. The carboxylate compound and the polyoxydiamine compound are usually reacted at a ratio of 1:1 molar. However, the carboxylate compound or polyoxydiamine compound can be used in molar excess relative to other compounds.

The carboxylate compound is generally electrophilic and the polyoxydiamine compound is generally nucleophilic, and the reaction between the carboxylate compound and the polyoxydiamine compound can be referred to as the amidation of the carboxylate compound. The carboxylate compound and the polyoxydiamine compound can be reacted via various techniques to form a fluorinated compound. For example, the carboxylate compound and the polyoxydiamine compound can be selectively placed in a container in the presence of a solvent, a vehicle, and/or a catalyst. The solvent may be any solvent different from the carboxylate compound and the polyoxydiamine compound, which is capable of dissolving the carboxylate compound and/or the polyoxydiamine compound. The vehicle may differ from the solvent in that the vehicle only partially dissolves or does not dissolve the fluorinated compound and/or the polyfunctional acrylate. Typically, a vehicle is used and one of the vehicles A specific example is 1,3-bistrifluoromethylbenzene.

The vessel is typically heated to a high temperature, such as 50 to 150 degrees Celsius (° C.), or 75 to 125 degrees Celsius (° C.), or 90 to 110 degrees Celsius (° C.). The vessel may be heated at elevated temperature for a period of time to effect a reaction between the carboxylate compound and the polyoxydiamine compound, for example, for 15 to 240 minutes, or 15 to 120 minutes, or 30 to 90 minutes.

The carboxylate compound and the polyoxydiamine compound are reacted according to the following reaction to form a fluorinated compound: R _f -COOR ¹ +RHN-(CH ₂ ) _a -SiR ¹ X-(OSiR ¹ X) _b -(CH _{2 c -} Y → R _f -CONR-(CH ₂ ) _a -SiR ¹ X-(OSiR ¹ X) _b -(CH ₂ ) _c -Y.

Those skilled in the art will readily understand how to modify a polyoxydiamine compound based on the desired structure of the resulting fluorinated compound. For example, X can be a different substituent as described above, and those skilled in the art understand how to modify or select an appropriate polyoxydiamine compound to form the desired fluorinated compound.

The progress of the reaction to form a fluorinated compound is monitored via various techniques, such as spectroscopy, such as infrared (IR) spectroscopy.

Fluorinated compounds can be used in a variety of compositions, end uses, and/or applications. Because the fluorinated compound includes at least one amine-containing group, the fluorinated compound can be said to be reactive because the amine-containing group has reactivity with certain functional groups. The fluorinated compound can be used as a discrete component, placed in a solvent or vehicle to form a composition, combined with one or more other components to form a composition, reacted with another compound, and the like. Alternatively, the fluorinated compound can be used in the surface treatment of various substrates, such as ceramic, glass or stone, discretely or in the form of a composition. Additionally, the fluorinated compound can be used in coating compositions such as coatings, or to modify other polymers.

The invention further provides fluorinated polymers. Fluorinated polymers are formed from fluorinated compounds. The fluorinated polymer comprises the reaction product of a fluorinated compound and a Michael addition reaction of a polyfunctional acrylate. The mic addition reaction is known in the art and involves nucleophilic addition. More specifically, the amine-containing group of the fluorinated compound reacts with the acrylate functional group of the polyfunctional acrylate via a megaaddition reaction to form a fluorinated polymer.

By polyfunctional acrylate, "polyfunctional" means that the polyfunctional acrylate is at least difunctional, that is, has two or more acrylate functional groups. In certain embodiments, the polyfunctional acrylate has at least 3, or at least 4, or at least 5, or at least 6, or at least 7, or at least 8, or at least 9, or at least 10 acrylic Ester functional group. Higher functionality may also be suitable, such as a tetrafunctional acrylate. The polyfunctional acrylates can be monomeric, oligomeric or polymeric in nature and can comprise combinations thereof. For example, the polyfunctional acrylate can comprise a combination of a monomeric polyfunctional acrylate and an oligomeric polyfunctional acrylate. The polyfunctional acrylate can be a combination of linear, branched or linear and branched polyfunctional acrylates.

The polyfunctional acrylate can be organic or polyoxyl. When the polyfunctional acrylate is an organic system, the polyfunctional acrylate comprises a carbon-based skeleton or chain, optionally having a hetero atom (for example, O) therein. Alternatively, when the polyfunctional acrylate is polyoxo-based, the polyfunctional acrylate comprises a main chain or chain based on a decane, the main chain or chain comprising a decane (Si-O) -Si) key. The polyfunctional acrylate may comprise a carbon-based chain and a decyl-based chain, such as a polyfunctional acrylate formed by hydrogenation of a hydrazine, in which case the polyfunctional acrylate is due to a decane bond therein. Existence and still referred to as polyoxo-based. In certain embodiments, when the polyfunctional acrylate is organic, the polyfunctional acrylate does not contain any The siloxane chain, or, does not contain any ruthenium atoms. Typically, the polyfunctional acrylate is organic.

Specific examples of polyfunctional acrylates suitable for reaction with fluorinated compounds to form fluorinated polymers include: difunctional acrylate monomers such as 1,6-hexanediol diacrylate, 1,4-butane Alcohol diacrylate, ethylene glycol diacrylate, diethylene glycol diacrylate, tetraethylene glycol diacrylate, tripropylene glycol diacrylate, neopentyl glycol diacrylate, 1,4-butanediol dimethyl Acrylate, poly(butylene glycol) diacrylate, tetraethylene glycol dimethacrylate, 1,3-butylene glycol diacrylate, triethylene glycol diacrylate, triisopropyl glycol diacrylate, polyethylene Alcohol diacrylate and bisphenol A dimethacrylate; trifunctional acrylate monomer such as trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, pentaerythritol monohydroxy triacrylate Ester and trimethylolpropane triethoxy triacrylate; tetrafunctional acrylate monomer such as neopentyl alcohol tetraacrylate and bis(trimethylolpropane) tetraacrylate; pentafunctional monomer or advanced Functional monomers such as dipentaerythritol hexaacrylate and new Tetrahydric (monohydroxy)pentaacrylate; bisphenol A epoxy diacrylate; hexafunctional aromatic urethane acrylate, aliphatic urethane diacrylate, and acrylate of tetrafunctional polyester acrylate Oligomer.

The polyfunctional acrylate may comprise a single polyfunctional acrylate or any combination of two or more polyfunctional acrylates. In certain embodiments, the polyfunctional acrylate comprises a pentafunctional acrylate or a higher polyfunctional acrylate, such as any polyfunctional acrylate from a pentafunctional acrylate to a doc-functional acrylate, which can be modified to be curable The curing of the composition. For example, in certain embodiments, the polyfunctional acrylate comprises at least 30 weight percent, or at least 50 weight percent, or at least 75 weight percent, or at least 80 weight percent, based on the total weight of the multifunctional acrylate. Amount of penta-functional acrylate or higher polyfunctional acrylate. Typically, the polyfunctional acrylate does not contain any fluorine atoms, such as fluorine. Replace the group.

