Novel (per)fluoropolyether polymers and uses thereof

Abstract

The present invention relates to a novel (per)fluoropolyether (PFPE) polymer, its manufacturing process and its use as an additive in coating compositions.Specifically, the present invention relates to a (per)fluoropolyether polymer [polymer (PP)] comprising a (per)fluoropolyoxyalkylene chain [chain (Rpf)] having two chain ends bonded to opposite sides of said chain (Rpf), wherein * one of said chain ends comprises at least one, preferably 1-3 groups (group [I]) selected from an alkoxysilane group [group (Si)] or a crosslinkable group, preferably an unsaturated moiety [group (U)] and an epoxide [group (E)]; and * the other chain end comprises at least one, preferably 1-3 groups (group [II]) selected from an optionally substituted piperidine, an optionally substituted pyridine or an optionally substituted pyrrole.

Description

[Technical field]

[0001] REFERENCE TO RELATED APPLICATIONS This application claims priority from European Patent Application Publication No. 22176290.9, filed May 31, 2022, the entire contents of which are incorporated herein by reference for all purposes.

[0002] The present invention relates to novel (per)fluoropolyether (PFPE) polymers endowed with improved UV stability, their preparation process and their use as additives in coating compositions. [Background technology]

[0003] The use of (per)fluoropolyether (PFPE) polymers as raw materials in the manufacture of antifouling coating compositions for coating different types of substrates is known in the art.For example, EP 3312242 (3M Innovative Properties Company) discloses protective coating compositions with mixed functionality, in which PFPE is the backbone mentioned among others; WO 2016 / 079195 (Solvay Specialty polymers Italy SpA) discloses zwitterionic derivatives of PFPE, which are disclosed as suitable for coating applications; WO 2019 / 106366 (Sphere Fluidic Limited) discloses surfactants containing perfluoropolyether structures.

[0004] Coatings based on (per)fluoropolyether (PFPE) polymers have been disclosed in the art, for example in US Pat. No. 5,623,037 and US Pat. No. 6,071,564 (both in the name of Ausimont SpA).

[0005] When a substrate is treated with a perfluoropolyether-containing silane compound, a film layer having hydrophobicity, oleophobicity, antifouling properties, low friction coefficient and durability can be formed on its surface. For example, US Patent Application Publication No. 2020 / 407378 (Guangzhou UR Materials Technology Co., Ltd.) is mentioned.

[0006] PFPE polymers containing alkoxy-silane groups and an aliphatic cyclic moiety containing at least one nitrogen atom are disclosed, for example, in U.S. Patent Application Publication No. 2018 / 0244844 (in the name of Daikin Industries, Ltd.).

[0007] China Patent No. 109642000 (in the name of Nissan Chemical Industries Ltd.) discloses a composition comprising a PFPE polymer having unsaturated moieties at both of its chain ends. Summary of the Invention

[0008] For example, the many different substrates currently used in the automotive sector require antifouling coatings which should meet particular requirements, not only regarding UV resistance, but also clarity (transparency), durability and oil- and water-repellency.

[0009] The applicant has recognized that, despite efforts made in the art, there remains a need for additives that can enhance the UV resistance of coating compositions for use on some substrates, without adversely affecting the transparency, durability, and oil- and water-repellency, as well as the stain-repellency properties.

[0010] Faced with the above technical problems, the Applicant has found that (per)fluoropolyether polymers bearing two different functional groups at their chain ends can be advantageously used as additives to enhance the UV-stability of coatings.

[0011] Thus, in a first aspect, the present invention provides a (per)fluoropolyoxyalkylene chain [chain (R pf)], wherein the chain (R pf A (per)fluoropolyoxyalkylene chain [chain (R pf (Per)fluoropolyether polymers [polymer (P P )], one of said chain ends comprises at least one, preferably 1 to 3 groups (groups [I]) selected from alkoxysilanes [groups (Si)] or crosslinkable groups preferably selected from unsaturated moieties [groups (U)] and epoxides [groups (E)]; and The other chain end is a (per)fluoropolyether polymer [polymer (P P )].

[0012] Advantageously, the (per)fluoropolyoxyalkylene chain (R pf The presence of different groups at the two chain ends of the PFPE polymer provides an "asymmetric PFPE polymer" that can be used as an additive that can impart outstanding UV resistance along with good durability over time.

[0013] Also advantageously, the polymer according to the invention (P P ) allows fine adjustment of the amount of groups [I] and [II], thereby P ) is prepared by a process which allows for the appropriate selection of the amount of the desired functional group [I] or [II] depending on the final composition in which it is intended to be used.

[0014] The polymer (P P ) is particularly preferred, but the present invention also relates to polymers (P P ) and at least one other polymer having either two groups [I] or two groups [II] at its chain ends.

[0015] Such compositions, when added as additives in coating compositions, are also useful for providing good UV resistance over time without negatively relying on the water and oil repellency, and easy to clean and stain release properties of the initial composition. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0016] For purposes of this description and the claims that follow: - For example, "Polymer (P P The use of parentheses around symbols or numbers identifying formulas, such as in expressions such as "(a)" and "b)" has the sole purpose of better distinguishing the symbols or numbers from the remainder of the text, and so said parentheses may be omitted; - the acronym "PFPE" stands for "(Per)Fluoropolyether" and, when used as a noun, is intended to mean either the singular or the plural, depending on the context; the term "(per)fluoropolyether" is intended to denote fully or partially fluorinated polyethers; - The terms "clear" and "transparent" are used synonymously.

[0017] The polymer (P P ) is a (per)fluoropolyoxyalkylene chain [Chain (R pf )], wherein the chain (R pf A (per)fluoropolyoxyalkylene chain [chain (R pf )], one of said chain ends comprises at least one group (group [I]) selected from alkoxysilanes [group (Si)] or crosslinkable groups preferably selected from unsaturated moieties [group (U)] or epoxides [group (E)]; and *The other chain end contains at least one group (group [II]) selected from one of optionally substituted piperidine, optionally substituted pyridine or optionally substituted pyrrole.

[0018] For the avoidance of doubt, the expression "selected from one of optionally substituted piperidine, optionally substituted pyridine or optionally substituted pyrrole" is used to indicate that group (II) is derived from any one of the optionally substituted compounds in that list. Group (II) is a group consisting of a chain (R pf )].

[0019] Polymer (P P ) may contain one, two or three groups (I) at one chain end and one, two or three groups (II) at the other chain end.

[0020] The polymer according to the present invention (P P ), the chain (R pf ) is preferably represented by the formula -D'-(CFX') z1 O(R f )(CFX) z2 -D- (In the formula, z1 and z2, which may be equal to or different from each other, are 1 or more, preferably 1 to 10, more preferably 1 to 3; X and X', which may be equal or different, are -F or -CF 3 and With the proviso that when z1 and / or z2 are greater than 1, X and X' are -F; D and D', which are equal or different from each other, are a sigma bond or a hydrogenated alkylene chain containing 1 to 6, even more preferably 1 to 3 carbon atoms, said alkyl chain being optionally substituted with at least one perfluoroalkyl group containing 1 to 3 carbon atoms; (R f ) comprises, and preferably consists of, repeat units R°, said repeat units being (i) -CFXO- (wherein X is F or CF 3 is); (ii) -CFXCFXO-, where X, equal or different at each occurrence, is F or CF 3 with the proviso that at least one of X is -F; (iii)-CF 2CF 2 CW 2 O- (wherein each of W, which is equal to or different from each other, is F, Cl, H); (iv)-CF 2 CF 2 CF 2 CF 2 O-; (v)-(CF 2 ) j -CFZ-O- (wherein j is an integer of 0 to 3, and Z is a group represented by the general formula -OR (f-a) -T group, R (f-a) is a fluoropolyoxyalkene chain containing 0 to 10 repeat units, the repeat units being -CFXO-, -CF 2 CFXO-, -CF 2 CF 2 CF 2 O-, -CF 2 CF 2 CF 2 CF 2 O-, and each X is independently selected from F or CF 3 and T is C 1 ~C 3 perfluoroalkyl group) (independently selected from the group consisting of It is a chain of.

