Curable composition

Abstract

The present invention provides a curable composition containing a silicone copolymer having two or more crosslinkable groups, the crosslinkable groups being groups containing a carbon-carbon double bond, a carbon-carbon triple bond, a cyclic ether group, a hydroxyl group, a mercapto group, an amino group, an azido group, a nitrogen-containing heterocyclic group, an isocyanate group, a halogen atom, a phosphorus-containing acid group, or a silane coupling group, or being a precursor group thereof, a fluorine-containing polyether group-containing compound, and a matrix-forming composition.

Description

Technical Field

[0001] This invention relates to curable compositions. Background Technology

[0002] It is known that a certain organosilicon compound can provide excellent antifouling properties when used for surface treatment of substrates (Patent Document 1). It is also known that a certain fluorine-containing compound can provide excellent water-repellent and oil-repellent properties when used for surface treatment of substrates (Patent Document 2).

[0003] Existing technical documents

[0004] Patent documents

[0005] Patent Document 1: Japanese Patent Application Publication No. 2009-143048

[0006] Patent Document 2: International Publication No. 97 / 07155 Summary of the Invention

[0007] The technical problem that the invention aims to solve

[0008] The layer obtained from the aforementioned surface treatment agent containing organosilicon compounds or fluorine compounds is applied as a so-called functional film to various substrates such as plastics, fibers, and building materials. However, while the organosilicon compounds described in Patent Document 1 can impart functions such as antifouling properties to the substrate, problems such as exudation sometimes occur after the surface treatment layer is formed. Furthermore, the fluorine-containing compounds described in Patent Document 2 sometimes have poor tactile properties such as slipperiness.

[0009] The object of the present invention is to provide a curable composition that can form a layer on a substrate made of various materials including resin, having water-repellent properties, excellent surface sliding properties, and being resistant to exudation.

[0010] Technical solutions for solving technical problems

[0011] [1] A curable composition comprising an organosilicon copolymer, a fluorinated polyether compound and a matrix-forming composition, wherein the organosilicon copolymer has two or more crosslinking groups, the crosslinking groups being groups comprising carbon-carbon double bonds, carbon-carbon triple bonds, cyclic ether groups, hydroxyl groups, mercapto groups, amino groups, azide groups, nitrogen-containing heterocyclic groups, isocyanate groups, halogen atoms, groups containing phosphate groups or silane coupling groups, or precursor groups thereof.

[0012] [2] The curable composition as described in [1] above, wherein the organosilicon copolymer has three or more crosslinking groups.

[0013] [3] The curable composition as described in [1] or [2] above, wherein the organosilicon copolymer is a chain copolymer.

[0014] [4] The curable composition as described in [3] above, wherein the chain copolymer is an addition copolymer.

[0015] [5] The curable composition as described in [4] above, wherein the addition copolymer is a free radical copolymer or an ionic copolymer.

[0016] [6] The curable composition as described in [4] above, wherein the addition copolymer is a free radical copolymer.

[0017] [7] The curable composition as described in any one of [1] to [6] above, wherein the organosilicon copolymer is a block copolymer.

[0018] [8] The curable composition as described in any one of [1] to [7] above, wherein the siloxane portion of the organosilicon copolymer is chain-like.

[0019] [9] The curable composition described in any one of [1] to [8] above, wherein the organosilicon copolymer is an organosilicon copolymer represented by formula (1) or (2).

[0020]

[0021] [In the formula,

[0022] R 1 It is a hydrogen atom or a carbon atom. 1－6 alkyl;

[0023] R 2 Each time it appears, it is independently represented by a hydrogen atom or a carbon atom. 1－6 alkyl;

[0024] m is an integer from 1 to 300;

[0025] R 4 Each occurrence is independently assigned the value R. 4a Or R 4b ;

[0026] R 4a Each time it appears, it is independently a divalent organic group with cross-linking properties;

[0027] R 4b Each time it appears, it is an independent divalent organic group that does not have a cross-linking group;

[0028] The aforementioned crosslinking groups are groups containing carbon-carbon double bonds, carbon-carbon triple bonds, cyclic ether groups, hydroxyl groups, mercapto groups, amino groups, azide groups, nitrogen-containing heterocyclic groups, isocyanate groups, halogen atoms, groups containing phosphate groups or silane coupling groups, or groups containing their precursor groups.

[0029] n is an integer from 1 to 90;

[0030] X a Each is an organic group that is independently divalent;

[0031] X b Each is an organic group that is independently divalent;

[0032] R a Each is independently an alkyl, phenyl, or -SR a1 -OR a2 、-NR a3 2.

[0033]

[0034] R a1 R a2 R a3 R a4 R a5 and R a6 Each can be independently an alkyl or phenyl group;

[0035] R a7 It can be a hydrogen atom or a halogen atom.

[0036]

[10] The curable composition as described in any one of [1] to [9] above, wherein the organosilicon copolymer has three or more crosslinking groups at the end.

[0037]

[11] The curable composition as described in any one of [1] to

[10] above, wherein the organosilicon copolymer is hydrophobic.

[0038]

[12] The curable composition as described in any one of [9] to

[11] above, wherein R 4 For R 4a .

[0039]

[13] The curable composition as described in any one of [9] to

[12] above, wherein R 4a It is a group represented by the following formula.

[0040]

[0041] [In the formula,

[0042] R 31 Each time it appears, it is independently represented by a hydrogen atom or an alkyl group;

[0043] R 32 Each time it appears, it is independently a hydrogen atom, a chlorine atom, a fluorine atom, or an alkyl group that can be substituted by fluorine;

[0044] R 33 Each time it appears, it is an independent cross-linking group;

[0045] Y 1 For single bonds, -C(=O)O-, -C(=O)NH-, -OC(=O)-, -NHC(=O)-, -O-, -N(R) c )-, aromatic ring, aromatic ring with substituents or carbazoyl group;

[0046] R c It is an organic group.

[0047] Y 2 It is a linker group consisting of single bonds or 1 to 16 atoms in the main chain.

[0048]

[14] The curable composition as described in any one of [1] to

[13] above, wherein the crosslinking group is an epoxy group, a glycidyl group, an alicyclic epoxy group, a vinyl group, an allyl group, a substituted acryloyl group, a cinnamoyl group, a 2,4-hexadienoyl group, a vinyl ether (vinyloxy) group, a hydroxy group, an oxetyl group, an isocyanate group, a catechol group, a mercapto group, an amino group, an alkylamino group, a dialkylamino group, an azide group, a phosphate group, a carboxyl group, an imidazole group, a triazole group, a benzotriazole group, a tetrazolium group, a halogen atom or a silane coupling group, or a precursor group thereof.

[0049]

[15] The curable composition as described in any one of [1] to

[14] above, wherein the crosslinking group is an epoxy group, a glycidyl group, an alicyclic epoxy group, an acryloyl group or a methacryloyl group.

[0050]

[16] The curable composition as described in any one of [9] to

[15] above, wherein n is an integer from 2 to 50.

[0051]

[17] The curable composition as described in any one of [9] to

[16] above, wherein n is an integer from 3 to 30.

[0052]

[18] The curable composition as described in any one of [9] to

[17] above, wherein R 2 Each occurrence is independently assigned the number C. 1－6 alkyl.

[0053]

[19] The curable composition as described in any one of [9] to

[18] above, wherein m is an integer from 2 to 250.

[0054]

[20] The curable composition as described in any one of [1] to

[19] above, wherein the fluorine content in the fluorinated polyether compound is in the range of 2 to 70% by weight.

[0055]

[21] The curable composition as described in any one of [1] to

[20] above, wherein the fluorine content in the fluorinated polyether compound is in the range of 10 to 60% by weight.

[0056]

[22] The curable composition as described in any one of [1] to

[21] above, wherein the fluorinated polyether compound is a chain copolymer.

[0057]

[23] The curable composition as described in

[22] above, wherein the chain copolymer is an addition copolymer.

[0058]

[24] The curable composition as described in

[23] above, wherein the addition copolymer is a free radical copolymer or an ionic copolymer.

[0059]

[25] The curable composition as described in

[23] above, wherein the addition copolymer is a free radical copolymer.

[0060]

[26] The curable composition as described in any one of [1] to

[25] above, wherein the fluorinated polyether compound is a block copolymer.

[0061]

[27] The curable composition as described in any one of [1] to

[26] above, wherein the fluorinated polyether compound is a fluorinated polyether compound represented by any one of the following formulas (3) to (5).

[0062]

[0063] [In the formula,

[0064] R F1 For Rf 1 -R F -O q -;

[0065] R F2 -Rf 2 p -R F -O q -;

[0066] Rf 1 C atoms that can be substituted by one or more fluorine atoms 1－16 alkyl;

[0067] Rf 2C atoms that can be substituted by one or more fluorine atoms 1－6 Alkylene;

[0068] R F Each is independently a divalent fluorinated polyether group;

[0069] p is 0 or 1;

[0070] q can be 0 or 1 independently;

[0071] R 4′ Each occurrence is independently assigned the value R. 4a′ Or R 4b′ ;

[0072] R 4a′ Each time it appears, it is independently an organic group with a divalent functional group selected from substituent group A;

[0073] R 4b′ Each time it appears, it is independently a divalent organic group that does not have a functional group selected from substituent group A;

[0074] The substituent group A mentioned above includes carbon-carbon double bonds, carbon-carbon triple bonds, cyclic ether groups, hydroxyl groups, mercapto groups, amino groups, azide groups, nitrogen-containing heterocyclic groups, isocyanate groups, halogen atoms, groups containing phosphate groups and silane coupling groups, as well as their precursor groups;

[0075] n ′ Integers from 1 to 100;

[0076] X a′ Each is an independent divalent organic group;

[0077] X b′ Each is an independent divalent organic group;

[0078] R a′ Each is independently an alkyl, phenyl, or -SR a1 -OR a2 、-NR a3 2.

[0079]

[0080] R a1 R a2 R a3 R a4 R a5 and R a6 Each can be independently an alkyl or phenyl group;

[0081] R a7 It can be a hydrogen atom or a halogen atom.

[0082]

[28] The curable composition as described in

[27] above, wherein R 4′ For R 4a′ .

[0083]

[29] The curable composition described in

[27] or

[28] above, wherein R 4a′ It is a group represented by the following formula.

[0084]

[0085] [In the formula,

[0086] R 31′ Each time it appears, it is independently represented by a hydrogen atom or an alkyl group;

[0087] R 32′ Each time it appears, it is independently a hydrogen atom, a chlorine atom, a fluorine atom, or an alkyl group that can be substituted by fluorine;

[0088] R 33′ Each time it appears, it is an independent cross-linking group;

[0089] Y 1′ For single bonds, -C(=O)O-, -C(=O)NH-, -OC(=O)-, -NHC(=O)-, -O-, -N(R) c )-, phenylene or carbazoyl group;

[0090] R c It is an organic group.

[0091] Y 2′ It is a linker group consisting of single bonds or 1 to 16 atoms in the main chain.

[0092]

[30] The curable composition as described in any one of

[27] to

[29] above, wherein the functional group selected from substituent group A is an epoxy group, an alicyclic epoxy group, a glycidyl group, or CH2=CX. 1′ -C(O)-(where X) 1′ (Represents a hydrogen atom, chlorine atom, fluorine atom, or an alkyl group having 1 to 10 carbon atoms that can be replaced by fluorine).

[0093]

[31] The curable composition as described in any one of

[27] to

[30] above, wherein n′ is an integer from 2 to 50.

[0094]

[32] The curable composition as described in any one of

[27] to

[31] above, wherein n′ is an integer from 3 to 30.

[0095]

[33] The curable composition as described in any one of

[27] to

[32] above, wherein the organosilicon copolymer is the organosilicon copolymer represented by formula (1) or (2) above, and the fluorinated polyether compound is the fluorinated polyether compound represented by formula (3) or (4) above.