When a fluorinated compound is used to form a fluorinated polymer, the fluorinated polymer can be selectively formed in the same vessel as the fluorinated compound. For example, when a carboxylate compound and a polyoxydiamine compound are reacted to form a fluorinated compound, the polyfunctional acrylate can be placed in a container to react with the fluorinated compound and form a fluorinated polymer. The polyfunctional acrylate can be placed in the container before, during or after the reaction between the carboxylate compound and the polyoxydiamine compound. Alternatively, if any residual amount of the carboxylic acid ester compound and/or polyoxymethylene diamine compound is present in the container, the fluorinated compound can be subjected to separation or purification. Alternatively, the fluorinated compound can be prepared and subsequently stored or shipped to a different container or geographic location prior to reacting with the polyfunctional acrylate to form a fluorinated polymer.

Typically, one acrylate functional group of one molecule of the polyfunctional acrylate reacts with an amine-containing group of one molecule of the fluorinated compound. In certain embodiments, only one of the one molecule of the fluorinated compound contains an amine group. Typically, the amine-containing group is terminal such that the resulting fluorinated polymer is linear. However, the amine-containing group can be a side chain in the fluorinated compound such that the fluorinated polymer is branched. Further, the fluorinated compound may have two or more amine-containing groups. In such embodiments, each amine-containing group of the fluorinated compound can be reacted with an acrylate functional group of the polyfunctional acrylate (and optionally, each amine-containing group of the fluorinated compound can be varied The acrylate functional group of the functional acrylate molecule reacts).

The molar ratio of the fluorinated compound and the polyfunctional acrylate can vary. For example, when a fluorine compound includes but only one amine group, a mole of a fluorine-containing group can be reacted with a mole of a polyfunctional acrylate. However, since the polyfunctional acrylate includes two or more acrylate functional groups, the two molar fluorine compound can be combined with one mole of polyfunctional C. The enoate reaction. Additionally, when the fluorinated compound includes two or more amine-containing groups, one mole of the fluorinated compound can react with more than one mole of the polyfunctional acrylate. Fluorine compounds and polyfunctional acrylates typically have a molar ratio of a fluorine compound to a polyfunctional acrylate of from 10:1 to 1:10; or from 5:1 to 1:5; or from 2:1 to 1:2. .

The methine addition reaction between the fluorinated compound and the polyfunctional acrylate can be carried out selectively in the presence of a solvent, a vehicle and/or a catalyst. Typically, the reaction is carried out in the absence of a solvent or vehicle, i.e., neat. The solvent may be any solvent other than the fluorinated compound and the polyfunctional acrylate, which is capable of dissolving the fluorinated compound and/or the polyfunctional acrylate. The vehicle may differ from the solvent in that the vehicle only partially dissolves or does not dissolve the fluorinated compound and/or the polyfunctional acrylate.

Generally, no catalyst is required to initiate the mic addition reaction between the fluorinated compound and the polyfunctional acrylate. However, if desired, a catalyst can be utilized to initiate and/or accelerate the Michael addition reaction between the fluorinated compound and the polyfunctional acrylate. Suitable catalysts include bases of conjugate acids. Typically, the conjugate acid and its corresponding base are organic. Specific examples of such bases include 1,4-dihydropyridine, methyldiphenylphosphino, methyldi-p-tolylphosphorane, 2-allyl-N-alkylimidazoline, tetra-tert-butyl Ammonium hydroxide, DBU (1,8-diazabicyclo[5.4.0]undec-7-ene) and DBN (1,5-diazabicyclo[4.3.0]non-5-ene), Potassium methoxide, sodium methoxide, sodium hydroxide and combinations thereof. If a catalyst is used, the catalyst is typically greater than 0 to 2.0 weight percent, or 0.05 to 1.0 weight percent, or from 0.1 to 1.0 weight percent, based on the total weight of the fluorinated compound and the polyfunctional acrylate. The concentration is utilized.

For the mic addition reaction between the fluorinated compound and the polyfunctional acrylate, the container is typically heated to a high temperature, such as 25 to 100 ° C, or 25 to 75 ° C, or 40 to 60 ° C. The vessel can be heated at elevated temperatures for a period of time to effect a mic addition reaction between the fluorinated compound and the polyfunctional acrylate, such as heating for 15 to 240 minutes, or 15 to 120 minutes, or 30 to 90 minutes.

For illustrative purposes only, the following is a specific example of the mechanism of the mic addition reaction between a fluorinated compound and a polyfunctional acrylate: In the above McAddition reaction mechanism, the PFPE segment corresponds to the R _f group described above. In addition, the definition of R above is limited to this schematic only for the purpose of clarity.

The process of forming a fluorinated polymer by monitoring the McAddition reaction via various techniques, such as spectroscopy, such as infrared (IR) spectroscopy, is monitored. Fluorinated polymers differ from fluorinated compounds due to their acrylate functionality and increased molecular weight. In addition, fluorinated polymers typically do not have There are any residual amine groups. The fluorinated polymer typically includes at least one acrylate functional group such that the fluorinated polymer itself can crosslink or undergo further reaction with a compound or functional group reactive with the acrylate functional group.

Fluorinated polymers can be used in a variety of compositions, end uses, and/or applications. The fluorinated polymer can be used as a discrete component, placed in a solvent or vehicle to form a composition, combined with one or more other components to form a composition, reacted with another compound, and the like. Alternatively, the fluorinated polymer can be used in the surface treatment of various substrates, such as ceramic, glass or stone, discretely or in the form of a composition. Additionally, fluorinated polymers can be used in coating compositions such as coatings, or to modify other polymers.

The invention further provides a curable composition. The curable composition comprises a fluorinated polymer and a polyfunctional acrylate.

The polyfunctional acrylate of the curable composition can be the same or different than the polyfunctional acrylate that reacts with the fluorinated compound to form a fluorinated polymer. Specific examples of suitable polyfunctional acrylates are described above. The polyfunctional acrylate can be used in the mic addition reaction in a molar excess compared to the fluorinated compound such that the curable composition can be formed in situ in the container upon formation of the fluorinated polymer. Typically, another amount of polyfunctional acrylate is combined with the fluorinated polymer to form a curable composition. Any by-product or any residual amount of polyfunctional acrylate and/or fluorinated compound in the propylene addition reaction between the fluorinated polymer and the polyfunctional acrylate and fluorinated compound prior to the preparation of the curable composition Separate or otherwise separate.

In these or other embodiments, the curable composition can further comprise a reinforcing filler. The reinforcing filler is used to provide increased hardness and scratch resistance to the cured product formed from the curable composition. The reinforcing filler usually contains cerium oxide. Cerium dioxide can be cerium oxide at any time. For example, cerium oxide may be fuming cerium oxide, precipitated cerium oxide, colloidal silica, or the like. Typically, the reinforcing filler comprises a phthalic acid gel.

As is understood in the art, the phthalic acid gel comprises a mixture or suspension of cerium oxide (i.e., cerium oxide particles) in a vehicle. The vehicle can be referred to as a dispersion medium. The cerium oxide particles of citric acid gum are typically amorphous and non-porous.

To remove the vehicle from the curable composition (and citric acid), the phthalic acid vehicle typically has a moderately low boiling temperature. For example, the vehicle typically has a boiling temperature of 30 to 200 ° C, or 40 to 150 ° C at atmospheric pressure (i.e., 1 atm).