[0021] More preferably, each of D' and D is a sigma bond or -CH 2 -It is.

[0022] Preferably, the chain (R f ) is expressed by the following formula: (R f -I)-[(CFX 1 O) g1 (CFX 2 CFX 3 O) g2 (CF 2 CF 2 CF 2 O) g3 (CF 2 CF 2 CF 2 CF 2 O) g4 ]- (In the formula, -X 1 -F and -CF 3 are independently selected from - X's that are equal or different from each other and for each occurrence 2 , X 3 are independently -F, -CF 3 with the proviso that at least one X is -F; - g1, g2, g3 and g4, which are equal to or different from one another, are independently integers greater than or equal to 0, such that g1+g2+g3+g4 ranges from 2 to 300, preferably from 2 to 100; if at least two of g1, g2, g3 and g4 are different from 0, the different repeat units are generally statistically distributed along the chain. Follow.

[0023] More preferably, the chain (R f ) is the formula: (R f -IIA)-[(CF 2 CF 2 O) a1 (CF 2 O) a2 ]- (In the formula, a1 and a2 are independently integers greater than or equal to 0, such that the number average molecular weight is between 400 and 10,000, preferably between 1,000 and 6,000; both a1 and a2 are preferably different from zero, the ratio a1 / a2 being preferably comprised between 0.1 and 10); (R f -IIB)-[(CF 2 CF 2 O) b1 (CF 2 O) b2 (CF(CF 3 )O) b3 (CF 2 CF(CF 3 )O) b4 ]- (In the formula, b1, b2, b3, and b4 are independently integers of 0 or more such that the number average molecular weight is 400 to 10,000, preferably 1,000 to 6,000; preferably, b1 is 0, b2, b3, and b4 are greater than 0, and the ratio b4 / (b2+b3) is 1 or more; (R f -IIC)-[(CF 2 CF 2 O) c1 (CF 2 O) c2 (CF 2 (CF 2 ) cw CF 2 O) c3 ]- (In the formula, cw=1 or 2; c1, c2 and c3 are independently integers greater than or equal to 0 selected such that the number average molecular weight is 400 to 10,000, preferably 1,000 to 6,000; preferably, c1, c2 and c3 are all greater than 0 and the ratio c3 / (c1+c2) is generally less than 0.2); (R f -IID)-[(CF 2 CF(CF 3 )O) d ]- (In the formula, d is an integer greater than 0 such that the number average molecular weight is 400 to 10,000, preferably 1,000 to 6,000; (R f -IIE)-[(CF 2 CF 2 C(Hal*) 2 O) e1 -(CF 2 CF 2 CH 2 O) e2 -(CF 2 CF 2 CH(Hal*)O) e3 ]- (In the formula, - Hal*, which is equal or different at each occurrence, is a halogen selected from fluorine and chlorine atoms, preferably a fluorine atom; - e1, e2 and e3, which are equal to or different from each other, are independently integers of 0 or more such that the sum (e1+e2+e3) is in the range of 2 to 300. The chain is selected from:

[0024] Even more preferably, the chain (R f ) is herein represented by the following formula (R f -III): (R f -III)-[(CF 2 CF 2 O) a1 (CF 2 O) a2 ]- (In the formula, a1 and a2 are integers greater than 0 such that the number average molecular weight is 400 to 10,000, preferably 1,000 to 6,000, and the ratio a1 / a2 is generally 0.1 to 10, more preferably 0.2 to 5. Follow.

[0025] As described above, the polymer (P P ) is advantageously an asymmetric polymer, in other words (P P ) comprises at least one group [I] at one chain end and at least one group [II] at the other chain end, wherein groups [I] and [II] are different from each other.

[0026] Preferably, the group [I] is linked to a chain (R pf ) is linked to

[0027] More preferably, the linking group has the formula: *-(R a ) t -(R b ) v -(R c ) u -§ (In the formula, * indicates a chain (R pf ), § indicates the bond to group [I]; R ais a poly(oxy)alkylene chain; t is 0 or an integer of 1 to 15, preferably 1 to 10; v is 0 or 1; R b is the expression: (R b -I)-OC(=O)-NH-(CH h ) e - (R b -II)-C(=O)-NR'-(CH h ) f - (R b -III)-O-(CH 2 ) g -C(=O)- (In the formula, e is an integer from 1 to 6; R' is H or a linear or branched alkyl chain having 1 to 6 carbon atoms; f is an integer from 1 to 4; g is an integer from 1 to 4, and Each h is independently 0 or an integer equal to 1 or 2, with the proviso that when h is 0, then e and f are each independently 1. is the basis of; R c is a linear or branched alkyl chain having 1 to 12 carbon atoms, optionally containing one or more oxygen atoms, or an optionally substituted aliphatic cycloalkyl containing 5 or 6 members; and u is 0 or 1) Follow.

[0028] As shown above, 1 to 3 groups [I] form a chain (R pf The presence of one, two or three groups [I] may be present at one of the chain ends of the group R b or R c It will be understood that the value depends on the valence of

[0029] For example, (R b ) is expressed as the above formula (R b -I) or (R b -II) When h is equal to 2, the carbon atom has two hydrogen atoms and one group [I], When h is equal to 1, the carbon atom bears one hydrogen atom and two groups [I]; When h is equal to 0, the carbon atom bears three groups [I].

[0030] Preferably, (R a ) is a poly(oxy)alkylene chain comprising 1 to 50 oxyalkylene units not containing fluorine. More preferably, said units, which are the same or different from each other, are represented by the formula: -OCH(J)CH(J*)- wherein each of J and J* is independently selected from a hydrogen atom, a linear or branched alkyl, or an aryl, preferably a hydrogen atom, a methyl, an ethyl, or a phenyl. Follow.

[0031] More preferably, -(R a ) t - is expressed by the following formula (R a -I)~(R a -III): (R a -I)-(OCH 2 CH 2 ) t1 - (R a -II)-[OCH(CH 3 )CH 2 ] t2 -, (R a -III)-[(OCH 2 CH 2 ) t3 -(OCH(CH 3 )CH 2 ) t4 ] tx - (In the formula, t1 and t2 are each independently an integer of 1 to 15, preferably 1 to 10; and t3, t4 and tx are integers greater than 1 such that the sum of t3 and t4 is 2 to 15, more preferably 2 to 10. Follow one of the following:

[0032] Preferably, the group [I] is a group (U).

[0033] More preferably, the group (U) is (UI)-OC(=O)-CR H =CH 2 (U-II)-OC(=O)-NH-CO-CR H =CH 2 (U-III)-C(=O)-R A -CR H =CH 2 wherein R H is H or C 1 ~C 6 is an alkyl group; R A is (R A -I) and (R A -II): (R A -I) [ka] (In the formula, Each j5 is independently 0 or 1; and R B C optionally contains at least one heteroatom selected from N, O and S; 1 ~C 10 Aliphatic group;C 3 ~C 12 Alicyclic group;C 5 ~C 14 a divalent, trivalent or tetravalent group selected from the group consisting of aromatic or alkylaromatic groups; (R A -II) [ka] (In the formula, j6 is 0 or 1; Each j7 is independently 0 or 1; RB’ C optionally contains at least one heteroatom selected from N, O and S; 1 ~C 10 Aliphatic group;C 3 ~C 12 Alicyclic group;C 5 ~C 14 is a divalent, trivalent or tetravalent group selected from the group consisting of aromatic or alkylaromatic groups; and R B* is R B’ or it has the same meaning as defined above for B -I): [ka] (In the formula, The substituent U is selected from the groups (UI) to (U-III) as defined above, and * and # are the same as in the above formula (R A -II) (based on is selected from the group consisting of:

[0034] Alternatively, the group [I] is a group (Si).