[0096]

[34] The curable composition as described in any one of [1] to

[25] above, wherein the fluorinated polyether compound is a fluorinated polyether compound represented by the following formula (5).

[0097] (R F1 -X c ) n2 -R 10 -(R 8 -OC(O)CR 9 =CH2) n3 (5)

[0098] [In the formula,

[0099] R F1 For Rf 1 -R F -O q -;

[0100] Rf 1 C atoms that can be substituted by one or more fluorine atoms 1－16 alkyl;

[0101] R F Each is independently a divalent fluorinated polyether group;

[0102] q is 0 or 1;

[0103] X c This can be expressed as: -(Q) d -(CFZ) e -(CH2) f - The group shown,

[0104] (Formula - (Q)) d -(CFZ) e -(CH2) f In the symbol - Q represents oxygen atom, phenylene, carbazolyl group, and -NR. a - or divalent polar group, formula -NR a - In the middle, R a Indicates a hydrogen atom or an organic group.

[0105] Z represents a hydrogen atom, a fluorine atom, or a lower fluorinated alkyl group.

[0106] d, e, and f are each an independent integer from 0 to 50, and the sum of d, e, and f is at least 1. The order of the repeating units enclosed in parentheses is arbitrary in the formula.

[0107] R 10 This indicates an organic group with (n2+n3) valence that can have a ring structure, heteroatoms, and / or functional groups.

[0108] R 8 Represents a divalent organic group.

[0109] R 9 This refers to an alkyl group containing 1 to 10 carbon atoms, including hydrogen, chlorine, fluorine, or fluorine-substituted carbon atoms.

[0110] n2 is an integer from 1 to 3.

[0111] n3 is an integer from 1 to 3.

[0112]

[35] The curable composition as described in any one of

[27] to

[34] above, wherein R F Separately, the formula is: -(OC6F 12 ) a -(OC5F) 10 ) b -(OC4F8) c -(OC3R) Fa 6) d -(OC2F4) e -(OCF2) f - The group shown.

[0113] [In the formula, R] Fa Each time it appears, it is independently represented by a hydrogen atom, a fluorine atom, or a chlorine atom.

[0114] a, b, c, d, e, and f are each independent integer from 0 to 200, and the sum of a, b, c, d, e, and f is 1 or more. The order of repeated units labeled a, b, c, d, e, or f and enclosed in parentheses is arbitrary in the formula.

[0115]

[36] The curable composition as described in

[35] above, wherein R Fa It is a fluorine atom.

[0116]

[37] The curable composition as described in any one of

[27] to

[36] above, wherein R F Each of these groups is independently represented by one of the following formulas (f1), (f2), (f3), (f4), or (f5).

[0117] -(OC3F6) d -(OC2F4)e - (f1)

[0118] [In the formula, d is an integer from 1 to 200, and e is 0 or 1.]

[0119] -(OC4F8) c -(OC3F6) d -(OC2F4) e -(OCF2) f - (f2)

[0120] [In the formula, c and d are independent integers from 0 to 30;]

[0121] e and f are independent integers from 1 to 200;

[0122] The sum of c, d, e, and f is an integer between 10 and 200;

[0123] The order of repeated units marked with subscripts c, d, e, or f and enclosed in parentheses is arbitrary in the formula.

[0124] -(R) 6 -R 7 ) g - (f3)

[0125] [In the formula, R] 6 It is either OCF2 or OC2F4;

[0126] R 7 Selected from OC2F4, OC3F6, OC4F8, OC5F 10 and OC6F 12 The group, or a combination of two or three groups selected from these groups;

[0127] g is an integer from 2 to 100.

[0128] -(OC6F 12 ) a -(OC5F) 10 ) b -(OC4F8) c -(OC3F6) d -(OC2F4) e -(OCF2) f - (f4)

[0129] [In the formula, e is an integer greater than 1 and less than 200, a, b, c, d, and f are each an independent integer greater than 0 and less than 200, the sum of a, b, c, d, e, and f is at least 1, and the order of the repeating units labeled a, b, c, d, e, or f and enclosed in parentheses is arbitrary in the formula.]

[0130] -(OC6F 12 ) a -(OC5F) 10 ) b -(OC4F8) c -(OC3F6) d -(OC2F4) e -(OCF2) f - (f5)

[0131] [In the formula, f is an integer greater than 1 and less than 200, a, b, c, d, and e are each an independent integer greater than 0 and less than 200, the sum of a, b, c, d, e, and f is at least 1, and the order of the repeated units labeled a, b, c, d, e, or f and enclosed in parentheses is arbitrary in the formula.]

[0132]

[38] The curable composition as described in any one of

[27] to

[37] above, wherein it further comprises at least one fluorinated oil represented by the following general formula (C).

[0133] Rf 2 -(OC4F8) a′ -(OC3F6) b′ -(OC2F4) c′ -(OCF2) d′ -Rf 3 …(C)

[0134] [In the formula,

[0135] Rf 2 It is an alkyl group having 1 to 16 carbon atoms that can be replaced by one or more fluorine atoms;

[0136] Rf 3 It is a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 16 carbon atoms that can be replaced by one or more fluorine atoms;

[0137] In the above formula (C), a′, b′, c′, and d′ represent the number of three repeating units of the perfluoro(poly)ether constituting the main backbone of the polymer, and are independent integers between 0 and 300. The sum of a′, b′, c′, and d′ is at least 1.

[0138] The order of repeated units marked with subscripts a′, b′, c′, or d′ and enclosed in parentheses is arbitrary in the formula.

[0139]

[39] The cured composition as described in any one of [1] to

[38] above, wherein the mass ratio of the organosilicon copolymer to the fluorinated polyether compound in the cured composition is in the range of 0.1:100 to 100:0.1.

[0140]

[40] The cured composition as described in any one of [1] to

[39] above, wherein the mass ratio of the organosilicon copolymer to the fluorinated polyether compound in the cured composition is in the range of 0.5:100 to 100:100.

[0141]

[41] A film formed from any one of the curable compositions described in [1] to

[40] above.

[0142]

[42] An article comprising a substrate and a layer formed on the surface of the substrate by any one of the curable compositions described in [1] to

[40] above.

[0143]

[43] The item described above in

[42] is an optical component.

[0144]

[44] The item described above in

[42] is a LiDAR cover component.

[0145]

[45] The item described above in

[42] is a sensor component.

[0146]

[46] The item described above in

[42] is a dashboard cover component.

[0147]

[47] The items described above in

[42] are automotive interior components.

[0148] Invention Effects

[0149] The curable composition of the present invention can form a layer with excellent water repellency and surface lubrication, and is not easily seeped out. Detailed Implementation

[0150] In this specification, "organic group" refers to a monovalent group containing carbon. Unless otherwise specified, an organic group can be a hydrocarbon group or its derivative. A hydrocarbon derivative refers to a group having one or more N, O, S, Si, amide, sulfonyl, siloxane, carbonyl, or carbonyloxy groups at the end of the hydrocarbon group or in the molecular chain. When simply referred to as "organic group," it means a monovalent organic group. Furthermore, "divalent organic group" refers to a divalent group containing carbon. Such divalent organic groups are not particularly limited; examples include divalent groups that have been separated from an organic group by one hydrogen atom.

[0151] In this specification, "hydrocarbon group" refers to a group containing carbon and hydrogen and having one hydrogen atom removed from a hydrocarbon. There is no particular limitation on such a hydrocarbon group; examples include those that can be substituted by one or more substituents, C... 1－20Hydrocarbon groups, such as aliphatic hydrocarbon groups and aromatic hydrocarbon groups. The aforementioned "aliphatic hydrocarbon groups" can be any type of straight-chain, branched, or cyclic, and can be either saturated or unsaturated. In addition, hydrocarbon groups can contain one or more ring structures.

[0152] In the context of this specification, the substituent for "hydrocarbon group" is not particularly limited, and examples include those selected from halogen atoms, those that can be substituted by one or more halogen atoms, and C. 1－6 Alkyl, C 2－6 alkenyl, C 2－6 alkynyl group, C 3－10 cycloalkyl, C 3－10 Unsaturated cycloalkyl groups, 5-10 membered heterocyclic groups, 5-10 membered unsaturated heterocyclic groups, C 6－10 One or more groups selected from aryl and 5- to 10-membered heteroaryl groups.

[0153] In this specification, unless otherwise specified, "alkyl" refers to alkyl groups having 1 to 12 carbon atoms (preferably 1 to 6, more preferably 1 to 3, and even more preferably 1) (e.g., methyl, ethyl, propyl, isopropyl). This "alkyl" can be linear or branched, preferably linear. Furthermore, this "alkyl" may contain functional groups.

[0154] The curable composition of the present invention will be described below.

[0155] The curable composition of the present invention contains an organosilicon copolymer, a fluorinated polyether compound, and a matrix-forming composition.

[0156] [Organosilicon copolymer]

[0157] The aforementioned organosilicon copolymer has two or more crosslinking groups, which are groups containing carbon-carbon double bonds, carbon-carbon triple bonds, cyclic ether groups, hydroxyl groups, mercapto groups, amino groups, azide groups, nitrogen-containing heterocyclic groups, isocyanate groups, halogen atoms, groups containing phosphate groups or silane coupling groups, or are their precursor groups.

[0158] In a preferred embodiment, the aforementioned organosilicon copolymer has three or more crosslinking groups. Having three or more crosslinking groups makes it less prone to exudation.

[0159] In a preferred embodiment, the aforementioned organosilicon copolymer is a chain copolymer. Here, the chain copolymer refers to a copolymer obtained through chain polymerization. When the organosilicon copolymer is a chain copolymer, exudation is less likely to occur.

[0160] In a more preferred embodiment, the aforementioned chain copolymer is an addition copolymer. Here, the addition copolymer refers to a copolymer obtained through addition polymerization. Since the copolymer is an addition copolymer made of silicone, it is less prone to exudation.

[0161] In a further preferred embodiment, the addition copolymer is a free radical copolymer or an ionic copolymer. Here, the free radical copolymer and ionic copolymer refer to copolymers obtained by free radical polymerization and ionic polymerization, respectively. Since the organosilicon copolymer is a free radical copolymer or an ionic copolymer, exudation is less likely to occur.

[0162] In a further preferred embodiment, the addition copolymer is a free radical copolymer. Since the organosilicon copolymer is a free radical copolymer, it is less prone to exudation.

[0163] In a preferred embodiment, the aforementioned organosilicon copolymer is a block copolymer. Because the organosilicon copolymer is a free radical copolymer, it is less prone to exudation.

[0164] In a preferred embodiment, the siloxane portion of the aforementioned organosilicon copolymer is chain-like. By having the siloxane portion of the organosilicon copolymer in a chain-like form, both the dynamic and static coefficients of friction can be further reduced.

[0165] In a preferred embodiment, the aforementioned organosilicon copolymer has crosslinking groups at its ends, preferably three or more crosslinking groups at the ends. Here, "having crosslinking groups at the ends" means that the crosslinking groups are located at any end of the molecular backbone closer to the siloxane moiety than the siloxane moiety. In other words, it means that there is no siloxane moiety between the crosslinking groups and any molecular end, or that the crosslinking groups are not sandwiched by the siloxane moiety.

[0166] In a preferred embodiment, the aforementioned organosilicon copolymer is hydrophobic. Here, hydrophobicity means that it dissolves in a non-aqueous solvent at a concentration of 5% by mass or more. The non-aqueous solvent can be, for example, methyl isobutyl ketone, methyl ethyl ketone, or butyl acetate.

[0167] In a preferred embodiment, the aforementioned organosilicon copolymer is dissolved in methyl isobutyl ketone at a concentration of 5% by mass or more, preferably 10% by mass or more, and more preferably 20% by mass or more.