Suitable vehicles for phthalic acid gels include polar and non-polar vehicles. Specific examples of such vehicles include water; alcohols such as methanol, ethanol, isopropanol, n-butanol and 2-methylpropanol; glycerides such as glyceryl triacetate (triacetin) Triacetin)), glyceryl tripropionate (tripropionin) and glyceryl tributyrate (tributyrin); polyglycols such as poly Ethylene glycol and polypropylene glycol; cyanidin, such as methyl cyproterone, ethyl cyanidin and butyl cyanidin; dimethyl acetamide; aromatic compounds such as toluene and xylene; acetate , such as methyl acetate; ethyl acetate; butyl acetate; ketones such as methyl isobutyl ketone; acetic acid; and acetone. In a particular embodiment, the phthalic acid gum vehicle is selected from the group consisting of water and alcohol. The citric acid gel may be referred to as a phthalic acid gum dispersion. Two or more different vehicles may be utilized, although such agents are generally compatible with each other, which renders the phthalic acid gum homogeneous. The phthalic acid gum vehicle is typically present in the citric acid gel at a concentration of, for example, 10 to 70 weight percent based on the total weight of the citric acid gum.

The cerium oxide particles of citric acid gum typically have an average particle size of less than 200 nanometers (nm), such as from 1 to 100 nanometers (nm), or from 1 to 50 nanometers (nm).

The cerium oxide particles of the citrate gel may be pure cerium oxide or may contain a nominal amount of impurities such as Al ₂ O ₃ , ZnO and/or cations such as Na ⁺ , K ⁺ , Ca ⁺⁺ , Mg ^{++ ,} etc. .

The citric acid gel can be selectively surface treated, for example, surface treated with a filler treating agent. The phthalic acid gel may be surface treated prior to incorporation into the curable composition or may be surface treated in situ.

The amount of filler treating agent used to treat the phthalic acid gel can vary depending on various factors such as whether the phthalic acid gel is treated in situ with a filler treating agent or pretreated prior to incorporation into the curable composition.

The filler treating agent may comprise decane, such as an alkoxy decane; an alkoxy-functional oligooxane; a cyclic polyorganooxane; a hydroxy-functional oligooxyalkylene such as dimethyloxane; methylphenyl hydrazine; Oxystane; stearate; or fatty acid.

Examples of the alkoxydecane suitable for the filler treating agent include: hexyltrimethoxydecane, octyltriethoxydecane, decyltrimethoxydecane, dodecyltrimethoxydecane, and tetradecyltrimethoxy Basearane, phenyltrimethoxydecane, phenylethyltrimethoxydecane, octadecyltrimethoxydecane, octadecyltriethoxydecane, and combinations thereof.

Alternatively, the alkoxydecane may comprise an ethylenically unsaturated group. The ethylenically unsaturated group may include a carbon-carbon double bond, a carbon-carbon triple bond, or a combination thereof. In these embodiments, the alkoxydecane can be represented by the formula R ³ _d ZSi(OR ⁴ ) _3-d . In the formula, R ³ is a substituted or unsubstituted monovalent hydrocarbon group which does not contain an aliphatic unsaturated bond. Specific examples thereof include an alkyl group, an aryl group, and a fluoroalkyl group. R ⁴ is an alkyl group which typically has from 1 to 10 carbon atoms. Z is a monovalent organic group having an aliphatic unsaturated bond. Specific examples of Z include an organic group containing a propenyl group such as a methacryloxy group, an acryloxy group, a 3-(methacryloxy)propyl group, and a 3-(acryloxy)oxy group; Alkenyl groups such as vinyl, hexenyl and allyl; styryl and vinyl ether groups. The subscript d is 0 or 1.

Specific examples of the alkoxydecane having an ethylenically unsaturated group include 3-(methacryloxy)propyltrimethoxydecane, 3-(methacryloxy)propyltriethoxydecane. , 3-(methacryloxy)propylmethyldimethoxydecane, 3-(acryloxy)propyltrimethoxydecane, vinyltrimethoxydecane, vinyltriethoxydecane , methyl vinyl dimethoxy decane and allyl triethoxy decane.

The alkoxy-functional oligooxane can be used either as a filler treating agent. Alkoxy-functional oligooxoxanes and methods for their preparation are known in the art. For example, suitable alkoxy-functional oligooxanes include such oligooxanes of the formula (R ⁵ O) _c Si(OSiR ⁵ ₂ R ₆ ) _(4-c) . In this formula, the subscript e is 1, 2 or 3, or 3. Each R ^{5 is} independently selected from saturated and unsaturated hydrocarbon groups having from 1 to 10 carbon atoms. Each R ⁶ is a saturated or unsaturated hydrocarbon group.

Alternatively, the indane alkane can be used as a filler treating agent either discretely or in combination with, for example, alkoxydecane.

Alternatively, the filler treating agent may be an organic cerium compound. Examples of organic hydrazine compounds include, but are not limited to, organochlorosilanes such as methyltrichloromethane, dimethyldichlorodecane, and trimethylchlorosilane; organic oxiranes such as hydroxy-terminated dimethyl methoxyoxane Oligomers, hexamethyldioxane and tetramethyldivinyldioxane; organodazepines such as hexamethyldioxane and hexamethylcyclotriazane; and organoalkoxy Alkane, such as methyltrimethoxydecane, vinyltrimethoxydecane, vinyltriethoxydecane, 3-glycidoxypropyltrimethoxydecane, and 3-methylpropenyloxypropyl Trimethoxydecane. Examples of stearates include calcium stearate. Examples of fatty acids include stearic acid, oleic acid, palmitic acid, tallow, coconut oil, and combinations thereof.

A residual amount of filler treating agent may be present in the curable composition, for example as Discrete component of citrate gel separation.

Alternatively, the cerium oxide particles of the citrate gel need not be surface treated by the treating agent. In such embodiments, the citrate gel may be referred to as an unmodified citric acid gel. Unmodified citric acid gums are typically in the form of acidic or basic dispersions.

If desired, another filler may be present in the curable composition, such as a filler other than phthalic acid gum. Examples thereof include alumina, calcium carbonate (e.g., fuming, melting, grinding, and/or precipitation), diatomaceous earth, talc, zinc oxide, chopped short fibers such as chopped KEVLAR®, onyx, cerium oxide, zinc oxide, Aluminum nitride, boron nitride, tantalum carbide, tungsten carbide; and combinations thereof.

The curable composition typically further comprises an alcohol-containing vehicle. The alcohol-containing vehicle may comprise, consist essentially of, or consist of an alcohol. The alcohol-containing vehicle is used to disperse the components of the curable composition. In certain embodiments, the alcohol-containing vehicle dissolves the components of the curable composition, in which case the alcohol-containing vehicle can be referred to as an alcohol-containing solvent.