[0035] Preferably, the group (Si) has the formula: -Si-(OR 30 ) 3 (In the formula, R 30 is a linear or branched alkyl chain having 1 to 12 carbon atoms. Follow.

[0036] Preferably, according to this embodiment, the chain ends comprise from 1 to 3 groups (Si) as defined above.

[0037] Alternatively, the group [I] is a group (E).

[0038] Preferably, according to this embodiment, the chain end comprises one group (E).

[0039] Preferably, the group (E) has the following formula: *-(R a ) t -(R c ) u -§ (where *, §, R a ,t,R c and u is as defined above. The chain (R pf )

[0040] Preferably, the group [II] is of the formula: *-(R a ) t -NH-§, or *-(R a ) t -O-§ (In the formula, * indicates a chain (R pf ) and § represents a bond to group [II], and R a and t each have the meaning given above for group [I]. The chain (R pf ) is bonded to D or D'.

[0041] According to this embodiment, the chain (R pf Each of the groups D and D' in is a hydrogenated alkylene chain containing 1 to 6 carbon atoms.

[0042] Alternatively, the group [II] has the formula: -(R a ) t -(R*) p C(=O)NH-(R**) q or -(R a ) t -(R***) r C(=O)O-(R****) s - (In the formula, p, q, r, and s each independently represent 0 or an integer of 1 to 6; R aand t has the meaning defined above, and Each of R*, R**, R*** and R**** is independently a linear or branched alkyl chain containing 1 to 6 carbon atoms. The chain (R pf )

[0043] According to this embodiment, the chain (R pf Each group D and D' in is a sigma bond.

[0044] Preferably, the group [II] is selected from those derived from substituted piperidine, substituted pyridine and substituted pyrrole.

[0045] Good results were obtained when the group [II] was a derivative of 4-amino-2,2,6,6-tetramethyl-piperidine.

[0046] In a second aspect, the present invention provides a method for producing a pharmaceutical composition comprising the steps of: - a polymer as defined above (P P )and; - (Per)fluoropolyoxyalkylene chain [Chain (R pf )], and the chain (R pf A (per)fluoropolyoxyalkylene chain [chain (R pf (Per)fluoropolyether polymers [polymer (P U )], both chain ends of which contain a group of formula [I] as defined above, U )]and; - (Per)fluoropolyoxyalkylene chain [Chain (R pf )], and the chain (R pf A (per)fluoropolyoxyalkylene chain [chain (R pf (Per)fluoropolyether polymers [polymer (P N )], both chain ends of which contain a group of formula [II] as defined above,N )]and A composition comprising [composition (C POL )].

[0047] Advantageously, the composition (C POL ) is at least 25% by weight of said polymer (P P ).

[0048] Preferably, the composition (C POL )teeth, - 2.0 to 50.0% by weight of polymer (P P )and, - 0.1 to 25.0% by weight of polymer (P N )and, - 25.0 to 95.0% by weight of polymer (P U )and Includes.

[0049] Composition (C POL ) is a (per)fluoropolyether chain [Chain (R pf )], and the chain (R pf (per)fluoropolyether chains [chains (R pf (Per)fluoropolyether polymers [polymer (P x (Per)fluoropolyether polymers [polymers (P)], one chain end of which contains a perfluoroalkyl group and the other chain end of which contains at least one group of either formula [I] or formula [II] as defined above. x )].

[0050] When present, the polymer (P X ) is a composition (C POL ) is preferably in an amount of 15.00% by weight or less, more preferably 0.01 to 12.00% by weight, and even more preferably 0.05 to 10.00% by weight, based on the total weight of the components (a) and (b).

[0051] Preferably, the polymer (P U ), polymer (P N) and polymer (P X ), the chain (R pf ), group [I] and group [II] each represent a polymer (P P ) is as defined above.

[0052] Preferably, the polymer (P x ) is -CF 3 , -C 2 F 5 , -C 3 F 7 , -CF 2 Cl, -CF 2 CF 2 Cl and -C 3 F 6 It contains at one chain end a perfluoroalkyl group selected from the group consisting of, more preferably, Cl.

[0053] The polymer (P) containing perfluoroalkyl groups as defined above x ) is a "monofunctional polymer (P x )"

[0054] As is known in the art, the functionality (F) of the polymer P according to the invention, i.e. the average number of functional groups per molecule of the polymer, is between 1.00 and 2.00. Bifunctional polymers P typically have a functionality (F) between 1.50 and 1.99, more preferably between 1.70 and 1.98, even more preferably between 1.85 and 1.95. The functionality (F) can be calculated, for example, as disclosed in EP 1 810 987 A (SOLVAY SOLEXIS SPA).

[0055] Polymer (P P The preparation process of composition (C POL Optionally, the composition (C POL ) is then reacted with the polymer (P P ) can be subjected to a purification step to obtain

[0056] The composition (C POL ) is advantageously a (per)fluoropolyether chain [chain (R pf )], and the chain (R pf (per)fluoropolyether chains [chains (R pf ), wherein the chain ends are of the formula -OH or -C(=O)OR 10 (In the formula, R 10 can be prepared starting from a (per)fluoropolyether (PFPE) polymer containing the group H or a linear or branched alkyl chain containing 1 to 6 carbon atoms, preferably 1 to 3 carbon atoms.

[0057] In a further aspect, the present invention relates to a composition as defined above (C POL ) in a process for synthesis.

[0058] Preferably, the composition (C POL The process of synthesizing - (Per)fluoropolyether chain [Chain (R pf )], wherein the chain (R pf (per)fluoropolyether chains [chains (R pf (Per)fluoropolyether polymers [polymer (P INT )], wherein one of the chain ends is of the formula -OH or -C(=O)OR 10 (In the formula, R 10 is as defined above) and the other chain end contains a group [II] as defined above. INT )]and; - (Per)fluoropolyether chain [Chain (R pf )], wherein the chain (R pf (per)fluoropolyether chains [chains (R pf) (per)fluoropolyether polymers [polymer PFPE] comprising a fluorocarbon polymer having a formula -OH or -C(=O)OR 10 (In the formula, R 10 is as defined above), and - (Per)fluoropolyether chain [Chain (R pf )], wherein the chain (R pf (per)fluoropolyether chains [chains (R pf (Per)fluoropolyether polymers [polymer (P II )], wherein both said chain ends comprise a group [II] as defined above. II )]and The method proceeds to synthesis of an intermediate composition [composition (INT)] comprising:

[0059] The composition (INT) as defined above is another aspect of the present invention.

[0060] Therefore, in a further aspect, the present invention provides a method for producing a composition comprising the steps of: (i) (per)fluoropolyether chain [chain (R pf )], wherein the chain (R pf (per)fluoropolyether chains [chains (R pf 2. providing a (per)fluoropolyether polymer [polymeric PFPE] comprising: (ii) replacing at least a portion of the -OH groups, if present, with leaving groups for nucleophilic substitution reactions or with groups of the formula -O(R***) r C(=O)O-(R V ) where R*** and r are as defined above, and R V is an alkyl chain containing 1 to 3 carbon atoms; (iii) reacting the PFPE polymer of step (i) or the composition obtained in step (ii) with a compound of the formula -OH or -NH 2 and a group derived from one of the optionally substituted piperidine, optionally substituted pyridine or optionally substituted pyrrole groups, thus obtaining a composition [composition (INT)] as defined above. The present invention relates to a process for synthesizing a composition (INT) as defined above, comprising:

[0061] The composition according to the present invention (C POL ) is advantageously (iv) providing a composition (INT) as defined above and mixing said composition (INT) a compound [A] having at least one group (U) as defined above and at least one halogen atom, an isocyanate group or an amino group; or a compound [B] having at least one group (E) as defined above and at least one halogen atom or at least one isocyanate group; or - a compound [C] having at least one group (Si) as defined above and at least one isocyanate or amino group; and contacting said composition (C POL ) It can be prepared starting from a composition (INT) as defined above, according to a process comprising:

[0062] Furthermore and advantageously, the composition (INT) as defined above comprises at least a polymer (P INT ) may be subjected to purification according to methods known in the art.