[0168] In a more preferred embodiment, the aforementioned organosilicon copolymer is dissolved in methyl isobutyl ketone and methyl ethyl ketone at a concentration of 5% by mass or more, preferably 10% by mass or more, and more preferably 20% by mass or more.

[0169] The above-mentioned organosilicon copolymers provide organosilicon copolymers as shown in formula (1) or (2).

[0170]

[0171] [In the formula,

[0172] R 1 It is a hydrogen atom or a carbon atom. 1－6 alkyl;

[0173] R 2 Each time it appears, it is independently represented by a hydrogen atom or a carbon atom. 1－6 alkyl;

[0174] m is an integer from 1 to 300;

[0175] R 4 Each occurrence is independently assigned the value R. 4a Or R 4b ;

[0176] R 4a Each time it appears, it is independently a divalent organic group with cross-linking properties;

[0177] R 4b Each time it appears, it is an independent divalent organic group that does not have a cross-linking group;

[0178] The aforementioned crosslinking groups are groups containing carbon-carbon double bonds, carbon-carbon triple bonds, cyclic ether groups, hydroxyl groups, mercapto groups, amino groups, azide groups, nitrogen-containing heterocyclic groups, isocyanate groups, halogen atoms, groups containing phosphate groups or silane coupling groups, or groups containing their precursor groups.

[0179] n is an integer from 1 to 90;

[0180] X a Each is an organic group that is independently divalent;

[0181] X b Each is an organic group that is independently divalent;

[0182] R a Each is independently an alkyl, phenyl, or -SR a1 -OR a2 、-NR a3 2.

[0183]

[0184] R a1 R a2 R a3 R a4 R a5 and R a6 Each can be independently an alkyl or phenyl group;

[0185] R a7 It can be a hydrogen atom or a halogen atom.

[0186] In equation (1) above, R 1 It is a hydrogen atom or a carbon atom. 1－6 alkyl.

[0187] The above R 1 C is preferred 1－6 Alkyl, more preferably C 1－4 alkyl.

[0188] In equations (1) and (2) above, R 2 Each time it appears, it is independently represented by a hydrogen atom or a carbon atom. 1－6 alkyl.

[0189] The above R 2 Each time it appears, C is independently preferred. 1－6 Alkyl, more preferably C 1－3 Alkyl group, more preferably methyl group.

[0190] In the above formulas (1) and (2), m is an integer from 1 to 300, preferably an integer from 2 to 250, more preferably an integer from 2 to 200, and even more preferably an integer from 5 to 150.

[0191] In equations (1) and (2) above, R 4 Each occurrence is independently assigned the value R. 4a Or R 4b .

[0192] The above R 4a Each time it appears, it is an independent divalent organic group with cross-linking properties.

[0193] The aforementioned cross-linking groups refer to groups that can react under specified conditions to form cross-linked structures.

[0194] The aforementioned crosslinking groups are preferably groups containing carbon-carbon double bonds, carbon-carbon triple bonds, cyclic ether groups, hydroxyl groups, mercapto groups, amino groups, azide groups, nitrogen-containing heterocyclic groups, isocyanate groups, halogen atoms, groups containing phosphate groups or silane coupling groups, or groups containing their precursor groups.

[0195] Examples of crosslinking groups include epoxy, glycidyl, alicyclic epoxy, vinyl, allyl, substituted acryloyl, cinnamoyl, 2,4-hexadienoyl, vinyl ether (vinyloxy), hydroxy, oxetyl, isocyanate, catechol, mercapto, amino, alkylamino, dialkylamino, azide, phosphate, carboxyl, imidazole, triazolyl, benzotriazolyl, tetrazolyl, halogen atom, or silane coupling group, or their precursor groups.

[0196] The alicyclic epoxy group described above is preferably a group represented by the following formula.

[0197]

[0198] (In the formula, n is an integer from 1 to 5.)

[0199] The above-mentioned alicyclic epoxy group is more preferably:

[0200]

[0201] The acryloyl group that can be substituted is CH2=CX. 1 The group represented by -C(O)-.

[0202] The above X 1 The alkyl group represents a hydrogen atom, a chlorine atom, a fluorine atom, or an alkyl group having 1 to 10 carbon atoms that can be replaced by fluorine, preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms, for example, methyl.

[0203] The acryloyl group that can be substituted is preferably acryloyl or methacryloyl. Hereinafter, acryloyl and methacryloyl will also be collectively referred to as "(meth)acryloyl".

[0204] The above-mentioned phosphate-containing groups are not particularly limited as long as they contain phosphate groups; for example, they can be C. 1－6 Alkylene – OP(O)(OH)(OR) (where R is a hydrogen atom or C) 1－3 alkyl).

[0205] In one embodiment, the crosslinking group may be an epoxy group, a glycidyl group, an alicyclic epoxy group, a vinyl group, an allyl group, a (meth)acryloyl group, a cinnamoyl group, a 2,4-hexadienoyl group, or a vinyl ether (vinyloxy) group.

[0206] In a preferred embodiment, the crosslinking group is an epoxy group, a glycidyl group, or CH2=CX. 1′ -C(O)-(where X) 1′ The group represents a hydrogen atom, a chlorine atom, a fluorine atom, or an alkyl group with 1 to 10 carbon atoms that can be replaced by fluorine, preferably an epoxy group, a glycidyl group, or a (meth)acryloyl group.

[0207] In another preferred embodiment, the crosslinking group can be an epoxy group, a glycidyl group, an alicyclic epoxy group, or a (meth)acryloyl group, preferably an epoxy group, a glycidyl group, or an alicyclic epoxy group, more preferably an epoxy group or a glycidyl group.

[0208] In the preferred embodiment, R 4a It is a group represented by the following formula.

[0209]

[0210] [In the formula,

[0211] R 31 Each time it appears, it is independently represented by a hydrogen atom or an alkyl group;

[0212] R 32 Each time it appears, it is independently a hydrogen atom, a chlorine atom, a fluorine atom, or an alkyl group that can be substituted by fluorine;

[0213] R 33 Each time it appears, it is an independent cross-linking group;

[0214] Y 1 For single bonds, -C(=O)O-, -C(=O)NH-, -OC(=O)-, -NHC(=O)-, -O-, -N(R) c )-, aromatic ring, aromatic ring with substituents or carbazoyl group;

[0215] R c It is an organic group;

[0216] Y 2 It is a linker group consisting of single bonds or 1 to 16 atoms in the main chain.

[0217] In the above formula, R 31 Each time it appears, it independently represents either a hydrogen atom or an alkyl group. The alkyl group is preferably C10. 1－6 Alkyl, more preferably C 1－3 Alkyl group, more preferably methyl or ethyl. R 31 Hydrogen atoms are preferred.

[0218] In the above formula, R 32 Each instance of the alkyl group represents a hydrogen atom, a chlorine atom, a fluorine atom, or an alkyl group that can be substituted with fluorine. The alkyl group is preferably C10. 1－6 Alkyl, more preferably C 1－3 Alkyl group, more preferably methyl or ethyl. R 32 Preferably, it is a methyl group or a hydrogen atom, more preferably a hydrogen atom.

[0219] The above R 33 Each time it appears, it is an independent cross-linking group. The meaning of this cross-linking group is the same as above.

[0220] In the preferred embodiment, R 33It can be an epoxy group, glycidyl group, alicyclic epoxy group, vinyl group, allyl group, substituted acryloyl group, cinnamoyl group, 2,4-hexadienoyl group, vinyl ether (vinyloxy) group, hydroxy group, oxetyl group, isocyanate group, catechol group, mercapto group, amino group, alkylamino group, dialkylamino group, azide group, phosphate group, carboxyl group, imidazole group, triazole group, benzotriazole group, tetrazolyl group, halogen atom or silane coupling group, or their precursor groups.

[0221] In a more preferred manner, R 33 It can be epoxy, glycidyl, alicyclic epoxy, vinyl, allyl, (meth)acryloyl, cinnamoyl, 2,4-hexadienoyl, or vinyl ether (vinyloxy) group.

[0222] In a further preferred embodiment, the crosslinking group can be an epoxy group, a glycidyl group, an alicyclic epoxy group, or a (meth)acryloyl group, preferably an epoxy group, a glycidyl group, or a (meth)acryloyl group.

[0223] In the above formula, Y 1 For single bonds, -C(=O)O-, -C(=O)NH-, -OC(=O)-, -NHC(=O)-, -O-, -N(R) c )-, phenylene or carbazolyl. Wherein, R c This indicates an organic group, preferably an alkyl group. The alkyl group is preferably C10. 1－6 Alkyl, more preferably C 1－3 Alkyl groups, more preferably methyl or ethyl. Regarding Y... 1 These groups are bonded to C on the left side and to Y on the right side. 2 Bonding.

[0224] In one approach, Y 1 are -C(=O)O-, -C(=O)NH-, -OC(=O)-, -NHC(=O)-, -O-, -N(R c )-, phenylene or carbazolyl. Wherein, R c This indicates an organic group, preferably an alkyl group.

[0225] Y 1 Preferably, it is -C(=O)O-, -O- or imidazolyl, more preferably -C(=O)O- or -O-, and even more preferably -C(=O)O-.

[0226] In the above formula, Y 2 Linking groups indicate that the number of atoms in a single bond or main chain is 1 to 16, preferably 2 to 12, and more preferably 2 to 10. The main chain mentioned above refers to Y... 2 Lieutenant General Y 1 With R 33The part connected by the minimum number of atoms.

[0227] As the Y 2 There are no specific limitations; for example, we can list:

[0228] -(CH2-CH2-O) p1 - (p1 represents an integer from 1 to 10, preferably an integer from 1 to 6, and more preferably an integer from 1 to 4);

[0229] -(CHR) d ) p2 -O-(p2 is an integer from 1 to 40, preferably an integer from 1 to 10, more preferably an integer from 1 to 6, even more preferably an integer from 1 to 4, even more preferably an integer from 2 to 4, R d (Indicates hydrogen or methyl);

[0230] -(CH2) p3 -O-(CH2) p4 - (p3 is an integer from 1 to 10, preferably an integer from 1 to 6, more preferably an integer from 1 to 4, p4 is an integer from 0 to 10, preferably an integer from 0 to 6, more preferably an integer from 0 to 4, and in one mode represents an integer from 1 to 10, preferably an integer from 1 to 6, more preferably an integer from 1 to 4);

[0231] -(CH2-CH2-O) p5 -CO-NH-CH2-CH2-O- (p5 represents integers from 1 to 10);

[0232] -(CH2) p6 - (p6 represents an integer from 1 to 6);

[0233] -(CH2) p7 -O-CONH-(CH2) p8 - (p7 represents an integer from 1 to 8, preferably 2 or 4; p8 represents an integer from 1 to 6, preferably 3);

[0234] -(CH2) p9 -NHC(=O)O-(CH2) p10 - (p9 represents an integer from 1 to 6, preferably 3; p10 represents an integer from 1 to 8, preferably 2 or 4); or

[0235] -O-(but Y) 1 Not for -O-).

[0236] Y is the preferred 2 Examples include -(CH2-CH2-O). p1 -(p1 represents an integer from 1 to 10), -(CHR) d ) p2-O-(p2 is an integer from 1 to 40, R) d (Indicates hydrogen or methyl), -(CH2) p3 -O-(CH2) p4 -(p3 represents an integer from 1 to 10, p4 represents an integer from 1 to 10) or -(CH2) p7 -O-CONH-(CH2) p8 - (p7 represents an integer from 1 to 8, preferably 2 or 4; p8 represents an integer from 1 to 6, preferably 3). Wherein, the left end of these groups is adjacent to the main chain side (Y). 1 The right end is bonded to a functional group selected from substituent group A (R) and bonded to the side. 33 (Side) bonding.