Specific examples of alcohols suitable for use in alcohol-containing vehicles include methanol, ethanol, isopropanol, butanol, isobutanol, ethylene glycol, diethylene glycol, triethylene glycol, ethylene glycol monomethyl ether, diethyl Glycol monomethyl ether, triethylene glycol monomethyl ether, and combinations thereof. When the alcohol-containing vehicle comprises or consists essentially of an alcohol, the alcohol-containing vehicle may further comprise another organic vehicle. Specific examples thereof include acetone, methyl ethyl ketone, methyl isobutyl ketone or the like ketone; toluene, xylene or the like aromatic hydrocarbon; hexane, octane, heptane or the like aliphatic hydrocarbon; chloroform , dichloromethane, trichloroethylene, carbon tetrachloride or similar organic chlorine-containing solvent; ethyl acetate, butyl acetate, isobutyl acetate or similar fatty acid esters. When the alcohol-containing vehicle comprises an additional organic vehicle, the alcohol-containing vehicle typically comprises from 10 to 90 weight percent, or from 30 to 70 weight percent, based on the total weight of the alcohol-containing vehicle, of alcohol The balance of the vehicle is an additional organic vehicle.

The curable composition may further comprise water as needed. If water is used, it is present in the curable composition for hydrolysis of the citric acid gum. For example, as is known in the art, the cerium oxide particles of ceric acid gel may include sterol groups at the surface of the cerium oxide particles. Water can be used as a vehicle for phthalic acid gels, in which case water is not required to be a discrete component of the curable composition. In addition, if the phthalic acid gel has been surface treated, water is similarly unfavorable.

In various embodiments, the curable composition may additionally comprise a photopolymerization initiator. Photopolymerization initiators are most commonly used if the curable composition is cured by irradiation with electromagnetic radiation. The photopolymerization initiator may be selected from known compounds capable of generating a radical under irradiation with electromagnetic radiation, such as an organic peroxide, a carbonyl compound, an organic sulfur compound, and/or an azo compound.

Specific examples of suitable photopolymerization initiators include acetophenone, ethyl phenyl ketone, benzophenone, xanthol, fluorine, benzaldehyde, hydrazine, triphenylamine, 4-methylacetophenone, 3-pentylacetophenone, 4-methoxyacetophenone, 3-bromoacetophenone, 4-allylacetophenone, p-diethylphenylbenzene, 3-methoxydiphenyl ketone, 4-methyldiphenyl ketone, 4-chlorodiphenyl ketone, 4,4-dimethoxydiphenyl ketone, 4-chloro-4-benzyldiphenyl ketone, 3-chloro Ketone, 3,9-dichloro Ketone, 3-chloro-8-fluorenyl Ketone, benzoin, benzoin methyl ether, benzoin butyl ether, bis(4-dimethylaminophenyl) ketone, benzyl methoxy ketal, 2-chlorothio Ketone, diethylacetophenone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl[4-(methylthio)phenyl]2- Lolinyl-1-propanone, 2,2-dimethoxy-2-phenylacetophenone, diethoxyacetophenone, and combinations thereof.

If a photopolymerization initiator is used, it is typically present in the curable composition in an amount of from 1 to 30 parts by weight, or from 1 to 20 parts by weight, based on 100 parts by weight of the polyfunctional acrylate.

The curable composition may further comprise a decane compound, if necessary. Its instance Including tetraalkoxydecanes such as tetramethoxynonane, tetraethoxydecane and tetraisopropoxydecane; and alkyl alkoxydecanes such as methyltrimethoxydecane, methyltriethoxydecane Methyl triisopropoxy decane, ethyl trimethoxy decane, ethyl triethoxy decane and ethyl triethoxy decane. The decane compound can be used as a discrete component or, as another example, for forming a sesquisestam in a curable composition.

Additional examples of additives that may be present in the curable composition include antioxidants; thickeners; surfactants such as leveling agents, defoamers, precipitation inhibitors, dispersants, antistatic agents, and anti-fog additives; Absorbent; colorant, such as various pigments and dyes; dibutylhydroxytoluene (BHT); (PTZ); organopolyoxyalkylene; and combinations thereof.

The curable composition can be prepared by various methods involving combinations of various components of the curable composition. In certain embodiments, the phthalic acid gel is surface treated prior to incorporation into the curable composition. The components may be heated individually or collectively before, during or after the preparation of the curable composition.

The curable composition can be used in a variety of end uses and applications. Most typically, the curable composition is used to form a cured product. The cured product can be in the form of fibers, coatings, layers, films, composites, articles, and the like.

The invention further provides a cured product formed from a curable composition, and a method of forming a cured product from the curable composition. The cured product and the method of forming the cured product are described together below.

A method of forming a cured product comprises applying a curable composition to a substrate. The method further includes curing the curable composition on the substrate to form a cured product on the substrate. For example, a method of forming a cured product comprises applying a curable composition On the substrate, a wet layer is formed on the substrate. The method further comprises curing the wet layer to form a cured product.

The substrate is not limited and can be any substrate on which the cured product is preferably formed. For example, the substrate can include electronic articles, optical articles, consumer appliances and components, automotive body and components, polymeric articles, and the like. The substrate can have any shape or configuration.

Examples of electronic articles typically include electronic objects having electronic displays such as liquid crystal displays (LCDs), light emitting diode (LED) displays, organic light emitting diode (OLED) displays, plasma displays, and the like. Wait. These electronic displays are commonly used in a variety of electronic devices, such as computer monitors, televisions, smart phones, global positioning system (GPS) units, music players, remote controls, handheld video games, portable readers, car displays. Panels and more.

As described above, the substrate can also be a metal object such as a consumer appliance and component. Exemplary articles include dishwashers, electric stoves, microwave ovens, refrigerators, freezers, and the like, which typically have a shiny metallic appearance such as stainless steel, brushed nickel, aluminum, and the like.

Alternatively, the substrate can be a vehicle body or component, such as an automobile body or component. For example, the curable composition can be applied directly to the top coat of an automobile body to form the layer, thereby imparting a bright appearance to the car body, which is aesthetically pleasing and resistant to stains such as dirt, etc. And the pollution from fingerprints.

Examples of suitable optical articles include inorganic materials such as glass plates, glass plates containing inorganic layers, ceramics, and the like. Additional examples of suitable optical articles include organic materials such as transparent plastic materials and transparent plastics comprising inorganic layers. Specific examples of optical objects include anti-reflection films, optical filters, optical lenses, spectacle lenses, beam splitters, xenon, reflection Mirror and so on.

Specific examples of organic materials and/or polymer articles include polyolefins (e.g., polyethylene, polypropylene, etc.), polycycloolefins, polyesters (e.g., polyethylene terephthalate, polyethylene naphthalate, etc.) Etc.), polyamines (eg nylon 6, nylon 66, etc.), polystyrene, polyvinyl chloride, polyimine, polyvinyl alcohol, vinyl vinyl alcohol, acrylics (eg polymethacrylic acid) Methyl ester), cellulose (for example, triethyl decyl cellulose, diethyl acetyl cellulose, cellophane, etc.), or a copolymer of such organic polymers. It should be understood that such materials can be used in ophthalmic components. Non-limiting examples of ophthalmic elements include corrective and non-corrective lenses, including single or multi-optical lenses, such as bifocal, trifocal, and progressive lenses, which may be segmented or non-segmented; Other components that protect or enhance vision, including but not limited to contact lenses, intraocular lenses, magnifiers, and goggles or goggles. Preferred materials for ophthalmic elements comprise one or more polymers selected from the group consisting of polycarbonates, polyamines, polyimines, polyfluorenes, polyethylene terephthalates, and polycarbonate copolymers, poly Olefins, especially polypyrene, diethylene glycol-bis(allyl carbonate) polymers - referred to as CR39- and copolymers, (meth)acrylic polymers and copolymers, especially derived from double (meth)acrylic acid polymers and copolymers of phenol A, thio (meth)acrylic acid polymers and copolymers, ethyl urethane and thioethyl ester polymers and copolymers, epoxy polymers and copolymers And episulfide polymers and copolymers.