[0063] According to this embodiment, the polymer (P INT ) is then contacted with at least one of the compounds [A], [B] or [C] as defined in step (iv) above, thus forming a polymer (PP ) is obtained as a pure compound.

[0064] According to one embodiment, the composition (C POL ) can be prepared by one-pot synthesis, i.e., without recovering composition (INT) from the reaction mixture.

[0065] According to this embodiment, the composition (C POL ) follow the steps below: (i*) (per)fluoropolyether chain [chain (R pf )], wherein the chain (R pf (per)fluoropolyether chains [chains (R pf providing a (per)fluoropolyether polymer [polymer PFPE] comprising a -C(=O)OR 10 or -OH (wherein R 10 is as defined above; (ii*) if present, at least a portion of said -OH groups can be substituted with leaving groups for nucleophilic substitution reactions or with groups of the formula -O(R***) r C(=O)O-(R V ) where R*** and r are as defined above, and R V is an alkyl chain containing 1 to 3 carbon atoms; (iii*) reacting the PFPE polymer of step (i) or the composition obtained in step (ii) with a compound of the formula -OH or -NH 2 and a group derived from one of the optionally substituted piperidine, optionally substituted pyridine or optionally substituted pyrrole groups, thus obtaining a composition (INT) as defined above; (iv*) the composition (INT) as obtained in step (iii), a compound [A] having at least one group (U) as defined above and at least one halogen atom, an isocyanate group or an amino group; or a compound [B] having at least one group (E) as defined above and at least one halogen atom or at least one isocyanate group; or - a compound [C] having at least one group (Si) as defined above and at least one isocyanate or amino group; and thus the composition (C POL ) and It is prepared by a process comprising:

[0066] The polymeric PFPE used as starting material in steps (i) and (i*) above preferably has the following formula: (PFPE-i)HO-(R pf )-OH (PFPE-ii)HO-[CH(J*)CH(J)O] t1 -(R pf )-[OCH(J)CH(J*)] t2 -OH (PFPE-iii)HO-(O=)C-(R pf )-C(=O)OH (In the formula, (R pf ) is as defined above, t1 and t2 are each independently an integer from 1 to 50; and J and J* are each independently (R a ) as defined above for is a PFPE polymer conforming to one of the above.

[0067] Good results have been obtained within the present invention when starting from polymeric PFPEs commercially available from Solvay Specialty Polymers Italy SpA under the trade names Fomblin® PFPE and Fluorolink® PFPE.

[0068] Advantageously, under step (ii) or step (ii*) above, at least a portion of said -OH groups in the PFPE polymer of formula (PFPE-i) or (PFPE-ii) are converted into leaving groups for nucleophilic substitution reactions, including, and preferably selected in the group consisting of, mesyl, tosyl, perfluorobutanesulfonyl or trifluoromethylsulfonyl groups.

[0069] Alternatively, under step (ii) or step (ii*) above, at least a portion of the -OH groups in the PFPE polymer of formula (PFPE-i) or (PFPE-ii) may be converted to a PFPE polymer of formula -O(R***) as defined above by reaction with methyl chloroacetate, methyl 3-bromopropionate, methyl 4-iodobutyrate. r C(=O)O-(R V ) group.

[0070] Such a reaction in step (ii) or step (ii*) can be appropriately controlled to convert a desired amount of such -OH groups. To do so, the skilled person can react with a compound of formula -O(R***) as defined above. r C(=O)O-(R V ) t The amount of reactant can be selected to provide the leaving group for nucleophilic displacement of a predetermined amount of the - group. The amount of -OH groups that can be converted is not limited and can be appropriately determined by those skilled in the art depending on the desired end product. For example, within the present invention, good results have been obtained by converting about 30% of the -OH groups in the starting PFPE polymer. However, about 1 to 100% of the -OH groups in the starting PFPE polymer can be converted to groups as described under step (ii) or step (ii*) above.

[0071] Preferably, said step (ii) or step (ii*) is carried out in the presence of a fluorinated solvent, preferably selected from the group comprising fluorinated hydrocarbons, α,α,α,α',α',α'-hexafluoro-m-xylene, α,α,α,α',α',α'-hexafluoro-p-xylene, chlorotrifluoro-toluene isomers (such as 4-chlorobenzenetrifluoride, 2-chlorobenzenetrifluoride), α,α,α-trifluorotoluene, hexafluorobenzene and mixtures thereof.

[0072] Preferably, in step (iii) or (iii*), a compound of formula -OH or -NH 2 and a group derived from one of the optionally substituted piperidine, optionally substituted pyridine or optionally substituted pyrrole is selected from 4-amino-2,2,6,6-tetramethylpiperidine, 2,2,6,6-tetramethyl-4-piperidinol, 2-(2,2,6,6-tetramethyl-piperidin-4-yl)-ethanol.

[0073] Preferably, in step (iv) or step (iv*), the reaction with said compound [A] carrying at least one group (U) and at least one isocyanate group is preferred.

[0074] Preferably, in step (iv) or step (iv*), the compound [A] is represented by the following formula: O=C=NR 20 -R 21 -CR H =CH 2 (In the formula, R H has the same meaning as defined above for the group (U); R 20 is a linear or branched alkyl chain having 1 to 6 carbon atoms, optionally substituted with a group including a tri-alkoxy-silyl group; R 21 is the formula -OC(=O)-, -OC(=O)-NH-CO-, -OC(=O)-RA -(In the formula, R A is a divalent radical as defined above for group (U-III) Follow.

[0075] More preferably, compound [A] is selected from the group consisting of isocyanatoethyl methacrylate (IEM), allyl isocyanate, 3-isopropenyl-α,α-dimethylbenzyl isocyanate, vinyl isocyanate, acryloyl isocyanate, methacryloyl isocyanate, 2-isocyanatoethyl acrylate, 1,1-(bisacryloyloxymethyl)ethyl isocyanate, 2-(2-methacryloyloxyethyloxy)ethyl isocyanate.

[0076] The polymer (P P ) or the composition (C POL ) is advantageously used as an additive in compositions for antifouling coatings.

[0077] Instead, the polymer (P P ) or the composition (C POL ) can be provided in a mixture with a suitable solvent and then used as an additive in a composition for antifouling coatings. The solvent is preferably a solvent that is P ) or composition (C POL ) is a solvent that can react with

[0078] In a further aspect, the present invention relates to a polymer comprising at least one polymer (P P ) or composition (C POL ) and at least one solvent (S) preferably selected from (per)fluoropolyether polymers having at their chain ends at least one functional group preferably selected from unsaturated groups, alkoxysilane groups or epoxy groups [composition (DIL)].

[0079] Preferably, the composition (DIL) contains 0.01 to 50.00% by weight, preferably 1.00 to 25.00% by weight of the composition (CPOL ) or polymer (P P ) and 50.00 to 99.99% by weight, preferably 75.00 to 99.00% by weight, of at least one solvent (S) as defined above, the amount being based on the total weight of the composition (DIL).

[0080] According to one embodiment, the polymer (P P When (Si) contains a group, said solvent (S) is chosen from at least one hydrofluoroether or (per)fluoropolyether polymer containing one silane group.

[0081] According to a preferred embodiment, the polymer (P P When (U) contains a group, said solvent (S) is chosen from (per)fluoropolyether polymers having at least one, more preferably at least two, unsaturated groups at their chain ends.