[0237] R 4a Further preferred are groups represented by the following formula.

[0238]

[0239] (In the formula, q2 is an integer from 1 to 10, preferably an integer from 1 to 6, more preferably an integer from 1 to 4, and even more preferably an integer from 2 to 4; q3 is an integer from 1 to 10, preferably an integer from 1 to 6, more preferably an integer from 1 to 4, and even more preferably an integer from 1 to 2.)

[0240] The above R 4b Each time it appears, it is an independent divalent organic group that does not have a cross-linking group.

[0241] R 4b Preferred option: -CHR 4c -CR 4d R 4e —. Here, R 4c and R 4d Each can be independently represented by a hydrogen atom or an alkyl group, R 4e Base is -Y 3 -R 4f Among them, Y 3 The meaning of Y above 1 Same, R 4f It is an organic group that does not have cross-linking groups, and the group R mentioned later... 4g Is it via a linker or directly with Y? 3 Bonded base.

[0242] The preferred linker is:

[0243] (a)-(CH2-CH2-O) s1 - (s1 represents an integer from 1 to 10, preferably an integer from 1 to 6, and more preferably an integer from 1 to 4);

[0244] (b)-(CHR4h ) s2 -O-(s2) represents the number of repetitions, which is an integer from 1 to 40, preferably an integer from 1 to 10, more preferably an integer from 1 to 6, even more preferably an integer from 1 to 4, and even more preferably an integer from 2 to 4. R 4h (Indicates a hydrogen atom or a methyl group);

[0245] (c)-(CH2) s3 -O-(CH2) s4 - (s3 is an integer from 1 to 10, preferably an integer from 1 to 6, more preferably an integer from 1 to 4, s4 is an integer from 0 to 10, preferably an integer from 0 to 6, more preferably an integer from 0 to 4, and in one mode, it represents an integer from 1 to 10, preferably an integer from 1 to 6, more preferably an integer from 1 to 4);

[0246] (d)-(CH2-CH2-O) s1 -CO-NH-CH2-CH2-O- (s1 has the same meaning as above);

[0247] (e)-(CH2) s5 -(s5 represents an integer from 1 to 6);

[0248] (f)-(CH2) s6 -O-CONH-(CH2) s7 - (s6 represents an integer from 1 to 8, preferably 2 or 4. s7 represents an integer from 1 to 6, preferably 3); or

[0249] (g)-O-(but Y 3 Not for -O-).

[0250] R 4g Preferably, the following groups are used.

[0251] (i) alkyl

[0252] For example: methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, hexyl, heptyl, octyl, dodecyl, octadecyl.

[0253] (ii) A chain group containing a fluorinated alkyl group

[0254] For example:

[0255]

[0256] (iii) A group containing one or more rings selected from monocyclic, dicyclic, tricyclic, and tetracyclic carbon rings.

[0257] For example:

[0258]

[0259] (iv) Hydrogen (but the hydrogen atom is not bonded to the oxygen atom of the linker)

[0260] (v) Groups containing imidazolium salts

[0261] For example:

[0262]

[0263] (vi) Silicon-containing groups

[0264]

[0265] In the above formula, R 11 R 12 R 13 R 14 R 15 R 16 and R 17 Each can be represented independently as either alkyl or aryl.

[0266] The alkyl group described above is not particularly limited, and examples include alkyl groups having 1 to 10 carbon atoms and cycloalkyl groups having 3 to 20 carbon atoms, with alkyl groups having 1 to 6 carbon atoms being preferred. Specifically, R 11 Preferably, it is n-butyl with a carbon number of atoms, R 12 ~R 17 Methyl is preferred.

[0267] The aryl group mentioned above is not particularly limited, and examples include aryl groups with 6 to 20 carbon atoms. The aryl group may contain two or more rings. A preferred aryl group is phenyl.

[0268] The aforementioned alkyl and aryl groups may contain heteroatoms, such as nitrogen, oxygen, and sulfur atoms, in their molecular chains or rings as needed.

[0269] Furthermore, the aforementioned alkyl and aryl groups can be substituted with one or more substituents as needed, wherein the substituents are selected from halogens; C can be substituted with one or more halogens. 1－6 Alkyl, C 2－6 alkenyl, C 2－6 alkynyl group, C 3－10 cycloalkyl, C 3－10 Unsaturated cycloalkyl groups, 5-10 membered heterocyclic groups, 5-10 membered unsaturated heterocyclic groups, C 6－10 Aryl, 5-10 aryl compounds.

[0270] In the above formula, R 18 This indicates a divalent organic group.

[0271] The above R 18 Preferably -(CH2)r" —(where r" is an integer of 1 to 20, preferably an integer of 1 to 10), more preferably —(CH2). r" —(where r" is an integer greater than 1 and less than 10).

[0272] In the above formula, n4 is an integer of 1 to 500. Preferably, n4 is 1 to 200, and more preferably 10 to 200.

[0273] R 4g More preferably, it is a hydrogen atom (but not including cases where it is bonded to O to form a hydroxyl group), or an alkyl group that can be fluorinated and can be linked via an ethylene chain or an oxyethylene chain, more preferably a hydrogen atom, methoxyethyl, isobutyl, or R 4i -CF2-(CF2) s6 -(CH2) s7 -O-(CH2)2-(R 4i (where s6 is an integer from 0 to 6 and s7 is an integer from 1 to 6), and more preferably 3-(perfluoroethyl)propoxyethyl [indicative formula: CF3-(CF2)-(CH2)3-O-(CH2)2-].

[0274] The above R 4 In the middle, structural unit R 4a and structural unit R 4b They can form segments individually or combine randomly.

[0275] In one approach, R 4 Medium structural unit R 4a and structural unit R 4b Each segment is formed separately.

[0276] In one approach, R 4 Medium structural unit R 4a and structural unit R 4b Combining randomly.

[0277] In one approach, R 4 For R 4a That is, R 4 Structural unit R with crosslinking groups 4a constitute.

[0278] In the preferred embodiment, R 4a The degree of aggregation is 1 to 90, preferably 2 to 70, more preferably 2 to 50, and even more preferably 3 to 30.

[0279] In one approach, R 4 For R 4b That is, R 4Structural unit R that does not have cross-linking groups 4b constitute.

[0280] In the preferred embodiment, R 4b The degree of aggregation is 1 to 90, preferably 2 to 70, more preferably 2 to 50, and even more preferably 3 to 30.

[0281] In the above formula, n is an integer from 1 to 90, preferably an integer from 2 to 70, more preferably an integer from 2 to 50, and even more preferably an integer from 3 to 30.

[0282] In equations (1) and (2) above, X a Each is an independent divalent organic group.

[0283] In equations (1) and (2) above, X b Each is an independent divalent organic group.

[0284] In the above formula, -X a -X b - This can be understood as combining Si and R in the organosilicon copolymers shown in formulas (1) and (2). 4 Part of the connecting group. Therefore, as long as the compounds shown in formulas (1) and (2) can exist stably, X a and X b It can be any divalent organic group.

[0285] In one manner, X a It can be a group as shown in the following formula.

[0286] -(O) e1 -(CH2) g2 -O-[(CH2) g3 -O-] g4

[0287] [In the formula,

[0288] e1 is either 0 or 1.

[0289] g2 and g3 are each independently an integer from 1 to 10, preferably an integer from 2 to 8, more preferably an integer from 2 to 6, and even more preferably an integer from 2 to 4.

[0290] g4 is either 0 or 1.

[0291] In these groups, the left end is bonded to Si, and the right end is bonded to X. b Bonding.

[0292] In the preferred embodiment, X a It can be a group as shown in the following formula.

[0293] -(CH2) g2 -O-(CH2) g3 -O-

[0294] [In the formula,

[0295] g2 is an integer from 1 to 10, preferably an integer from 2 to 8, more preferably an integer from 2 to 6, and even more preferably an integer from 2 to 4, for example, 3.

[0296] g3 is an integer from 1 to 10, preferably an integer from 2 to 8, more preferably an integer from 2 to 6, and even more preferably an integer from 2 to 4, for example, 2.

[0297] In these groups, the left end is bonded to Si, and the right end is bonded to X. b Bonding.

[0298] In the above formula, X b Each is an independent divalent organic group.

[0299] In one manner, X b It can be a group as shown in the following formula.

[0300] -CO-R b3 -CR b1 R b2 -

[0301] [In the formula,

[0302] R b1 and R b2 Each is independently a hydrogen atom and a carbon atom. 1－3 Alkyl, phenyl, or -CN

[0303] R b3 For a single bond or a C that can be replaced 1－6 Alkylene.

[0304] Among them, the left end of these groups is connected to X. a Bonding, right end with R 4 Bonding.

[0305] The above R b1 and R b2 C is preferred independently. 1－3 Alkyl, phenyl, or -CN, more preferably C 1－3 Alkyl or -CN. C 1－3 The alkyl group is preferably methyl or ethyl, and more preferably methyl.

[0306] In one approach, R b1 C 1－3 Alkyl, preferably methyl, R b2 It can be a hydrogen atom or -CN.

[0307] The above R b3 The "C that can be replaced" 1－6 The substituents in "alkylene" are preferably C 1－3 Alkyl or phenyl, preferably C 1－3 Alkyl group. C 1－3 The alkyl group is preferably methyl or ethyl, more preferably methyl. There may be one substituent or two or more substituents.

[0308] The above R b3 C in 1－6 Alkylene is preferably C 1－3 Alkylene, more preferably C 2－3 Alkylene, for example, can be dimethylene.

[0309] In one approach, R b3 It is a single key.

[0310] In another way, R b3 C can be replaced 1－6 Alkylene, preferably C 1－6 Alkylene.

[0311] In the above formula, R a alkyl, phenyl, -SR a1 -OR a2 、-NR a3 2.

[0312]

[0313] R a It can be part of a so-called RAFT agent.

[0314] In the above formula, R a1 R a2 R a3 R a4 R a5 and R a6 Each can be an alkyl or phenyl group, independently.

[0315] The above R a1 C is preferred 1－20 Alkyl, more preferably C 3－18 Alkyl, more preferably C 4－12 alkyl.

[0316] The above R a2 Preferably phenyl or C 1－20 Alkyl group. The C 1－20 Alkyl groups are preferably C 1－10 Alkyl, more preferably C 1－6 Alkyl, more preferably C 1－3 alkyl.

[0317] The above R a3 C is preferred 1－20 Alkyl, more preferably C 1－10 Alkyl, more preferably C 1－6 Alkyl, more preferably C 1－3 alkyl.

[0318] The above R a4 C is preferred 1－6 Alkyl, more preferably C 1－3 Alkyl groups, with methyl groups being more preferred.

[0319] The above R a5 C is preferred 1－6 Alkyl, more preferably C 1－3 Alkyl groups, with methyl groups being more preferred.

[0320] The above R a6 C is preferred 1－6 Alkyl, more preferably C 1－3 Alkyl groups, with methyl groups being more preferred.

[0321] The above R a7 It is a hydrogen atom or a halogen atom (e.g., fluorine, chlorine, bromine or iodine, preferably chlorine).

[0322] In one approach, R a For -SR a1 OR a2 .

[0323] The number-average molecular weight of the above-mentioned organosilicon copolymers is not particularly limited and can be 2 × 10⁻⁶. 2 ~1×10 5 Preferably 1×10 3 ~5×10 4 More preferably 3×10 3 ~2×10 4 The number-average molecular weight can be determined by gel permeation chromatography (GPC).

[0324] The aforementioned organosilicon copolymers can be synthesized, for example, using so-called RAFT (Reversible addition-fragmentation chain transfer) type free radical polymerization.