The substrate can comprise any of the materials described above, but other than the particular articles described herein. For example, the substrate can comprise a metal or alloy that is not part of a consumer appliance or vehicle body.

In addition to the articles/substrates described above, the curable composition can be applied to other substrates, such as window components for automobiles or aircraft, thus providing advanced functionality.

Alternatively, the substrate can include cement, stone, paper, cardboard, ceramics, and the like.

Alternatively or additionally, the substrate can comprise an anti-reflective coating. In these embodiments, the anti-reflective coating can include one or more layers of material disposed on the underlying substrate. Antireflective coatings typically have a lower index of refraction than underlying substrates. The anti-reflective coating can be multiple layers. The multilayer anti-reflective coating comprises two or more layers of dielectric material on the underlying substrate, at least one of which has a refractive index that is higher than the refractive index of the underlying substrate. Such multilayer anti-reflective coatings are often referred to as anti-reflective film stacks.

The anti-reflective coating can be formed from a variety of materials. In certain embodiments, the anti-reflective coating comprises a thin metal oxide film, such as a thin sputter coated metal oxide film. Alternatively, the thin metal oxide film can be formed by thermal evaporation. As used herein, "metal oxide" includes oxides of single metals (including metalloids) as well as oxides of metal alloys. An example of a metal oxide is cerium oxide, which can deplete oxygen (i.e., where the amount of oxygen in the oxide is less than a stoichiometric amount). Further suitable metal oxides include oxides of the following and mixtures thereof: tin, titanium, bismuth, zinc, zirconium, hafnium, tantalum, aluminum, lanthanum, tungsten, cerium, indium. Specific examples include SiO ₂ , SnO ₂ , TiO ₂ , Nb ₂ O ₅ , ZnO, ZrO ₂ , Ta ₂ O ₅ , Y ₂ O ₃ , Al ₂ O ₃ , CeO ₂ , WO ₃ , Bi ₂ O, In ₂ O ₃ and ITO (indium tin oxide), as well as combinations and alternating layers thereof.

If desired, the underlying substrate can have a primed surface prior to deposition of the antireflective coating. For example, the coated substrate can be formed by coating a chemical undercoat such as an acrylic layer, or chemical etching, electron beam irradiation, corona treatment, plasma etching, or co-extrusion from an adhesion promoting layer. These primed substrates are commercially available.

The method by which the curable composition can be applied to a substrate can vary. For example, in certain embodiments, the step of applying the curable composition to the substrate is coated with a wet coating method. Specific examples of wet coating methods suitable for use in the process include dip coating, spin coating, shower coating, spray coating, roll coating, gravure coating, sputtering, slot coating, and combinations thereof. The alcohol-containing vehicle, along with any other vehicle or solvent pre-set in the curable composition and the wet layer, can be removed from the wet layer via heat or other known methods.

The curable composition can be applied to the substrate to any thickness to provide the desired level of water repellency, oil repellency, soil repellency and soil repellency. In certain embodiments, the cured product may be referred to as a layer or film, although the cured product may have any shape or form other than that associated with the layer or film. In these embodiments, the cured product has a thickness greater than 0 to 20 micrometers (μm), or greater than 0 to 10 micrometers (μm), or greater than 0 to 5 micrometers (μm). In certain embodiments, the cured product has a thickness of at least 15 angstroms, or at least 20 angstroms, or at least 30 angstroms, and in these embodiments, the upper limit is 20 micrometers (μm).

The curable composition and the wet layer formed thereby can be rapidly cured by irradiation with active energy rays (ie, high energy rays). Active energy rays can include ultraviolet light, electron beams or other electromagnetic waves or radiation. From the standpoint of low cost and high stability, the use of ultraviolet rays is preferred. Sources of ultraviolet radiation may include high pressure mercury lamps, medium pressure mercury lamps, Xe-Hg lamps or deep UV lamps.

The step of curing the wet layer typically comprises exposing the wet layer to radiation at a dose sufficient to cure at least a portion of the wet layer, or the entirety. The dose of radiation used to cure the wet layer is typically from 10 to 8000 millijoules per square centimeter (mJ/cm ² ). In certain embodiments, heating is used in conjunction with illumination to cure the wet layer. For example, the wet layer can be heated before, during, and/or after the wet layer is irradiated with active energy rays. While the active energy ray typically initiates curing of the curable composition, residual amounts of the alcohol-containing vehicle or any other vehicle and/or solvent may be present in the wet layer, which may be volatilized by heating and driven off. Typical heating temperatures range from 50 to 200 °C. The cured wet layer provides a cured product.

The cured product has excellent physical properties and is suitable for use as a protective coating on a variety of substrates. For example, the cured product has excellent (i.e., high) hardness, durability, adhesion to the substrate, and resistance to stains, contamination, and scratches. In certain embodiments, the cured product has at least 90 degrees (°), or at least 100 degrees (°), or at least 105 degrees (°), or at least 108 degrees (°), or at least 110 degrees (°). The water contact angle. In these embodiments, the upper limit is typically 120°. The water contact angle of the cured product is typically within this range, even after subjecting the cured product to an abrasion test, which illustrates the excellent durability of the cured product. For example, for a cured product with less durability, the water contact angle decreases after abrasion, which generally indicates that the cured product has been at least partially degraded.

In these embodiments, the cured product typically also has a sliding (dynamic) coefficient of friction (μ) greater than 0 to less than 0.2, or greater than 0 to less than 0.15, or greater than 0 to less than 0.125, or greater than 0 to less than 0.10. ). Although the coefficient of friction is unitless, it is often expressed in μ.

For example, a sliding (dynamic) coefficient of friction can be obtained by placing an object having a defined surface area and mass on the solidified product with a selected material (eg, a standard legal paper size paper). Measured between the cured product. Next, a force perpendicular to gravity is applied to slid the object across the solidified product by a predetermined distance, which is capable of calculating the coefficient of sliding friction of the cured product.

In some embodiments, the invention is in any of the following numbered aspects.

Aspect 1. A fluorinated compound having the formula (1): R _f -CONR-(CH ₂ ) _a -SiR ¹ X-(OSiR ¹ X) _b -(CH ₂ ) _c -Y(1); wherein R _f is a fluorine-substituted group; R is H or a substituted or unsubstituted hydrocarbon group; each R ¹ is an independently selected substituted or unsubstituted hydrocarbon group; each X is independently R ¹ or an amine group; Y Is a terminal group selected from R and X; subscripts a and c are each independently selected from 0 and an integer from 1 to 10; and subscript b is an integer from 2 to 20; however, the fluorinated compound includes at least one An amine group specified by X or Y.