[0082] According to a preferred embodiment, the polymer (P P ) comprises a group (U), said composition (DIL) is advantageously F The polymer (P P ) is added to the composition (C F 0.01 to 8.00 wt. %, more preferably 0.50 to 5.00 wt. %, based on the total weight of the at least one polymer (P P ), at least one solvent (S) as defined above, and at least one UV-curable component [composition (C F ) is added to a composition containing at least one UV-curable component to provide a

[0083] Preferably, the composition according to the invention (C F ) may advantageously be prepared by contacting and optionally mixing a composition as defined above (DIL) with said composition comprising at least one UV-curable component.

[0084] At least one further ingredient may be added to the above-mentioned compositions depending on the final intended use.

[0085] Such at least one further ingredient is preferably selected from crosslinkers, transparent fillers, photoinitiators, volatile or non-volatile additives such as selected from binders, catalysts, levelling agents, wetting agents, anti-crater agents, dyes, rheology control agents, antioxidants and / or light stabilizers.

[0086] Suitable crosslinking agents are selected, for example, from transesterification crosslinking agents, amino resin crosslinking agents such as melamine-formaldehyde resins; trisalkoxycarbonylaminotriazine crosslinking agents, and the like.

[0087] Suitable transparent fillers are for example selected from silica, more preferably nanosilica.

[0088] Each of the additional ingredients and additives is preferably selected from the group consisting of compositions (C F ) is used in a conventional amount, for example, 8.00% by weight or less, more preferably in an amount of 0.01 to 5.00% by weight, based on the total weight of the component (I).

[0089] In a further aspect, the present invention relates to a method for providing a transparent coating on at least one surface of a substrate, comprising the steps of: P ), composition (C POL ), composition (DIL) or composition (C F ) regarding its use.

[0090] Composition (DIL) or Composition (C F ) can be applied to at least the surface of a suitable substrate to form a clear (ie, transparent) coating layer.

[0091] In a still further aspect, the present invention provides a method of providing a transparent coating on at least one surface of a substrate, comprising the steps of: (i) providing at least one glass substrate having at least one surface; (ii) treating said at least one surface with composition (DIL) or composition (C F and contacting the The present invention relates to a method comprising the steps of:

[0092] Suitable methods and conditions for contacting the composition with the substrate can be selected by one skilled in the art depending on the composition and substrate used.

[0093] For example, the step (ii) of contacting may be carried out by contacting the composition (DIL) or the composition (C F ) onto at least the surface of a suitable substrate to provide a film.

[0094] More preferably, composition (DIL) or composition (C F ) is a polymer (P P ), the coating has a thickness of less than 1 μm, even more preferably between 10 and 50 nm.

[0095] More preferably, composition (DIL) or composition (C F ) is a polymer (P P ), the coating has a thickness of 20 to 500 μm, and even more preferably 30 to 250 μm.

[0096] Preferably, composition (DIL) or composition (C F ) is a polymer (P P When the composition (DIL) or the composition (C F A step (iii) of UV curing is then performed.

[0097] The curing conditions are as follows: F ) and from the context in which the coating and curing process is carried out.

[0098] Any radiation source can be used. The radiation dose depends on the composition (DIL) or (C F ) can be adjusted by the person skilled in the art based on the radiation. Good results have been obtained by applying radiation of 200-750 W. Preferably, when the curing step is carried out using UV, the curing time is 1-50 seconds, more preferably 5-30 seconds.

[0099] The present invention will hereinafter be illustrated in more detail by the examples contained in the experimental section below, which are illustrative only and should not be construed as limiting the scope of the invention in any way. EXAMPLES

[0100] Materials and Methods Fluorolink® E10H and Fomblin® Z DOL were obtained from Solvay Specialty Polymers Italy SpA. Bis(trifluoromethyl)benzene, triethylamine, methanesulfonyl chloride, acid chloride (37% sol), potassium hydroxide, ethanol, methanol, 2,6-di-tert-butyl-4-methylphenol (BHT), 2-isocyanatoethyl methacrylate, 4-amino-2,2,6,6-tetramethylpiperidine, methyl chloroacetate and sodium methoxide solution in methanol (25 wt%), dibutyltin dilaurate, ethyl methyl ketone, potassium tert-butoxide, tert-butanol, epibromohydrin were obtained from Aldrich. 3-(Trimethoxysilyl)propyl isocyanate was obtained from TCI. SnapCure TM 1030 was obtained from Alfa Aesar Gmbh & Co.

[0101] 1 H-NMR and 19 F-NMR is 1 H: 499.86MHz and 19F was recorded on an Agilent System 500 operating at 470.30 MHz.

[0102] FT-IR spectra were measured on a ThermoScientific FTIR spectrophotometer on liquid samples as thin films on KBr. Spectra were measured using a 2 cm -1 The images were acquired by coadding 256 scans at a resolution of 100 s.

[0103] Example 1 – Synthesis of Composition A Step 1: A 0.5 L four-neck round bottom flask kept under nitrogen and equipped with a condenser, mechanical stirrer, thermometer probe and dropping funnel was charged with 150 g (EW=908 g / mol; 165.2 meq) of Fluorolink® E10H, 100 g of 1,3-bis(trifluoromethyl)benzene and 6.0 g of triethylamine (59.4 meq). The flask was then cooled and 5.8 g of methanesulfonyl chloride (50.1 meq) was added at such a rate as to keep the temperature in the range of 15-30° C. When the methanesulfonyl chloride addition was complete, the reaction mixture was left under stirring at 25-30° C. for an additional 6 hours. 70 g of a 4 M aqueous solution of HCl was then added to the reaction mixture and the organic phase formed thereby was separated. After distillation of the fluorinated solvent under reduced pressure (T=80° C., P=2 Pa), 151.9 g of a clear liquid was isolated and characterized. 1 H-NMR analysis confirmed that the resulting product was the starting Fluorolink® E10H with 29% of the -OH groups converted to mesylate esters.

[0104] Step 2: 30 g of 1,3-bis(trifluoromethyl)benzene, 15 g of ethanol, 100 g of the product obtained in step 1 and 11.5 g of 4-amino-2,2,6,6-tetramethylpiperidine (73.6 mmol) were charged into a 0.5 L four-neck round bottom flask kept under nitrogen atmosphere and equipped with a condenser, mechanical stirrer, thermometer probe and dropping funnel. The resulting mixture was heated to 70° and cooled to room temperature after 20 hours of vigorous stirring, 100 g of potassium hydroxide solution (10% by weight) in ethanol and 50 g of 1,3-bis(trifluoromethyl)benzene were added. After 3 hours of stirring, 100 g of water was added to the reaction mass and the organic phase formed thereby was separated and subjected to three additional washes by treatment with 100 g of water and 50 g of ethanol. Finally, the lower organic phase was separated and distilled under reduced pressure (T=80° C., P=2 Pa) to remove the solvent, giving 103.5 g of the target PFPE-amine derivative, the structure of which was 1 This was confirmed by 1 H NMR analysis.

[0105] Step 3: Add 90 g of the product obtained in step 2, 3.5*10 g of the product, and 100 g of the product into a 100 ml four-neck round bottom flask equipped with a condenser, mechanical stirrer, dropping funnel, and thermometer probe. -2 g 2,6-di-tert-butyl-4-methylphenol (BHT), 8.6*10 -2 g's SnapCure TM 1030 was charged and the resulting mixture was heated to 50° C. Then 10.8 g of 2-isocyanatoethyl methacrylate (69.4 mmol) was slowly added, the temperature was increased to 60° C. and the reaction mixture was left under vigorous stirring for 3 hours. After that, 1.0 g of methanol was added and the reaction mixture was stirred for an additional 2 hours and dried under reduced pressure (T=60° C., P=2 Pa) to obtain 98.1 g of composition A.