[0325] First, a RAFT agent having a siloxane backbone is prepared. For example, by reacting a compound (A) having a RAFT backbone (-SC(=S)-) with a compound (B1) or (B2) having a siloxane backbone, a chain transfer agent (1a) or (2a) having a siloxane backbone can be obtained.

[0326]

[0327] [In the formula, R] a R 1 R 2 X a X b The meaning of 'm' is the same as above;

[0328] L 1 and L 2 These are the detached parts.

[0329]

[0330] [In the formula, R] a R 1 R 2 X a X b The meaning of 'm' is the same as above.

[0331] By reacting the chain transfer agent (1a) or (2a) obtained above with a monomer having unsaturated bonds, the compound shown in formula (1) or (2) above can be obtained. This reaction is called RAFT polymerization, and the reaction conditions can be those commonly used in RAFT polymerization.

[0332] [Fluoro-containing polyether compounds]

[0333] There are no particular limitations on the above-mentioned fluorinated polyether compounds as long as they contain fluorinated polyether groups.

[0334] Here, the fluorinated polyether group is -(C x R 2x O) y - (where R is a hydrogen atom, fluorine atom, or chlorine atom, x is an integer from 1 to 8, y is an integer greater than 1, and at least one R is a fluorine atom) group.

[0335] In one embodiment, the fluorine content of the aforementioned fluorinated polyether compound is in the range of 2 to 70% by weight, preferably 10 to 60% by weight. By ensuring the fluorine content of the fluorinated polyether compound is within this range, the water-repellent and oil-repellent properties are further improved.

[0336] In a preferred embodiment, the fluorinated polyether compound is a chain copolymer. Here, the chain copolymer refers to a copolymer obtained through chain polymerization. By making the fluorinated polyether compound a chain copolymer, exudation is less likely to occur.

[0337] In a more preferred embodiment, the aforementioned chain copolymer is an addition copolymer. Here, the addition copolymer refers to a copolymer obtained through addition polymerization. By making the fluorinated polyether compound an addition copolymer, exudation is less likely to occur.

[0338] In a further preferred embodiment, the addition copolymer is a free radical copolymer or an ionic copolymer. Here, the free radical copolymer and ionic copolymer refer to copolymers obtained by free radical polymerization and ionic polymerization, respectively. By making the fluorinated polyether compound a free radical copolymer or an ionic copolymer, exudation is less likely to occur.

[0339] In a further preferred embodiment, the addition copolymer is a free radical copolymer. By making the fluorinated polyether compound a free radical copolymer, exudation is less likely to occur.

[0340] In a preferred embodiment, the aforementioned fluorinated polyether compound is a block copolymer. By making the organosilicon copolymer a free radical copolymer, exudation is less likely to occur.

[0341] In one embodiment, the fluorinated polyether compound is a fluorinated polyether compound represented by any of the general formulas (3) to (5).

[0342]

[0343] (R F1 -X c ) n2 -R 10 -(R 8 -OC(O)CR 9 =CH2) n3 (5)

[0344] In a preferred embodiment, the fluorinated polyether compound is a fluorinated polyether compound of general formula (3) or (4).

[0345]

[0346] [In the formula,

[0347] R F1 For Rf 1 -R F -O q -;

[0348] R F2 -Rf 2 p -R F -O q -;

[0349] Rf 1C atoms that can be substituted by one or more fluorine atoms 1－16 alkyl;

[0350] Rf 2 C atoms that can be substituted by one or more fluorine atoms 1－6 Alkylene;

[0351] R F Each is independently a divalent fluorinated polyether group;

[0352] p is 0 or 1;

[0353] q can be 0 or 1 independently;

[0354] R 4′ Each occurrence is independently assigned the value R. 4a′ Or R 4b′ ;

[0355] R 4a′ Each time it appears, it is independently an organic group with a divalent functional group selected from substituent group A;

[0356] R 4b′ Each time it appears, it is independently a divalent organic group that does not have a functional group selected from substituent group A;

[0357] The substituent group A mentioned above includes carbon-carbon double bonds, carbon-carbon triple bonds, cyclic ether groups, hydroxyl groups, mercapto groups, amino groups, azide groups, nitrogen-containing heterocyclic groups, isocyanate groups, halogen atoms, groups containing phosphate groups and silane coupling groups, as well as their precursor groups;

[0358] n ′ Integers from 1 to 100;

[0359] X a′ Each is an independent divalent organic group;

[0360] X b′ Each is an independent divalent organic group;

[0361] R a′ Each is independently an alkyl, phenyl, or -SR a1 -OR a2 、-NR a3 2.

[0362]

[0363] R a1 R a2 R a3 R a4 R a5 and R a6Each can be independently an alkyl or phenyl group;

[0364] R a7 It can be a hydrogen atom or a halogen atom.

[0365] The curable composition of the present invention, by containing the above-mentioned organosilicon copolymer and the above-mentioned fluorinated polyether compound, further improves the water and oil repellency and friction durability of the surface treatment layer.

[0366] In equation (3) above, R F1 For Rf 1 -R F -O q -.

[0367] In equation (4) above, R F2 -Rf 2 p -R F -O q -.

[0368] In the above formula, Rf 1 Each is an independent C that can be substituted by one or more fluorine atoms. 1－16 alkyl.

[0369] The above C atoms that can be substituted by one or more fluorine atoms 1－16 The "C" in alkyl 1－16 "alkyl" can be straight-chain or branched, preferably straight-chain or branched C. 1－6 Alkyl groups, especially C 1－3 Alkyl groups, more preferably straight-chain C4 groups 1－6 Alkyl groups, especially C 1－3 alkyl.

[0370] The above Rf 1 Preferably, C atoms are substituted with one or more fluorine atoms. 1－16 Alkyl groups, more preferably CF2H-C 1－15 Perfluoroalkylene, more preferably C 1－16 Perfluoroalkyl.

[0371] The above C 1－16 Perfluoroalkyl groups can be straight-chain or branched, preferably straight-chain or branched C. 1－6 Perfluoroalkyl, especially C 1－3 Perfluoroalkyl, more preferably straight-chain C 1－6 Perfluoroalkyl, especially C 1－3 Perfluoroalkyl, specifically -CF3, -CF2CF3 or -CF2CF2CF3.

[0372] In the above formula, Rf 2C atoms that can be substituted by one or more fluorine atoms 1－6 Alkylene.

[0373] The above C atoms that can be substituted by one or more fluorine atoms 1－6 The "C" in alkylene 1－6 "alkylene" can be straight-chain or branched, preferably straight-chain or branched C 1－3 Alkylene, more preferably straight-chain C 1－3 Alkylene.

[0374] The above Rf 2 Preferably, C atoms are substituted with one or more fluorine atoms. 1－6 Alkylene, more preferably C 1－6 Perfluoroalkylene, more preferably C 1－3 Perfluoroalkylene groups.

[0375] The above C 1－6 Perfluoroalkylene groups can be straight-chain or branched, preferably straight-chain or branched C. 1－3 Perfluoroalkylene, more preferably straight-chain C 1－3 Perfluoroalkyl, specifically -CF2-, -CF2CF2-, or -CF2CF2CF2-.

[0376] In the above formula, p is either 0 or 1. In one approach, p is 0. In another approach, p is 1.

[0377] In the above formula, q is either 0 or 1 independently. In one case, q is 0. In another case, q is 1.

[0378] In equations (3) and (4) above, R F Each is independently a divalent fluorinated polyether group.

[0379] R F Preferred formula: -(OC6F 12 ) a -(OC5F) 10 ) b -(OC4F8) c -(OC3R) Fa 6) d -(OC2F4) e -(OCF2) f - The group shown.

[0380] [In the formula,

[0381] R Fa Each time it appears, it is independently represented by a hydrogen atom, a fluorine atom, or a chlorine atom.

[0382] a, b, c, d, e, and f are each an independent integer from 0 to 200, and the sum of a, b, c, d, e, and f is 1 or greater. The order of the repeating units labeled a, b, c, d, e, or f and enclosed in parentheses is arbitrary in the formula.

[0383] R Fa Preferably, it is a hydrogen atom or a fluorine atom, more preferably a fluorine atom.

[0384] a, b, c, d, e, and f are preferably independent integers from 0 to 100.

[0385] The sum of a, b, c, d, e, and f is preferably 5 or more, more preferably 10 or more, for example, 15 or more or 20 or more. The sum of a, b, c, d, e, and f is preferably 200 or less, more preferably 100 or less, and even more preferably 60 or less, for example, 50 or less or 30 or less.

[0386] These repeating units can be linear or branched. For example, regarding the repeating unit mentioned above, -(OC6F 12 )- can be -(OCF2CF2CF2CF2CF2CF2)-, -(OCF(CF3)CF2CF2CF2CF2)-, -(OCF2CF(CF3)CF2CF2CF2)-, -(OCF2CF2CF(CF3)CF2CF2)-, -(OCF2CF2CF2CF(CF3)CF2)-, -(OCF2CF2CF2CF2CF(CF3))-, etc. -(OC5F 10 - can be any of -(OCF2CF2CF2CF2CF2)-, -(OCF(CF3)CF2CF2CF2)-, -(OCF2CF(CF3)CF2CF2)-, -(OCF2CF2CF(CF3)CF2)-, -(OCF2CF2CF2CF(CF3))-, etc. -(OC4F8)- can be any of -(OCF2CF2CF2CF2)-, -(OCF(CF3)CF2CF2)-, -(OCF2CF(CF3)CF2)-, -(OCF2CF2CF(CF3))-, -(OC(CF3)2CF2)-, -(OCF2C(CF3)2)-, -(OCF(CF3)CF(CF3))-, -(OCF(C2F5)CF2)-, and -(OCF2CF(C2F5))-. -(OC3F6)-(that is, R in the above formula) Fa The fluorine atom can be any one of -(OCF2CF2CF2)-, -(OCF(CF3)CF2)-, and -(OCF2CF(CF3))-. -(OC2F4)- can be any one of -(OCF2CF2)- and -(OCF(CF3))-.

[0387] In one embodiment, the repeating units are in a straight chain shape. By making the repeating units in a straight chain shape, the surface lubricity and friction durability of the surface treatment layer can be improved.

[0388] In one embodiment, the repeating units are branched. By making the repeating units branched, the coefficient of dynamic friction of the surface treatment layer can be increased.

[0389] In one approach, R F Each of the following formulas (f1) to (f5) can be a group that is independently represented by a group.

[0390] -(OC3F6) d -(OC2F4) e - (f1)

[0391] [In the formula, d is an integer from 1 to 200, and e is 0 or 1.]

[0392] -(OC4F8) c -(OC3F6) d -(OC2F4) e -(OCF2) f - (f2)

[0393] In the formula, c and d are independent integers above 0 and below 30, and e and f are independent integers above 1 and below 200.

[0394] The sum of c, d, e, and f is 2 or more.

[0395] The order of repeated units marked with subscripts c, d, e, or f and enclosed in parentheses is arbitrary in the formula.

[0396] -(R) 6 -R 7 ) g - (f3)

[0397] [In the formula, R] 6 It is either OCF2 or OC2F4.

[0398] R 7 Selected from OC2F4, OC3F6, OC4F8, OC5F 10 and OC6F 12 The groups, or combinations of two or three groups selected independently from these groups,

[0399] g is an integer from 2 to 100.

[0400] -(OC6F 12 ) a -(OC5F)10 ) b -(OC4F8) c -(OC3F6) d -(OC2F4) e -(OCF2) f - (f4)

[0401] [In the formula, e is an integer greater than 1 and less than 200, a, b, c, d, and f are each an independent integer greater than 0 and less than 200, the sum of a, b, c, d, e, and f is at least 1, and the order of the repeated units marked a, b, c, d, e, or f and enclosed in parentheses is arbitrary in the formula.]