Aspect 2. A fluorinated compound according to aspect 1, wherein R is H such that the fluorinated compound has the formula (2): R _f -CONH-(CH ₂ ) _a -SiR ¹ X-(OSiR ¹ X) _b -(CH ₂ ) _c -Y(2); wherein R _f , R ¹ , X, Y and subscripts a, b and c are as defined in Aspect 1.

Aspect 3. A fluorinated compound according to aspect 2, wherein X is R ¹ and Y is an amine-containing group such that the fluorinated compound has the formula (3): R _f -CONH-(CH ₂ ) _a -SiR ¹ ₂ - ( OSiR ¹ ₂ ) _b -(CH ₂ ) _c -NHR(3); wherein R _f , R, R ¹ and subscripts a, b and c are as defined in Aspect 1.

Aspect 4. A fluorinated compound according to aspect 3, wherein the subscripts a and c are each 0 such that the fluorinated compound has the formula (4): R _f -CONH-SiR ¹ ₂ -(OSiR ¹ ₂ ) _b -NHR (4 Wherein R _f , R, R ¹ and subscript b are as defined in Aspect 1.

Aspect 5. A fluorinated compound according to any of the preceding aspects, wherein R _f :(i) is partially fluorinated; (ii) comprises a perfluoropolyether segment; or (iii) has both (i) and (ii) Both.

Aspect 6. A fluorinated compound according to aspect 5, wherein R _f comprises the perfluoropolyether segment, the perfluoropolyether segment comprising a moiety of the formula (5): (C ₃ F ₆ O) _x -(C ₂ F ₄ O _y -(CF ₂ ) _z -(5); wherein the subscripts x, y and z are each independently selected from 0 and an integer from 1 to 40, except that x, y and z are not 0 at the same time.

Aspect 7. A fluorinated polymer comprising the reaction product of a fluorinated compound of any of the foregoing aspects and a methine addition reaction of a polyfunctional acrylate.

Aspect 8. A curable composition comprising a fluorinated polymer such as aspect 7 And polyfunctional acrylates.

Aspect 9. A curable composition according to aspect 8, which further comprises a reinforcing filler.

Aspect 10. A cured product formed from the curable composition of any of the aspects 8 to 9.

Aspect 11. A cured product of the aspect 10, which comprises a film having a thickness greater than 0 to 20 micrometers (μm).

Aspect 12. A cured product of any of the aspects 10 and 11 which is disposed on a substrate.

Aspect 13. A cured product of any of the aspects 10 to 12 which has at least 100. The water contact angle.

Aspect 14. A method of forming a cured product, the method comprising: applying a curable composition according to any of the aspects 8 to 9 to a substrate; and curing the curable composition on the substrate so that The cured product is formed on the substrate.

It is to be understood that the scope of the appended claims is not limited to the particular embodiments of the invention, which are described in the scope of the appended claims. With regard to the Markush group in this specification for the specific features or aspects of the various embodiments, different, special and/or unexpected results may be obtained from each member of the respective Markusi group. And independent of all other Markusi members. The individual members of a Markusi group may be utilized individually or in combination, and sufficient support is provided for specific embodiments that fall within the scope of the appended claims.

In addition, any range and sub-ranges by which the various embodiments of the invention are described are independent of the scope of the accompanying claims and are to be construed as All ranges including the whole and/or some of the values are contemplated, even if such values are not explicitly described in this specification. It is readily recognized by those skilled in the art that the scope and sub-ranges are fully described and the various embodiments of the invention can be practiced, and such ranges and sub-ranges can be further described as related halved, Three equal parts, four equal parts, five equal parts, and so on. The following is only an example. A range of "0.1 to 0.9" can be further described as the lower third (ie 0.1 to 0.3), the middle third (ie 0.4 to 0.6) and the upper third (ie 0.7 to 0.9), which are individually and collectively within the scope of the accompanying claims, and which can be relied upon individually and/or collectively, and which are fully provided for the specific embodiments falling within the scope of the accompanying claims stand by. In addition, terms relating to defining or modifying a range, such as "at least", "greater than", "less than", "not exceeding", and the like, are understood to include such sub-ranges and/or upper or lower limits. As another example, a range of "at least 10" naturally includes at least a sub-range of 10 to 35, a sub-range of at least 10 to 25, a sub-range of 25 to 35, and the like, and may be individually and/or collectively Sub-scopes and full support for specific embodiments falling within the scope of the appended claims. Finally, the individual numbers falling within the scope of the disclosure are fully provided, and the specific embodiments that fall within the scope of the appended claims are fully supported. For example, a range of "from 1 to 9" includes various individual integers such as 3, and individual numbers including a decimal point (or fraction) such as 4.1, which can be relied upon and fall within the scope of the accompanying patent application. Specific embodiments provide sufficient support.

The following examples are intended to illustrate the invention and should not be construed as limiting the scope of the invention in any way.

Instance

Preparation Examples 1-3

In the preparation of Examples 1-3, a fluorinated compound according to the present invention was prepared.

Preparation Example 1:

A fluorinated compound is prepared by reacting a carboxylate compound and a polyoxydiamine compound. In particular, the carboxylate compound is commercially available from E. I. du Pont de Nemours and Company of DE Wilmington under the trade name Krytox® methyl ester (weight average molecular weight of about 2,000). The polyoxydiamine compound comprises 1,3-bis(3-aminopropyl)tetramethyldioxane.

In detail, 14.9 g of the polyoxydiamine compound and 20.0 g of 1,3-bistrifluoromethylbenzene were placed in a dry three-necked flask and heated to 100 °C. 20 g of the carboxylic acid ester compound in 20 g of 1,3-bistrifluoromethylbenzene was placed dropwise into the flask over a period of 1 hour. The contents of the flask were stirred at 100 ° C for an additional hour until the methyl ester group of the carboxylate compound was no longer detected via infrared (IR) spectroscopy. A reaction product comprising a fluorinated compound is obtained. After cooling to room temperature, 1,3-bistrifluoromethylbenzene is stripped from the reaction product, and the fluorinated compound is placed in 1,3-bistrifluoromethylbenzene at a concentration of 20 wt.%. This is called the final solution of Preparation Example 1.

Preparation Example 2:

A fluorinated compound is prepared by reacting a carboxylate compound and a polyoxydiamine compound. In particular, the carboxylate compound is commercially available from E. I. du Pont de Nemours and Company of DE Wilmington under the trade name Krytox® methyl ester (weight average molecular weight of about 2,000). The polyoxydiamine compound comprises an aminopropyl-terminated poly(dimethyl)oxirane (viscosity of 10-15 centistokes (cSt) at 25 ° C).

In detail, 50.4 g of the polyoxydiamine compound and 20.0 g of 1,3-bistrifluoromethylbenzene were placed in a dry three-necked flask and heated to 100 °C. 20 g of the carboxylic acid ester compound in 20 g of 1,3-bistrifluoromethylbenzene was placed dropwise into the flask over a period of 1 hour. The contents of the flask were stirred at 100 ° C for an additional hour until the methyl ester group of the carboxylate compound was no longer detected via infrared (IR) spectroscopy. A reaction product comprising a fluorinated compound is obtained. After cooling to room temperature, 1,3-bistrifluoromethylbenzene is stripped from the reaction product, and the fluorinated compound is placed in 1,3-bistrifluoromethylbenzene at a concentration of 20 wt.%. This is called the final solution of Preparation 2.