[0106] Example 2 - Synthesis of Composition B Step 1: A 0.5 L four-neck round-bottom flask kept under nitrogen and equipped with a condenser, mechanical stirrer, thermometer probe and dropping funnel was charged with 250 g (EW=g / mol 871; 287.0 meq) of Fomblin® ZDOL, 125 g of 1,3-bis(trifluoromethyl)benzene and 18.7 g of sodium methoxide (25% by weight) in methanol. The flask was then heated up to 60° C. and left under stirring for 1 h under nitrogen and a gentle nitrogen flow. Afterwards, 9.7 g of methyl chloroacetate (89.0 meq) was added and the reaction mixture was left under stirring for a further 4 h. Then, 100 g of a 4 M aqueous solution of HCl and 10 g of methanol were added to the reaction mixture and the organic phase formed thereby was separated. After distillation of the fluorinated solvent under reduced pressure (T=80° C., P=2 Pa), 253.9 g of a clear liquid was isolated and characterized. 1 H-NM and 19 F-NMR analysis confirmed that the resulting product was the starting Fomblin® ZDOL with 29% of the methylol groups converted to the corresponding methyleneoxymethyl acetate.

[0107] Step 2: A 0.25 L four-neck round bottom flask kept under nitrogen and equipped with a condenser, mechanical stirrer, thermometer probe and dropping funnel was charged with 40 g of 1,3-bis(trifluoromethyl)benzene, 11.0 g (70.0 mmol) of 4-amino-2,2,6,6-tetramethylpiperidine and 150 g of the product obtained in step 1. The resulting mixture was heated to 70° and left under vigorous stirring for 36 hours. Distillation under reduced pressure (T=80° C., P=2 Pa) to remove the solvent and excess 4-amino-2,2,6,6-tetramethylpiperidine gave 154.8 g of a clear liquid, which was characterized. 1 1 H NMR and FT-IR analyses confirmed the quantitative conversion of the methyl ester to the target amide.

[0108] Step 3: Add 100 g of the product obtained in step 2, 3.9*10, to a 100 mL four-neck round bottom flask equipped with a condenser, mechanical stirrer, dropping funnel and thermometer probe. -2 g 2,6-di-tert-butyl-4-methylphenol (BHT), 9.7*10 -2 g's SnapCure TM 1030 was charged and the resulting mixture was heated to 50° C. Then 12.3 g of 2-isocyanatoethyl methacrylate (79.1 meq) was slowly added, the temperature was raised to 60° C. and the reaction mixture was left under vigorous stirring for 3 hours. Afterwards 1.2 g of methanol was added and the reaction mixture was stirred for a further 2 hours and dried under reduced pressure (T=60° C., P=2 Pa) to obtain 110.7 g of composition B.

[0109] Example 3 - Synthesis of Composition C A 50 ml three-neck round bottom flask equipped with a condenser, a thermometer probe, a rubber septum and a magnetic stir bar was charged with 40 g of the product obtained in step 2 of Example 2, 6.50 g of 3-(trimethoxysilyl)propyl isocyanate (31.6 mmol) and the mixture was heated to 50° C. Then, 187 μl of DBTDL solution (20 wt % in ethyl methyl ketone) was added, the temperature was increased to 60° C. and the reaction was left under vigorous stirring for 3 hours. After that, 0.5 g of methanol was added and the reaction mixture was stirred for an additional 2 hours and dried under reduced pressure (T=60° C., P=2 Pa) to obtain 45.1 g of composition C.

[0110] Example 4 – Synthesis of Composition D Step 1: A 0.5 L four-neck round-bottom flask kept under nitrogen and equipped with a condenser, mechanical stirrer, thermometer probe and dropping funnel was charged with 200 g (EW=g / mol 871; 229.6 meq) of Fomblin® ZDOL, 150 g of 1,3-bis(trifluoromethyl)benzene and 52.1 g of a solution of sodium methoxide in methanol (25% by weight). The flask was then heated up to 60° C. and left under stirring for 1 hour under nitrogen and a gentle nitrogen flow. Afterwards, 26.7 g of methyl chloroacetate (245.7 meq) were added and the reaction mixture was left under stirring for a further 4 hours. Then, 150 g of a 4 M aqueous solution of HCl and 20 g of methanol were added to the reaction mixture and the organic phase formed thereby was separated. After distillation of the fluorinated solvent under reduced pressure (T=80° C., P=2 Pa), 211.5 g of a clear liquid was isolated and characterized. 1 H-NMR and 19 N-NMR analysis confirmed 100% conversion of the methylol groups to the corresponding methyloxymethyl acetates.

[0111] Step 2: A 0.25 L four-neck round bottom flask kept under nitrogen and equipped with a condenser, mechanical stirrer, thermometer probe and dropping funnel was charged with 60 g of 1,3-bis(trifluoromethyl)benzene, 7.7 g (49.3 mmol) of 4-amino-2,2,6,6-tetramethylpiperidine and 150 g of the product obtained in step 1. The resulting mixture was heated to 70° and left under vigorous stirring for 36 hours. Distillation under reduced pressure (T=80° C., P=2 Pa) to remove the solvent gave 152.1 g of a clear liquid, which was characterized. 1 1 H NMR confirmed 30% conversion of the methyl ester group to the target amide.

[0112] Step 3: A 0.25 L four-neck round bottom flask kept under nitrogen and equipped with a condenser, mechanical stirrer and thermometer probe was charged with 100 g of 1,3-bis(trifluoromethyl)benzene, 50 g of the product obtained in step 2 of Example 4 and 2.4 g (40.8 mmol) of oxiran-2-amine. The resulting mixture was heated to 65° and left under vigorous stirring for 35 hours. Distillation under reduced pressure (T=80° C., P=2 Pa) to remove the solvent gave 50.2 g of composition D.

[0113] Test A - UV resistance evaluation A composition (A) was prepared by mixing 90% by weight of Fluorolink® MD700 with 10% by weight of composition B according to the invention, prepared as described in example 2. Composition (B) containing 100% by weight of Fluorolink® MD700 was used as a comparison.

[0114] Specimens were coated with a composition according to the invention (A) and with a comparative composition (B) and then exposed to UV radiation for 300 hours (QUV test exposure). After this time, the coatings were visually inspected and the gloss was measured using the following settings: UVB: 310nm; Irradiance 0.63W / m 2 ; Cold shower time 3 min / hour; Dark board temperature 63℃ The measurements were taken after QUV test exposure at 60° (ASTM D2457-60°).

[0115] The coating obtained with the composition according to the invention (A) appears to be homogeneous, whereas the coating obtained with the comparative composition (B) exhibits slight damaged areas with a gloss of less than 100.

Claims

1. (Per) fluoropolyoxyalkylene chain [chain (R ｐｆ )] and the chain (R ｐｆ (Per)fluoropolyoxyalkylene chain having two chain ends bonded to the opposite side of (R) ｐｆ (P) Fluoropolyether polymer containing ) )] [polymer (P Ｐ ) ] and * One of the chain ends comprises at least one, preferably 1 to 3, crosslinkable groups (group [I]) selected from alkoxysilane [group (Si)], or unsaturated moieties [group (U)] and epoxide [group (E)]; and * The other chain ends contain at least one, preferably 1 to 3 groups (group [II]) selected from optionally substituted piperidine, optionally substituted pyridine, or optionally substituted pyrrole, (per)fluoropolyether polymer [polymer (P Ｐ )].