[0402] -(OC6F 12 ) a -(OC5F) 10 ) b -(OC4F8) c -(OC3F6) d -(OC2F4) e -(OCF2) f - (f5)

[0403] [In the formula, f is an integer greater than 1 and less than 200, a, b, c, d, and e are each an independent integer greater than 0 and less than 200, the sum of a, b, c, d, e, and f is at least 1, and the order of the repeated units marked a, b, c, d, e, or f and enclosed in parentheses is arbitrary in the formula.]

[0404] In the above formula (f1), d is preferably an integer from 5 to 200, more preferably from 10 to 100, even more preferably from 15 to 50, and for example from 25 to 35. In one embodiment, e is 1. In another embodiment, e is 0. The above formula (f1) is preferably -(OCF2CF2CF2) d - or - (OCF(CF3)CF2) d The group shown is more preferably -(OCF2CF2CF2). d - The group shown.

[0405] In the above formula (f2), e and f are each preferably integers of 5 or more and 200 or less, more preferably 10 to 200. Furthermore, the sum of c, d, e, and f is preferably 5 or more, more preferably 10 or more, for example, 15 or more or 20 or more. In one embodiment, the above formula (f2) is preferably -(OCF2CF2CF2CF2) c -(OCF2CF2CF2) d -(OCF2CF2) e -(OCF2) f- The group shown. In another embodiment, formula (f2) can be -(OC2F4). e -(OCF2) f - The group shown.

[0406] In the above equation (f3), R 6 Preferably, it is OC2F4. In (f3) above, R 7 Preferably, the group is selected from OC2F4, OC3F6, and OC4F8, or a combination of two or three groups independently selected from these groups, more preferably a group selected from OC3F6 and OC4F8. There is no particular limitation on the combination of two or three groups independently selected from OC2F4, OC3F6, and OC4F8; examples include -OC2F4OC3F6-, -OC2F4OC4F8-, -OC3F6OC2F4-, -OC3F6OC3F6-, -OC3F6OC4F8-, -OC4F8OC4F8-, -OC4F8OC3F6-, -OC4F8OC2F4-, -OC2 F4OC2F4OC3F6-、-OC2F4OC2F4OC4F8-、-OC2F4OC3F6OC2F4-、-OC2F4OC3F6OC3F6-、-OC2F4OC4F8OC2F4-、-OC3F6OC2F4OC2F4-、-OC3F6OC2F4OC3F6-、-OC3F6OC3F6OC2F4- and -OC4F8OC2F4OC2F4- etc. In the above formula (f3), g is preferably an integer of 3 or more, more preferably 5 or more. The above g is preferably an integer of 50 or less. In the above formula (f3), OC2F4, OC3F6, OC4F8, OC5F 10 and OC6F 12 It can be either a straight chain or a branched chain, preferably a straight chain. In this method, the above formula (f3) is preferably -(OC2F4-OC3F6). g - or - (OC2F4 - OC4F8) g -.

[0407] In the above formula (f4), e is preferably an integer of 1 to 100, more preferably 5 to 100. The sum of a, b, c, d, e and f is preferably 5 or more, more preferably 10 or more, for example 10 to 100.

[0408] In the above formula (f5), f is preferably an integer of 1 to 100, more preferably 5 to 100. The sum of a, b, c, d, e and f is preferably 5 or more, more preferably 10 or more, for example, 10 to 100.

[0409] In one approach, the aforementioned R FThe group is represented by the formula (f1) above.

[0410] In one approach, the aforementioned R F The group is represented by the formula (f2) above.

[0411] In one approach, the aforementioned R F The group is represented by the formula (f3) above.

[0412] In one approach, the aforementioned R F The group is represented by the formula (f4) above.

[0413] In one approach, the aforementioned R F The group is represented by the formula (f5) above.

[0414] In the above R F In this compound, the ratio of e to f (hereinafter referred to as the "e / f ratio") is 0.1 to 10, preferably 0.2 to 5, more preferably 0.2 to 2, even more preferably 0.2 to 1.5, and even more preferably 0.2 to 0.85. By making the e / f ratio 10 or less, the sliding properties, friction durability, and chemical resistance (e.g., resistance to artificial sweat) of the surface-treated layer obtained from this compound are further improved. The smaller the e / f ratio, the better the sliding properties and friction durability of the surface-treated layer. On the other hand, by making the e / f ratio 0.1 or more, the stability of the compound can be further improved. The larger the e / f ratio, the better the stability of the compound.

[0415] In one embodiment, the e / f ratio is preferably 0.2 to 0.95, more preferably 0.2 to 0.9.

[0416] In one embodiment, from the viewpoint of heat resistance, the e / f ratio is preferably 1.0 or higher, more preferably 1.0 to 2.0.

[0417] In the above-mentioned fluorinated polyether compounds, R F1 and R F2 The number-average molecular weight of the fraction is not particularly limited, but is, for example, 500 to 30,000, preferably 1,500 to 30,000, and more preferably 2,000 to 10,000. In this specification, R... F1 and R F2 The number average molecular weight is obtained through 19 The value measured by F-NMR.

[0418] In another way, R F1 and R F2The number average molecular weight of the fraction can be 500 to 30,000, preferably 1,000 to 20,000, more preferably 2,000 to 15,000, even more preferably 2,000 to 10,000, for example 3,000 to 6,000.

[0419] In another way, R F1 and R F2 The number average molecular weight of the fraction can be 4,000 to 30,000, preferably 5,000 to 10,000, and more preferably 6,000 to 10,000.

[0420] In the above formula, R 4′ Each occurrence is independently assigned the value R. 4a′ Or R 4b′ .

[0421] The above R 4a′ Each time it appears, it is independently a divalent organic group having a functional group selected from substituent group A.

[0422] As for the above-mentioned "functional group selected from substituent group A", examples include epoxy, glycidyl, alicyclic epoxy, vinyl, allyl, substituted acryloyl, cinnamoyl, 2,4-hexadienoyl, vinyl ether (vinyloxy) group, hydroxy, oxetyl, isocyanate, catechol, mercapto, amino, alkylamino, dialkylamino, azide, phosphate group, carboxyl, imidazole, triazolyl, benzotriazolyl, tetrazolyl, halogen atom or silane coupling group, or their precursor groups.

[0423] The meaning of the above-mentioned alicyclic epoxy groups is the same as that of the above-mentioned crosslinking groups.

[0424] The meaning of the acryloyl group that can be replaced is the same as that described for the crosslinking group.

[0425] The meaning of the phosphate group mentioned above is the same as that of the crosslinking group mentioned above.

[0426] In one embodiment, the functional group selected from the substituent group A above can be epoxy, glycidyl, alicyclic epoxy, vinyl, allyl, (meth)acryloyl, cinnamoyl, 2,4-hexadienoyl, or vinyl ether (vinyloxy) group.

[0427] In a preferred embodiment, the functional group selected from the above substituent group A can be an epoxy group, a glycidyl group, or CH2=CX. 1′ -C(O)-(where X) 1′The group represents a hydrogen atom, a chlorine atom, a fluorine atom, or an alkyl group with 1 to 10 carbon atoms that can be replaced by fluorine, preferably an epoxy group, a glycidyl group, or a (meth)acryloyl group.

[0428] In another preferred embodiment, the functional group selected from the above substituent group A can be epoxy, glycidyl, alicyclic epoxy or (meth)acryloyl, preferably epoxy, glycidyl or alicyclic epoxy, more preferably epoxy or glycidyl.

[0429] R 4a′ Preferably, it contains the group shown in the following formula.

[0430]

[0431] In the above formula, R 31′ Each time it appears, it independently represents either a hydrogen atom or an alkyl group. The R... 31′ Hydrogen atoms are preferred.

[0432] In the above formula, R 32′ Each time it appears, it independently represents a hydrogen atom, a chlorine atom, a fluorine atom, or an alkyl group that can be substituted with fluorine. The R... 32′ Preferably, it is a methyl group or a hydrogen atom, more preferably a hydrogen atom.

[0433] In the above formula, R 33′ Each occurrence independently represents an organic group having a functional group selected from substituent group A.

[0434] As the functional group selected from substituent group A, the same groups as those described above can be listed, preferably epoxy, glycidyl, alicyclic epoxy, or CH2=CX. 1′ -C(O)-(where X) 1′ This refers to an alkyl group containing 1 to 10 carbon atoms (indicating hydrogen, chlorine, fluorine, or carbon atoms that can be replaced by fluorine), specifically glycidyl, CH2=C(CH3)-C(O)- or CH2=CH-C(O)-.

[0435] In the above formula, Y 1′ Represents single bonds, -C(=O)O-, -C(=O)NH-, -OC(=O)-, -NHC(=O)-, -O-, -N(R) c )-, phenylene or carbazolyl. Wherein, R c This indicates an organic group, preferably an alkyl group. Regarding Y... 1′ These groups are bonded to C on the left side and to Y on the right side. 2′ Bonding.

[0436] Y 1′Preferably, it is -C(=O)O-, -O- or imidazolyl, more preferably -C(=O)O- or -O-, and even more preferably -C(=O)O-.

[0437] In the above formula, Y 2′ Linking groups indicate that the number of atoms in a single bond or main chain is 1 to 16 (more preferably 2 to 12, and even more preferably 2 to 10).

[0438] As the Y 2′ There are no specific limitations; for example, we can list:

[0439] -(CH2-CH2-O) p1′ -(p1′ represents an integer from 1 to 10)

[0440] -(CHR) d′ ) p2′ -O-(p2′ is an integer from 1 to 40, R) d′ (representing hydrogen or methyl)

[0441] -(CH2-CH2-O) p3′ -CO-NH-CH2-CH2-O- (p3′ represents an integer from 1 to 10),

[0442] -CH2-CH2-O-CH2-CH2-,

[0443] -(CH2) p4′ -(p4′ represents an integer from 1 to 6)

[0444] -(CH2) p5′ -O-CONH-(CH2) p6′ - (p5′ represents an integer from 1 to 8, preferably 2 or 4; p6′ represents an integer from 1 to 6, preferably 3)

[0445] -(CH2) p7′ -NHC(=O)O-(CH2) p8′ - (p7′ represents an integer from 1 to 6, preferably 3; p8′ represents an integer from 1 to 8, preferably 2 or 4), or

[0446] -O-(but Y) 1′ Not for -O-).

[0447] Y is the preferred 2′ Examples include -(CH2-CH2-O). p1′ -(p1′ represents an integer from 1 to 10) or -(CHR) d′ ) p2′ -O-(p2′ is an integer from 1 to 40, R) d′(Representing hydrogen or methyl), specifically -CH2-CH2-O-. The left end of these groups is adjacent to the main chain side (Y). 1′ The right end is bonded to a functional group selected from substituent group A (R) and bonded to the side. 33′ (Side) bonding.

[0448] R 4a′ Further preferred are the groups shown in the following formula.

[0449]

[0450] In the above formula, X 1′ The denoting element represents a hydrogen atom, a chlorine atom, a fluorine atom, or an alkyl group having 1 to 10 carbon atoms that can be replaced by fluorine, preferably an alkyl group having 1 to 10 carbon atoms, such as methyl. q2′ is an integer from 1 to 10, preferably an integer from 1 to 5, for example, 1. q3′ is an integer from 1 to 10, preferably an integer from 1 to 5, for example, 2.

[0451] The above R 4b′ Each time it appears, it is independently a divalent organic group that does not have a functional group selected from substituent group A.

[0452] As mentioned above, R 4b′ Examples of R mentioned above can be listed. 4b The preferred method for the recorded functional groups is also the same.

[0453] The above R 4′ In the middle, structural unit R 4a′ and structural unit R 4b′ They can form segments individually or combine randomly.

[0454] In one approach, R 4′ Medium structural unit R 4a′ and structural unit R 4b′ Each segment is formed separately.