Preparation Example 3:

A fluorinated compound is prepared by reacting a carboxylate compound and a polyoxydiamine compound. In particular, the carboxylate compound is commercially available from E. I. du Pont de Nemours and Company of DE Wilmington under the trade name Krytox® methyl ester (weight average molecular weight of about 2,000). The polyoxydiamine compound comprises an aminopropyl-terminated poly(dimethyl)oxirane (viscosity at 25 ° C of 20-30 centistokes (cSt)).

In detail, 94.8 g of the polyoxydiamine compound and 20.0 g of 1,3-bistrifluoromethylbenzene were placed in a dry three-necked flask and heated to 100 °C. 20 g of the carboxylic acid ester compound in 20 g of 1,3-bistrifluoromethylbenzene was placed dropwise into the flask over a period of 1 hour. The contents of the flask were stirred at 100 ° C for an additional hour until the methyl ester group of the carboxylate compound was no longer detected via infrared (IR) spectroscopy. A reaction product comprising a fluorinated compound is obtained. After cooling to room temperature, 1,3-bistrifluoromethylbenzene is stripped from the reaction product, and the fluorinated compound is placed in 1,3-bistrifluoromethylbenzene at a concentration of 20 wt.%. This is called the final solution of Preparation 3.

Examples 1-3 and Comparative Example 1:

In Examples 1-3, fluorinated polymers were prepared from the fluorinated compounds of Preparation Examples 1-3, respectively. In particular, fluorinated polymers are prepared in situ in a curable composition. Comparative Example 1 illustrates a curable composition that does not include such a fluorinated polymer.

The following components were used for the curable compositions of Examples 1-3 and Comparative Example 1: the polyfunctional acrylate comprises dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate (1:1 molar ratio) a blend obtained from Nippon Kayaku Co., Ltd. of Tokyo, Japan under the trade name Kayarad dPHA; the reinforcing filler comprises a phthalic acid gel (30 wt.% SiO ₂ ) monodispersed in isopropanol, Houston, TX available from Nissan Chemical America Corporation of commercially available under the trade name ORGANOSILICASOL ^TM MEK-ST.

The photopolymerization initiator comprises 1-hydroxycyclohexyl phenyl ketone available from BASF Corporation of NJ Florham Park under the trade name Irgacure® 184.

The filler treating agent contains 3-methacryloxypropyltrimethoxydecane.

Example 1:

16.3 g of 2-butanone, 21.3 g of polyfunctional acrylate, 2 g of the final solution of Preparation Example 1, and 0.49 g of aminopropyl-terminated poly(dimethyl)oxime (viscosity at 25 ° C of 20) -30 cc (cSt)) was placed in a dry three-necked flask and heated at 50 ° C for 1 hour with stirring. A portion of the final solution was prepared in situ fluorinated compound of Example 1 in which the polyfunctional acrylate ä reaction of the fluorinated polymer to form in the flask. 5.3 g of the filler treatment agent, 53.3 g of the reinforcing filler, and 0.46 g of deionized water were placed in the flask while heating at 50 ° C for an additional hour with stirring. After cooling to room temperature, 2.0 g of a photopolymerization initiator was placed in a flask to obtain a curable composition.

Example 2:

16.3 g of 2-butanone, 21.3 g of polyfunctional acrylate, 2 g of the final solution of Preparation 2, and 0.49 g of aminopropyl-terminated poly(dimethyl)decane (viscosity at 25 ° C of 20) -30 cc (cSt)) was placed in a dry three-necked flask and heated at 50 ° C for 1 hour with stirring. The fluorinated compound in the final solution of Preparation Example 2 was reacted in situ with a portion of the polyfunctional acrylate to form a fluorinated polymer in the flask. 5.3 g of the filler treatment agent, 53.3 g of the reinforcing filler, and 0.46 g of deionized water were placed in the flask while heating at 50 ° C for an additional hour with stirring. After cooling to room temperature, 2.0 g of a photopolymerization initiator was placed in a flask to obtain a curable composition.

Example 3:

16.3 g of 2-butanone, 21.3 g of polyfunctional acrylate, 2 g of the final solution of Preparation 3 and 0.49 g of aminopropyl-terminated poly(dimethyl)decane (viscosity at 25 ° C of 20) -30 cc (cSt)) was placed in a dry three-necked flask and heated at 50 ° C for 1 hour with stirring. The fluorinated compound in the final solution of Preparation Example 3 was reacted in situ with a portion of the polyfunctional acrylate to form a fluorinated polymer in the flask. 5.3 g of the filler treatment agent, 53.3 g of the reinforcing filler, and 0.46 g of deionized water were placed in the flask while heating at 50 ° C for an additional hour with stirring. After cooling to room temperature, 2.0 g of a photopolymerization initiator was placed in a flask to obtain a curable composition.

Comparative Example 1:

16.3 g of 2-butanone, 21.3 g of polyfunctional acrylate, 5.3 g of filler treatment, 53.3 g of reinforcing filler and 0.46 g of deionized water were placed in a dry three-necked flask and heated at 50 ° C for 1 hour with stirring. . After cooling to room temperature, 2.0 g of a photopolymerization initiator was placed in a flask to obtain a curable composition. The curable composition of Comparative Example 1 did not include a fluorinated polymer formed by a mic addition reaction between a fluorinated compound and a polyfunctional acrylate, which is different from the curable composition of Examples 1-3.

Cured product:

The curable compositions of Examples 1-3 and Comparative Example 1 were passed through a syringe filter (polytetrafluoroethylene having glass microfibers; 30 mm (mm) diameter; 0.45 micrometer (μm) pore size; available from UK Little Chalfront GE Healthcare is available under the trade name Whatman®. A sample of the curable compositions of Examples 1-3 and Comparative Example 1 was applied to a polycarbonate substrate. Specifically, the sample of the curable composition was applied by spin coating using a spin coater (available from SÜSS MicroTec, CA Sunnvale) at 200 revolutions per minute (rpm) for 20 seconds and then 1,000 rpm for 30 seconds. The substrate is provided to provide a wet film on different substrates. The wet film was dried at 70 ° C for 10 minutes, and cured by UV irradiation at a dose of ² J/cm ² for a period of time sufficient to cure the wet film and obtain a cured product. The cured product is placed on the substrate in the form of a film.

The physical properties of the cured product formed from the curable compositions of Examples 1-3 and Comparative Example 1 were measured as described below.

Contact angle:

The static contact angle of water and hexadecane on each cured product was evaluated. Specifically, the static contact angles of water and hexadecane are measured via a VCA Optima XE goniometer available from AST Products, Inc. of MA Billerica. The measured water contact angle is based on the static contact angle of 2 [mu]L of droplets on each cured product. The contact angle of water is called WCA (water contact angle), and the contact angle of hexadecane is called HCA (hexadecane contact angle). WCA and HCA are degrees (°).