2. Chain (R ｐｆ ) is the formula '(C') ｚ１ () ｆ (()) ｚ２  (In the formula, z1 and z2, which are equal to or different from each other, are 1 or more, preferably 1 to 10, more preferably 1 to 3; X and X' that are equal to or different from each other are -F or -CF ３ And, However, if z1 and / or z2 are greater than 1, then X and X' are -F; D and D', which are equal to or different from each other, are sigma bonds or hydrogenated alkylene chains containing 1 to 6, more preferably 1 to 3, carbon atoms, wherein the alkyl chain is optionally substituted with at least one perfluoroalkyl group containing 1 to 3 carbon atoms; (R ｆ ) includes repeating units R°, preferably consisting of them, and the repeating units are (i) -CFXO-(wherein X is F or CF) ３ (is); (ii) - CFXCFXO - (wherein each occurrence X is equal to or different from F or CF) ３ (wherein at least one of X is -F); (iii)-CF ２ CF ２ CW ２ O - (wherein the formula, each of W that is equal to or different from each other is F, Cl, or H); (iv)-CF ２ CF ２ CF ２ CF ２ O-; (v) - (CF ２ ) ｊ -CFZ-O-(wherein j is an integer from 0 to 3, and Z is the general formula -O-R) （ｆ－ａ） -T is the base, R （ｆ－ａ） This is a fluoropolyoxyalkene chain containing 0 to 10 repeating units, wherein the repeating units are -CFXO-, -CF ２ CFXO-, -CF ２ CF ２ CF ２ O-, -CF ２ CF ２ CF ２ CF ２ Selected from O-, each of X independently becomes F or CF ３ And T is C １ ~C ３ (It is a perfluoroalkyl group.) (Selected independently from the group consisting of) The polymer (P) according to claim 1, which is a chain of Ｐ ).

3. The group [I] is connected to the chain (R) via a linking group. ｐｆ The polymer (P) described in claim 1 is linked to the polymer (P) Ｐ ).

4. The aforementioned linking group is given by the following formula: *-(R ａ ) ｔ -(R ｂ ) ｖ -(R ｃ ) ｕ -§ (In the formula, * indicates chain (R ｐｆ This shows a binding to ), § indicates a bond to the group [I]; R ａ is a poly(oxy)alkylene chain; t is an integer of 0 or 1 to 15, preferably 1 to 10; v is either 0 or 1; R ｂ The formula is: (R ｂ -I)-O-C(=O)-NH-(CH ｈ ) ｅ - (R) ｂ -II)-C(=O)-NR'-(CH ｈ ) ｆ - (R ｂ -III)-O-(CH ２ ) ｇ -C(=O)- (In the formula, e is an integer from 1 to 6. R' is a linear or branched alkyl group having H or 1 to 6 carbon atoms. f is an integer between 1 and 4. g is an integer from 1 to 4, and Each h is an independent integer equal to 0, 1, or 2, except that if h is 0, then e and f are each independently 1. It is the basis of; R ｃ is a linear or branched alkyl chain having 1 to 12 carbon atoms, optionally containing one or more oxygen atoms, or an optionally substituted aliphatic cycloalkyl having 5 or 6 members; and (u is either 0 or 1) The polymer (P) according to claim 3. Ｐ ).

5. (R ａ The polymer (P) described in claim 4 is a poly(oxy)alkylene chain containing 1 to 50 oxyalkylene units that do not contain fluorine. Ｐ ).

6. Base [I] is base (U), and said base (U) is (U-I)-O-C(=O)-CR Ｈ =CH ２ (----)-O-C(=O)-+---CR Ｈ =CH ２ (U-III)-O-C(=O)-R Ａ -CR Ｈ =CH ２ (In the formula, R Ｈ is H or C １ ~C ６ It is an alkyl group; R Ａ is, (R Ａ -I) and (R Ａ -II): (R Ａ -I) 【Chemistry 1】 (In the formula, Each of j5 is independently either 0 or 1, and R Ｂ C optionally contains at least one heteroatom selected from N, O, and S. １ ~C １０ Aliphatic group; C ３ ~C １２ Alicyclic group; C ５ ~C １４ (A divalent, trivalent, or tetravalent group selected from the group consisting of aromatic groups or alkyl aromatic groups); () Ａ .)) 【Chemistry 2】 (In the formula, j6 is either 0 or 1; Each of j7 is independently either 0 or 1; R Ｂ’ C optionally contains at least one heteroatom selected from N, O, and S. １ ~C １０ Aliphatic group; C ３ ~C １２ Alicyclic group; C ５ ~C １４ A divalent, trivalent, or tetravalent group selected from the group consisting of aromatic groups or alkyl aromatic groups; and R Ｂ＊ has the same meaning as defined above for R Ｂ’ or it is of the formula (R Ｂ -I): 【Transformation 3】 (In the formula, Substituent U is selected from the groups (U-I) to (U-III) as defined above, and * and # are the same as in the above formula (R Ａ -II) Shows the bonding site to the nitrogen atom. (It is the basis of) (Selected from the group consisting of) A polymer (P) selected from the group consisting of the group comprising the group described in claim 1. Ｐ ).

7. The group [I] is the group (Si), and the group (Si) is given by formula: -Si-(OR ３０ ) ３ (wherein, R ３０ is a linear or branched alkyl chain having 1 to 12 carbon atoms) The polymer (P) according to claim 1. Ｐ ).

8. Base [I] is base (E), and base (E) is given by the following formula: *-(R ａ ) ｔ -(R ｃ ) ｕ -§ (In the formula, *, §, R ａ ,t,R ｃ (and u have the meanings described in claim 4) The chain (R) is connected via a linking group according to the following ｐｆ The polymer (P) according to claim 1 is bonded to the polymer (P) Ｐ ).

9. Base [II] is, - Formula: *-(R ａ ) ｔ -NH-§ or *-(R ａ ) ｔ -O-§ (In the formula, * indicates chain (R ｐｆ ) indicates bonding to group [II], and § indicates bonding to group [II], and R ａ (Each of and t has the meaning described in claim 4) Chain (R) via the group ｐｆ ) is bonded to each of the groups D or D', and Chain (R ｐｆ Each of the groups D and D' in ) is a hydrogenated alkylene chain containing 1 to 6 carbon atoms; or Base [II] is, - Formula: -(R ａ ) ｔ -(R* ｐ C(=O)NH-(R** ｑ Or -(R ａ ) ｔ -(R*** ｒ C(=O)O-(R**** ｓ - (In the formula, p, q, r, and s are each independently 0 or an integer from 1 to 6. R ａ And t have the meanings defined above, and Each of R*, R**, R***, and R**** is independently a linear or branched alkyl chain containing 1 to 6 carbon atoms. Chain (R) via the group ｐｆ ) is bonded to each of the groups D or D', and Chain (R ｐｆ The polymer (P) in which each group D and D' is a sigma bond, according to claim 1. Ｐ ).

10. The group [II] is selected from substituted piperidine, substituted pyridine and substituted pyrrole, and is the polymer (P) according to claim 1. Ｐ ).

11. The polymer (P) according to claim 1, wherein group [II] is a derivative of 4-amino-2,2,6,6-tetramethylpiperidine. Ｐ ).

12. - Polymer (P) according to claim 1 Ｐ )and; - (Per)fluoropolyoxyalkylene chain [chain (R ｐｆ )] and the chain (R ｐｆ (Per)fluoropolyoxyalkylene chain having two chain ends bonded to the opposite side of (R) ｐｆ (P) Fluoropolyether polymer containing ) )] [polymer (P Ｕ )] and both chain ends contain a (per)fluoropolyether polymer [polymer (P Ｕ )]and; - (Per)fluoropolyoxyalkylene chain [chain (R ｐｆ )] and the chain (R ｐｆ (Per)fluoropolyoxyalkylene chain having two chain ends bonded to the opposite side of (R) ｐｆ (P) Fluoropolyether polymer containing ) )] [polymer (P Ｎ )] and both chain ends contain a (per)fluoropolyether polymer [polymer (P Ｎ )]and Composition containing [Composition (C ＰＯＬ )].

13. (Per) fluoropolyether chain [chain (R ｐｆ )] and the chain (R ｐｆ (Per)fluoropolyether chain having two chain ends bonded to the opposite side of (R) ｐｆ (P) Fluoropolyether polymer containing ) )] [polymer (P ｘ The composition according to claim 12 (C) further comprising, one chain end comprising a perfluoroalkyl group and the other chain end comprising at least one group of formula [I] or formula [II] as described in claim 1. ＰＯＬ ).