[0455] In one approach, R 4′ Medium structural unit R 4a′ and structural unit R 4b′ Combining randomly.

[0456] In one approach, R 4′ For R 4a′ That is, R 4′ Structural unit R with functional groups selected from substituent group A 4a constitute.

[0457] In the preferred embodiment, R 4a′ The degree of aggregation is 1 to 100, preferably 2 to 70, more preferably 2 to 50, and even more preferably 2 to 30.

[0458] In one approach, R 4′ For R 4b′ That is, R 4′ Structural unit R that does not have functional groups selected from substituent group A 4b′ constitute.

[0459] In the preferred embodiment, R 4b′ The degree of aggregation is 1 to 100, preferably 2 to 70, more preferably 2 to 50, and even more preferably 2 to 30.

[0460] In the above formula, n′ is an integer from 1 to 100, preferably an integer from 2 to 70, more preferably an integer from 2 to 50, and even more preferably an integer from 3 to 30.

[0461] In the above formula, X a′ Each is an independent divalent organic group.

[0462] In the above formula, X b′ Each is an independent divalent organic group.

[0463] In the above formula, -X a′ -X b′ - This can be understood as R being incorporated into the fluorinated polyether compounds shown in formulas (3) and (4). F1 With R 4′ Part of the connecting group. Therefore, as long as the compounds shown in formulas (3) and (4) can exist stably, X a′ and X b′ It can be any divalent organic group.

[0464] In one manner, X a′ Each of these groups is independently represented by the formula below.

[0465] -(Q) e -(CFZ) f -(CH2) g -

[0466] In the formula, e, f, and g are independent integers from 0 to 10, the sum of e, f, and g is 1 or more, and the order of the repeating units enclosed in parentheses is arbitrary in the formula.

[0467] In the above formula, Q is independently represented by an oxygen atom, a phenylene group, an imidazolyl group, or a -NR group each time it appears. q -(where R) q1 Q represents a hydrogen atom or an organic group, or a divalent polar group. Preferably, Q is an oxygen atom or a divalent polar group.

[0468] As for the "divalent polar group" in Q above, there is no particular limitation; examples include -C(O)- and -C(=NR). b )- and -C(O)NR q2 -(in these formulas R) q2 (Indicates a hydrogen atom or a lower alkyl group). The "lower alkyl group" is, for example, an alkyl group having 1 to 6 carbon atoms, such as methyl, ethyl, n-propyl, which may be substituted with one or more fluorine atoms.

[0469] In the above formula, Z is independently a hydrogen atom, a fluorine atom, or a lower fluoroalkyl group each time it appears, preferably a fluorine atom. The "lower fluoroalkyl group" is, for example, a fluoroalkyl group with 1 to 6 carbon atoms, preferably 1 to 3 carbon atoms, preferably a perfluoroalkyl group with 1 to 3 carbon atoms, more preferably trifluoromethyl or pentafluoroethyl, and even more preferably trifluoromethyl.

[0470] X a′ Preferably, it contains the group shown in the following formula.

[0471] -(O) e -(CF2) f -(CH2) g -.

[0472] [In the formula, e, f, and g have the same meaning as above, and the order of the repeating units enclosed in parentheses is arbitrary.]

[0473] Among them, the left end of these groups is connected to R F1 Bonding.

[0474] In one manner, X a′ It can be a group as shown in the following formula:

[0475] -(O) e1′ -(CH2) g2′ -O-[(CH2) g3′ -O-] g4′ ,

[0476] -(O) e1′ -(CF2) f2′ -(CH2) g2′ -O-[(CH2) g3′ -O-] g4′ .

[0477] [In the formula,

[0478] e1′ is 0 or 1.

[0479] f2′, g2′, and g3′ are each an independent integer from 1 to 10.

[0480] g4′ is either 0 or 1.

[0481] Among them, the left end of these groups is connected to R F1 Bonding.

[0482] In the preferred embodiment, X a′ It can be a group as shown in the following formula.

[0483] -(CH2) g2′ -O-

[0484] [In the formula, g2′ is an integer from 1 to 10.]

[0485] Wherein, the left end of this group is connected to R F1 Bonding.

[0486] In the above formula, X b′ Each is an independent divalent organic group.

[0487] As for the above X b′ Examples of X can be listed above. b The preferred method for the recorded functional groups is also the same.

[0488] As mentioned above, R a′ Examples of R mentioned above can be listed. a The preferred method for the recorded functional groups is also the same.

[0489] In a preferred embodiment, the fluorinated polyether compound described above may be a fluorinated polyether compound as shown in formula (3).

[0490] The number-average molecular weight of the above-mentioned fluorinated polyether compounds is not particularly limited and can be 2 × 10⁻⁶. 2 ~1×10 5 Preferably 1×10 3 ~5×10 4 More preferably 3×10 3 ~2×10 4 By achieving a number-average molecular weight within this range, it is possible to further increase the solubility in solvents and the contact angle of the surface-treated layer. This number-average molecular weight can be determined using gel permeation chromatography (GPC).

[0491] The polydispersity (weight-average molecular weight (Mw) / number-average molecular weight (Mn)) of the above-mentioned fluorinated polyether-based compound is preferably 3.0 or less, more preferably 2.5 or less, even more preferably 2.0 or less, and even more preferably 1.5 or less. By reducing the polydispersity, a more homogeneous surface treatment layer can be formed, and the durability of the surface treatment layer can be further improved.

[0492] The aforementioned fluoropolymers can be synthesized, for example, using so-called RAFT (Reversible addition-fragmentation chain transfer) type free radical polymerization.

[0493] First, a RAFT agent having a perfluoropolyether group is prepared. For example, by reacting a compound (A) having a perfluoropolyether group with a compound (B3) or (B4) having a RAFT backbone (-SC(=S)-), a chain transfer agent (3a) or (4a) having a perfluoropolyether group can be obtained.

[0494]

[0495] R F1 -X a’ -L 2’ (B3)

[0496] L 2’ -X a’ -R F2 -X a’ -L 2’ (B4)

[0497] [In the formula, R] a’ R F1 R F2 X a’ and X b’ The meaning is the same as above;

[0498] L 1’ and L 2’ These are the detached parts.

[0499]

[0500] [In the formula, R] a’ R F1 R F2 X a’ and X b’ The meaning is the same as above.

[0501] By reacting the chain transfer agent (3a) or (4a) obtained above with a monomer having unsaturated bonds, the compound shown in formula (3) or (4) above can be obtained. This reaction is called RAFT polymerization, and the reaction conditions can be those commonly used in RAFT polymerization.

[0502] In another preferred embodiment, the fluorinated polyether compound is a fluorinated polyether compound of general formula (5).

[0503] (R F1 -X c )n2 -R 10 -(R 8 -OC(O)CR 9 =CH2) n3 (5)

[0504] [In the formula,

[0505] R F1 The meaning is the same as above.

[0506] X c It is expressed as follows: -(Q) d -(CFZ) e -(CH2) f -The group shown,

[0507] (Formula - (Q)) d -(CFZ) e -(CH2) f In the symbol - Q represents oxygen atom, phenylene, carbazolyl group, and -NR. a - or divalent polar group, formula -NR a - In the middle, R a Z represents a hydrogen atom or organic group, Z represents a hydrogen atom, a fluorine atom, or a lower fluorinated alkyl group, d, e, and f are each independent integers greater than 0 and less than 50, the sum of d, e, and f is at least 1, and the order of the repeating units enclosed in parentheses is arbitrary in the formula.

[0508] R 10 This indicates an organic group with (n2+n3) valence that can have a ring structure, heteroatoms, and / or functional groups.

[0509] R 8 Represents a divalent organic group.

[0510] R 9 This refers to an alkyl group containing 1 to 10 carbon atoms, including hydrogen, chlorine, fluorine, or fluorine-substituted carbon atoms.

[0511] n2 is an integer from 1 to 3.

[0512] n3 is an integer from 1 to 3.

[0513] In the above formula (3), X C Formula: -(Q) d -(CFZ) e -(CH2) f - The group shown. Wherein, d, e and f are independent integers above 0 and below 50, the sum of d, e and f is at least 1, and the order of the repeating units enclosed in parentheses is arbitrary in the formula.

[0514] In the above formula, Q represents an oxygen atom, a phenylene group, an imidazolyl group, or -NR. a -(where R is in the formula) a (representing a hydrogen atom or an organic group) or a divalent polar group, preferably an oxygen atom or a divalent polar group, more preferably an oxygen atom.

[0515] As for the "divalent polar group" in Q above, there is no particular limitation; examples include -C(O)- and -C(=NR). b )- and -C(O)NR b -(in these formulas R) b (Indicates a hydrogen atom or a lower alkyl group). The "lower alkyl group" is, for example, an alkyl group having 1 to 6 carbon atoms, such as methyl, ethyl, n-propyl, which may be substituted with one or more fluorine atoms.

[0516] In the above formula, Z represents a hydrogen atom, a fluorine atom, or a lower fluorinated alkyl group, preferably a fluorine atom.

[0517] The aforementioned "lower fluoroalkyl group" is, for example, a fluoroalkyl group having 1 to 6 carbon atoms, preferably 1 to 3 carbon atoms, more preferably a perfluoroalkyl group having 1 to 3 carbon atoms, more preferably trifluoromethyl or pentafluoroethyl, and even more preferably trifluoromethyl.

[0518] X C The preferred formula is: -(O) d -(CF2) e -(CH2) f - (In the formula, d, e and f have the same meaning as above, and the order of the repeating units enclosed in parentheses is arbitrary in the formula) the group shown.

[0519] As in the above expression: -(O) d -(CF2) e -(CH2) f The group indicated by - can be exemplified by -(O). d′ -(CF2) e′ -(CH2) f′ -O-[(CH2) f″ -O-] f″′ (In the formula, d′ is 0 or 1, e′, f′ and f″ are independent integers from 1 to 10, and f″′ is 0 or 1) the group shown.

[0520] In equation (3) above, R 10 This refers to an organic group with (n2+n3) valence that can have a ring structure, heteroatoms, and / or functional groups.

[0521] In the above formula (3), n2 is an integer from 1 to 3.

[0522] In the above formula (3), n3 is an integer from 1 to 3.

[0523] Ideally, n2+n3 should be 3, for example, n2 should be 1 and n3 should be 2, or n2 should be 2 and n3 should be 1.

[0524] As mentioned above, R 10 The phrase "organic groups with (n2+n3) valences that may have ring structures, heteroatoms, and / or functional groups" can be used to list, for example, groups derived by further removing (n2+n3-1) hydrogen atoms from a monovalent organic group.

[0525] R 10 Preferably, the group is represented by the following formula:

[0526]

[0527] More preferably R 10 For groups represented by the following formula:

[0528]

[0529] In equation (3) above, R 8 This indicates a divalent organic group. The R... 8 Preferably -O-(CH2) r -(where r is an integer from 1 to 10, preferably an integer from 1 to 3), -NH-(CH2) r -(where r has the same meaning as above), more preferably -O-(CH2). r -(where r is an integer from 1 to 3).

[0530] In equation (3) above, R 9 It represents an alkyl group containing 1 to 10 carbon atoms, including hydrogen, chlorine, fluorine, or fluorine atoms.

[0531] R 9 Preferably, it is an alkyl group having 1 to 10 hydrogen atoms, more preferably an alkyl group having 1 to 6 hydrogen atoms, and even more preferably a hydrogen atom or a methyl group.

[0532] In another embodiment, the fluoropolymer (3) is at least one fluoropolymer obtained by reacting the NCO group present in the triisocyanate formed by polymerizing (a) diisocyanate with the active hydrogen of at least one active hydrogen compound shown in formula (a1) and / or (a2) and at least one active hydrogen compound shown in formula (a3).