Pencil hardness:

The pencil hardness of each cured product was measured according to ASTM D3363-04 (2011) 32 entitled "Standard Test Method for Film Hardness by Pencil Test". As understood in the art, pencil hardness values are typically based on graphite grades ranging from 9H (hardest value) to 9B (softest value).

Cross Hatch Adhesion Test:

The cross-cutting adhesion test is based on ASTM D 3002 entitled "Evaluation of Coatings Applied to Plastics" and ASTM D 3359-09e2 entitled "Standard Test Methods for Measuring Adhesion by Tape Test", using a right angle cut (which is a cross cut) Line) is performed on the underlying substrate in the cured product. The cutting edge and the loss of cracking and adhesion are checked based on the following ASTM standards: ASTM Class 5B: The cutting edge is completely smooth, and the square formed by the cross-line test is in the form of a grid. Detachment of the substrate; ASTM Class 4B: flaking of the flakes at the intersection of the cured product; the affected cross-cut area is significantly no more than 5 area%; ASTM Class 3B: the cured product flakes along the cutting edge and at the intersection tangent; The cross-cut area affected is significantly greater than 5 area%, but is significantly no more than 15 area%; ASTM Class 2B: The cured product is partially or wholly exfoliated along the cutting edge with large strips, and/or cross-line test The different squares formed in the form of a grid are partially or wholly exfoliated; the affected cross-cut area is significantly greater than 15 area%, but significantly no more than 35 area%; ASTM Class 1B: cured product along the cutting edge Some strips in the form of a grid formed by stripping of large strips and/or cross-hatching tests have been partially or wholly detached from the underlying substrate; the affected cross-cut area is significantly larger than 35 area% , but significantly no more than 65 area%; ASTM category 0B: sheet peeling that cannot be classified as any degree of ASTM category 1B-5B.

Anti-wear test:

The anti-wear test utilizes a reciprocating wear tester Model-5900 available from Taber Industries of North Tonawanda, New York. The wear material used was CS-17 Wearaser® from Taber Industries. The wear material has a size of 6.5 mm x 12.2 mm. The reciprocating attrition machine operates 10, 25 and 100 cycles at a stroke speed of 1 Torr and a load of 10.0 N at a speed of 25 cycles per minute. After each cycle, the surface of the cured product was visually inspected to determine the abrasion. The following ratings are specified based on this visual inspection: Grade 1: no damage to the cured product; Grade 2: slight scratching of the cured product; Grade 3: medium scratch on the cured product; grade 4: partially visible through the cured product; and grade 5: the substrate is completely visible through the cured product.

Smudge mark test:

The stain marking test optically measures the ability of the cured product to exhibit stain resistance. In particular, in the stain marking test, a line was drawn on each of the cured products using a Super Sharpie® oily marking pen (available from Newell Rubbermaid Office Products of IL Oak Brook). Each line was optically inspected to determine whether the line cured product was beaded. The "1" level indicates that the line is completely beaded into small droplets, while the "5" level indicates that the line is not beaded. After thirty seconds to draw a line on each of the cured product, a piece of paper (Kimtech Science ^TM Kimwipes ^TM, available from the TX Irving Kimberly-Clark Worldwide, Inc. Commercially available) to wipe five consecutive lines. The "1" level indicator line (or its beaded part) is completely removed from the substrate, while the "5" level indicator line is not removed.

Table 1 below illustrates the physical properties of each of the cured products based on the tests described above. In Table 1, "Ex." specifies an instance; and "C.E." specifies a comparison example.

As clearly stated above, especially since the formation does not include any such fluorination The cured product of the curable composition of Comparative Example 1 of the polymer, including an example of a fluorinated polymer prepared by a microaddition reaction between a polyfunctional acrylate and each of the fluorinated compounds of Preparation Examples 1-3 The curable composition of 1-3 forms a cured product having excellent physical properties.

The present invention has been described in an illustrative manner, and it is understood that the terms used are intended to be illustrative and not limiting. Obviously many modifications and variations of the present invention are possible in the light of the teachings herein. The invention may be embodied in other specific forms than those specifically described.

Claims (12)

A fluorinated compound having the formula (1): R _f -CONR-(CH ₂ ) _a -SiR ¹ X-(OSiR ¹ X) _b -(CH ₂ ) _c -Y (1); wherein R _f a fluorine-substituted group; R is H or a substituted or unsubstituted hydrocarbon group; each R ¹ is an independently selected substituted or unsubstituted hydrocarbon group; each X is independently R ¹ or an amine-containing group; Y is a terminal group selected from R and X; subscripts a and c are each independently selected from 0 and an integer from 1 to 10; and subscript b is an integer from 2 to 20; however, the fluorinated compound includes at least one An amine group specified by X or Y. The fluorinated compound of claim 1, wherein R is H such that the fluorinated compound has the formula (2): R _f -CONH-(CH ₂ ) _a -SiR ¹ X-(OSiR ¹ X) _b -(CH ₂ ) _c -Y (2); wherein R _f , R ¹ , X, Y and subscripts a, b and c are as defined in claim 1. A fluorinated compound according to claim 2, wherein X is R ¹ and Y is an amine group-containing group such that the fluorinated compound has the formula (3): R _f -CONH-(CH ₂ ) _a -SiR ¹ ₂ - ( OSiR ¹ ₂ ) _b -(CH ₂ ) _c -NHR (3); wherein R _f , R, R ¹ and the subscripts a, b and c are as defined in claim 1. The fluorinated compound of claim 3, wherein the subscripts a and c are each 0 such that the fluorinated compound has the formula (4): R _f -CONH-SiR ¹ ₂ -(OSiR ¹ ₂ ) _b -NHR (4 Wherein R _f , R, R ¹ and the subscript b are as defined in claim 1. A fluorinated compound according to any one of the preceding claims, wherein R _f :(i) is partially fluorinated; (ii) comprises a perfluoropolyether segment; or (iii) has both (i) and (ii) . A fluorinated compound according to claim 5, wherein R _f comprises the perfluoropolyether segment, the perfluoropolyether segment comprising a moiety of the formula (5): -(C ₃ F ₆ O) _x -(C ₂ F ₄ O) _y -(CF ₂ ) _z - (5); wherein the subscripts x, y and z are each independently selected from 0 and an integer from 1 to 40, except that x, y and z are not 0 at the same time. A fluorinated polymer comprising the reaction product of a methine addition reaction of a fluorinated compound of claim 1 and a polyfunctional acrylate. A curable composition comprising the fluorinated polymer of claim 7 and a polyfunctional acrylate; or a curable composition comprising the fluorinated polymer of claim 7, a polyfunctional acrylate, and a fortification filler. A cured product formed from the curable composition of claim 8. The cured product of claim 9, the cured product comprising a film having a thickness greater than 0 to 20 micrometers (μm); or a cured product as claimed in claim 9 disposed on a substrate; or the cured product comprising having greater than 0 A film having a thickness of up to 20 micrometers (μm) disposed on a substrate. The cured product of any one of claims 9 to 10 having a water contact angle of at least 100°. A method of forming a cured product, the method comprising: applying a curable composition according to claim 8 to a substrate; and curing the curable composition on the substrate to form the substrate Cured product.