14. - (Per)fluoropolyether chain [chain (R ｐｆ )] and the chain (R ｐｆ (Per)fluoropolyether chain having two chain ends bonded to the opposite side of (R) ｐｆ (P) Fluoropolyether polymer containing ) )] [polymer (P ＩＮＴ )] and one of the chain ends is of the formula -OH or -C(=O)OR １０ (In the formula, R １０ The polymer (P) contains a group (which is a linear or branched alkyl chain containing H or 1 to 6 carbon atoms), and the other chain ends contain a group [II], a (per) fluoropolyether polymer [polymer (P ＩＮＴ )]and; - (Per)fluoropolyether chain [chain (R ｐｆ )] and the chain (R ｐｆ (Per)fluoropolyether chain having two chain ends bonded to the opposite side of (R) ｐｆ A (per)fluoropolyether polymer [polymer PFPE] comprising ) ], wherein both chain ends are of the formula -OH or -C(=O)OR １０ (In the formula, R １０ (As defined above) a (per)fluoropolyether polymer [polymer PFPE] containing the group; - (Per)fluoropolyether chain [chain (R ｐｆ )] and the chain (R ｐｆ (Per)fluoropolyether chain having two chain ends bonded to the opposite side of (R) ｐｆ (P) Fluoropolyether polymer containing ) )] [polymer (P ＩＩ )] and both of the chain ends contain the group [II], a (per)fluoropolyether polymer [polymer (P ＩＩ )]and A composition containing [Composition (INT)].

15. The composition [composition (INT)] according to claim 14, wherein base [II] is as described in claim 9.

16. (Per) fluoropolyether chain [chain (R ｐｆ )] and the chain (R ｐｆ (Per)fluoropolyether chain having two chain ends bonded to the opposite side of (R) ｐｆ (P) Fluoropolyether polymer containing ) )] [polymer (P ＩＮＴ )] and one of the chain ends is of the formula -OH or -C(=O)OR １０ (In the formula, R １０ The polymer (P) contains a group (which is a linear or branched alkyl chain containing H or 1 to 6 carbon atoms), and the other chain ends contain a group [II], a (per) fluoropolyether polymer [polymer (P ＩＮＴ )].

17. Group [II] is as described in claim 9, the (per)fluoropolyether polymer [polymer (P ＩＮＴ )].

18. A process for synthesizing the composition (INT) described in claim 14, (i) (per)fluoropolyether chain [chain (R ｐｆ )] and the chain (R ｐｆ (Per)fluoropolyether chain having two chain ends bonded to the opposite side of (R) ｐｆ To provide a (per)fluoropolyether polymer [polymer PFPE] comprising ) ], wherein both chain ends are -OH or -C(=O) OR １０ (In the formula, R １０ (This is a linear or branched alkyl chain containing H or 1 to 6 carbon atoms.) To provide, including a base selected from; (ii) If present, at least a portion of the group -OH is a leaving group for a nucleophilic substitution reaction or a group of the formula -O(R***) ｒ C(=O)O-(R Ｖ ) (wherein R*** and r are as defined above, R Ｖ This involves converting to a group of alkyl chains containing one to three carbon atoms; (iii) The PFPE polymer from step (i) or the composition obtained in step (ii) is given the formula -OH or -NH ２ Contact with a group and at least one compound containing a group derived from one of optionally substituted piperidine, optionally substituted pyridine, or optionally substituted pyrrole, and thus obtain composition [composition (INT)]. A process that includes this.

19. The composition according to claim 12 (C ＰＯＬ The process of synthesizing ) (iv) to provide the composition (INT) according to claim 13, and to provide the composition (INT), - A compound [A] having at least one group (U) as defined above and at least one halogen atom, isocyanate group or amino group; or - A compound [B] having at least one group (E) as defined above and at least one halogen atom or at least one isocyanate group; or - A compound having at least one group as defined above (Si) and at least one isocyanate group or amino group [C] The composition (C) is brought into contact with at least one compound selected from the group consisting of the above, and therefore the composition (C ＰＯＬ ) to obtain; or (i*) (per) fluoropolyether chain [chain (R ｐｆ )] and chain (R ｐｆ (Per)fluoropolyether chain having two chain ends bonded to the opposite side of (R) ｐｆ To provide a (per)fluoropolyether polymer [polymer PFPE] comprising ) ], wherein both chain ends are -OH or -C(=O)OR １０ (In the formula, R １０ The material provides a group selected from H or a linear or branched alkyl chain containing 1 to 6 carbon atoms; (ii*) If present, at least a portion of the -OH group is a leaving group for a nucleophilic substitution reaction or a group of the formula -O(R***) ｒ C(=O)O-(R Ｖ ) (wherein R*** and r are as defined above, R Ｖ This involves converting to a group of alkyl chains containing 1 to 3 carbon atoms; (iii*) The PFPE polymer from step (i) or the composition obtained in step (ii) is given the formula -OH or -NH ２ Contact with at least one compound containing the group and a group derived from one of optionally substituted piperidine, optionally substituted pyridine, or optionally substituted pyrrole. 、 And thus obtain composition (INT); (iv*) A composition (INT) obtained in step (iii), - A compound [A] having at least one group (U) as described in claim 6 and at least one halogen atom, isocyanate group or amino group; or - A compound [B] having at least one group (E) and at least one halogen atom or at least one isocyanate group as described in claim 8; or - A compound having at least one group (Si) and at least one isocyanate group or amino group as described in claim 7 [C] The mixture is brought into contact with at least one compound selected from the group consisting of C ＰＯＬ ) to obtain A process that includes this.

20. In step (iv) or step (iv*), compound [A] is of the following formula: O=C=N-R ２０ -R ２１ -CR Ｈ =CH ２ (In the formula, R Ｈ This has the same meaning as defined above for the base (U); R ２０ This is a linear or branched alkyl chain having 1 to 6 carbon atoms, optionally substituted with a group containing a trial-alkoxy-silyl group; R ２１ has the formula -OC(=O)-, -OC(=O)-NH-CO-, -OC(=O)-R Ａ - (wherein, R Ａ (This is a divalent group of the group (U-III) as defined above.) The process according to claim 19.

21. Formula -OH or -NH ２ The process according to claim 18, wherein the compound comprising the group and a group derived from one of optionally substituted piperidine, optionally substituted pyridine, or optionally substituted pyrrole is selected from 4-amino-2,2,6,6-tetramethylpiperidine, 2,2,6,6-tetramethyl-4-piperidinol, and 2-(2,2,6,6-tetramethyl-piperidine-4-yl)ethanol.

22. At least one polymer (P) according to claim 1 Ｐ ) or the composition according to claim 12 (C ＰＯＬ )and; (Per)fluoropolyether polymers having at least one functional group selected from unsaturated groups, alkoxysilane groups, or epoxy groups at the end of their chains, preferably at least one solvent (S) and A composition containing [Composition (DIL)].

23. Composition [Composition (C Ｆ )] a polymer (P) comprising the group (U) described in claim 6, at least one polymer (P) Ｐ The composition (DIL) according to claim 22, which includes ) At least one UV-curable component and The composition (C Ｆ ) polymer (P Ｐ The amount of the composition (C Ｆ A composition containing 0.01 to 8.00% by weight based on the total weight of ) [Composition (C Ｆ )].

24. A method for providing a transparent coating on at least the surface of a substrate, (i) to provide at least one substrate having at least one surface; (ii) The polymer (P) described in claim 1 on at least one of the surfaces Ｐ ), the composition according to claim 12 (C ＰＯＬ ), the composition (DIL) according to claim 22 or the composition (C) according to claim 23 Ｆ To bring into contact with at least one selected from the group consisting of ) A method that includes this.

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