[0533] R F1 -OC(Z)F(CF2) g -(CH2) g -OH (a1)

[0534] HO-(CH2) h -(CF2) g C(Z)FOR F2 -OC(Z)F(CF2) g -(CH2) h -OH (a2)

[0535] [In the formula, R] F1 R F2 The meanings of Z, g, and h are the same as above.

[0536] CH2=CR 9 C(O)OR 30 -OH (a3)

[0537] [In the formula, R] 9 The meaning is the same as above.

[0538] R 30 This indicates a divalent organic group.

[0539] R in equation (a3) 30 Preferably -(CH2) r′ -(where r′ is an integer of 1 to 10, preferably an integer of 1 to 3), -CH(CH3)-, -CH(CH2CH3)-, -CH(CH2OC6H5)-, more preferably -(CH2). r′ -(where r′ is an integer from 1 to 3).

[0540] The fluorinated polyether compound shown in formula (5) above can have 5 × 10 2 ~1×10 5 The number average molecular weight is [not specified]. Within this range, from the viewpoint of friction durability, a number average molecular weight of 2,000 to 10,000 is preferred. This number average molecular weight can be determined by [variables / measurements]. 19 Obtained by F-NMR.

[0541] [Matrix-forming composition]

[0542] The aforementioned matrix-forming composition refers to a composition containing a compound having at least one carbon-carbon double bond, such as compositions containing monofunctional and / or polyfunctional acrylates and methacrylates (hereinafter also collectively referred to as "(meth)acrylates"), monofunctional and / or polyfunctional urethane (meth)acrylates, and monofunctional and / or polyfunctional epoxy (meth)acrylates, but without particular limitation. The composition forming the matrix is ​​not particularly limited and is generally considered to be a hard coating agent or an antireflective agent; examples include hard coating agents containing polyfunctional (meth)acrylates or antireflective agents containing fluorinated (meth)acrylates. For example, the hard coating agent can be BEAMSET 502H, 504H, 505A-6, 550B, 575CB, 577, 1402 (trade names) sold by Arakawa Chemical Industry Co., Ltd., EBECRYL40 (trade name) sold by Daicel-Cytec, and HR300 series (trade names) sold by Yokohama Rubber. The aforementioned antireflective agent can be, for example, OPTOOL AR-110 (trade name) sold by Daikin Industries, Ltd.

[0543] Compositions forming the above-mentioned matrix are preferably compositions containing monofunctional and / or polyfunctional epoxy compounds. For example, epoxides such as bisphenol A diglycidyl ether, 2,2′-bis(4-glycidoxycyclohexyl)propane, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexane carboxylate, vinylcyclohexene dioxide, 2-(3,4-epoxycyclohexyl)-5,5-spiro-(3,4-epoxycyclohexane)-1,3-dioxane, bis(3,4-epoxycyclohexyl)adipic acid ester, 1,2-cyclopropane dicarboxylic acid diglycidyl ester, and triglycidyl isocyanurate can be used. In addition, although there is overlap with the above compounds, hydrogenated epoxy resins, alicyclic epoxy resins, or epoxy resins containing isocyanurate rings, or bisphenol A type epoxy resins, bisphenol F type epoxy resins, phenolic varnish type epoxy resins, cresol phenolic varnish type epoxy resins, naphthalene type epoxy resins, biphenyl type epoxy resins, phenolic alkyl type epoxy resins, biphenyl alkyl type epoxy resins, hydrogenated epoxy resins obtained by hydrogenating the aromatic rings of the above various epoxy resins, and dicyclopentadiene type epoxy resins can be used.

[0544] [Curved Composition]

[0545] In one embodiment, the mass ratio of the organosilicon copolymer to the fluorinated polyether compound in the cured composition is in the range of 0.1:100 to 100:0.1, preferably 0.5:100 to 100:100. By setting the mass ratio of the organosilicon copolymer to the fluorinated polyether compound to such a range, higher water repellency and surface lubrication, as well as the effect of inhibiting exudation, can be obtained.

[0546] In one embodiment, the organosilicon copolymer and the fluorinated polyether compound comprise 0.01 to 20% by mass, preferably 0.01 to 10% by mass, and more preferably 0.1 to 10% by mass, relative to the solid component of the composition forming the matrix.

[0547] In a preferred embodiment, the organosilicon copolymer is an organosilicon copolymer of formula (1) or (2), and the fluorinated polyether compound is a fluorinated polyether compound of formula (3) or (4).

[0548] The curable composition of the present invention may also contain at least one fluorinated oil of the following general formula (C) (hereinafter also referred to as "fluorinated oil (C)").

[0549] Rf 2 -(OC4F8) a′ -(OC3F6) b′ -(OC2F4) c′ -(OCF2) d′ -Rf 3 …(C)

[0550] In the above formula (C), Rf 2 Rf represents an alkyl group having 1 to 16 carbon atoms that can be replaced by one or more fluorine atoms. 3 Represents a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 16 carbon atoms that can be substituted by one or more fluorine atoms. Rf is preferred. 2 and Rf 3 Each of the above is an alkyl group having 1 to 3 carbon atoms that can be replaced by one or more fluorine atoms, more preferably a perfluoroalkyl group having 1 to 3 carbon atoms.

[0551] In formula (C) above, a′, b′, c′, and d′ represent the number of three repeating units of the perfluoro(poly)ether constituting the main backbone of the polymer, and are independent integers of 0 to 300, preferably 0 to 200. The sum of a′, b′, c′, and d′ is at least 1, preferably 1 to 300. The order of the repeating units marked with subscripts a′, b′, c′, or d′ and enclosed in parentheses is arbitrary in the formula. Among these repeating units, -(OC4F8)- can be any one of -(OCF2CF2CF2CF2)-, -(OCF(CF3)CF2CF2)-, -(OCF2CF(CF3)CF2)-, -(OCF2CF2CF(CF3))-, -(OC(CF3)2CF2)-, -(OCF2C(CF3)2)-, -(OCF(CF3)CF(CF3))-, -(OCF(C2F5)CF2)-, and -(OCF2CF(C2F5)), preferably -(OCF2CF2CF2CF2)-. -(OC3F6)- can be any one of -(OCF2CF2CF2)-, -(OCF(CF3)CF2)-, and -(OCF2CF(CF3))-, preferably -(OCF2CF2CF2)-. -(OC2F4)- can be either -(OCF2CF2)- or -(OCF(CF3))-, with -(OCF2CF2)- being preferred.

[0552] As an example of the fluorinated oil represented by the above general formula (C), compounds represented by any of the following general formulas (C1) and (C2) can be listed (which may be one or a mixture of two or more).

[0553] Rf 2 -(OCF2CF2CF2) b" -Rf 3 …(C1)

[0554] [In the formula, Rf] 2 and Rf 3 As mentioned above, b" is an integer from 0 to 300, and the order of repeated units marked with subscript b" and enclosed in parentheses is arbitrary in the formula.

[0555] Rf 2 -(OCF2CF2CF2CF2) a" -(OCF2CF2CF2) b" -(OCF2CF2) c" -(OCF2) d" -Rf 3 …(C2)

[0556] [In the formula, Rf] 2 and Rf 3As mentioned above, a" and b" are independent integers from 0 to 30, and c" and d" are independent integers from 0 to 300. The order of the repeating units marked with subscripts a", b", c", and d" and enclosed in parentheses is arbitrary in the formula.

[0557] The aforementioned fluorinated oil (C) can have an average molecular weight of about 1,000 to 30,000. This allows for the attainment of high surface lubricity.

[0558] In the curable composition of the present invention, the fluorinated oil (C) may contain, for example, 0 to 80 parts by mass, preferably 0 to 40 parts by mass, relative to the total of the above-mentioned fluorinated polyether compounds (or the total of two or more, the same below) of 100 parts by mass.

[0559] In the curable composition of the present invention, the fluorinated oil (C) preferably contains 40% by mass or less relative to the total of the above-mentioned fluorinated polyether compound and the fluorinated oil (C).

[0560] The aforementioned fluorinated oil (C) helps to improve the surface lubrication of the surface treatment layer.

[0561] In addition to the above-mentioned components, the curable composition of the present invention may also contain other components, such as silicone oil, active energy ray free radical curing initiator, hot acid generator, active energy ray cationic curing initiator, etc.

[0562] As the aforementioned silicone oil, linear or cyclic silicone oils with siloxane bonds of 2,000 or less can be used. Linear silicone oils can be so-called linear silicone oils and modified silicone oils. Examples of linear silicone oils include dimethyl silicone oil, methylphenyl silicone oil, and methyl hydrogenated silicone oil. Examples of modified silicone oils include modified silicone oils obtained by modifying linear silicone oils with polyethers, higher fatty acid esters, fluoroalkyl groups, amino groups, epoxy groups, carboxyl groups, alcohols, etc. Cyclic silicone oils include, for example, cyclic dimethylsiloxane oil.

[0563] In the curable composition of the present invention, the silicone oil may contain, for example, 0 to 50 parts by mass, preferably 0 to 10 parts by mass, relative to the total of the above-mentioned organosilicon copolymer and fluorinated polyether compound (or the total of two or more compounds, the same below).

[0564] As an active energy ray free radical curing initiator, for example, electromagnetic waves in the wavelength region below 350 nm, such as ultraviolet rays, electron rays, X-rays, and gamma rays, can be used to generate free radicals, which can initiate the curing (crosslinking reaction) of curable sites (such as carbon-carbon double bonds) of organosilicon copolymers and fluorinated polyether compounds. Substances that generate free radicals using ultraviolet rays are usually used as catalysts.

[0565] The active energy ray free radical curing initiator in the curable composition of the present invention can be appropriately selected according to the type of curable site in the organosilicon copolymer and the fluorinated polyether compound, the type (wavelength region, etc.) of the active energy ray used, and the irradiation intensity, etc. Generally speaking, the following substances can be cited as examples of initiators for curing organosilicon copolymers and fluorinated polyether compounds with curable sites (carbon-carbon double bonds) that have free radical reactivity using active energy rays in the ultraviolet region.

[0566] ·Acetophenone series

[0567] Acetophenone, chloroacetophenone, diethoxyacetophenone, hydroxyacetophenone, α-aminoacetophenone, hydroxyacetophenone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinylpropane-1-one, etc.

[0568] ·Benzoin series

[0569] Benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzoyl dimethyl ketal, etc.

[0570] ·Benzophenone series

[0571] Benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, hydroxypropylbenzophenone, acrylated benzophenone, Michelone, etc.

[0572] ·Thioxanones

[0573] Thioxanone, chlorothioxanone, methylthioxanone, diethylthioxanone, dimethylthioxanone, etc.

[0574] ·other

[0575] Benzoyl, α-acyl oxime ester, acylphosphine oxide, glyoxylate, 3-coumarinone, 2-ethylanthraquinone, camphorquinone, anthraquinone, etc.

[0576] These active energy ray curing initiators can be used alone or in combination of two or more.

[0577] The above-mentioned active energy ray curing initiator is not particularly limited. Relative to 100 parts by mass of the organosilicon copolymer, the fluorinated polyether compound, and the fluorinated oil (C) in the presence, the initiator may contain 0.01 to 1,000 parts by mass, preferably 0.1 to 500 parts by mass.

[0578] By using the aforementioned hot acid generator, the heat causes the cationic compounds to decompose, initiating the curing (crosslinking reaction) of the curable sites of the organosilicon copolymers and fluorinated polyether compounds (e.g., cyclic ethers).

[0579] As the above-mentioned hot acid generating agent, the compound shown in the following general formula (a) is preferred, for example.

[0580] (R 1 a R 2 b R 3 c R 4 d Z) +m (AX n ) －m (a)

[0581] (In the formula, Z represents an element selected from at least one of S, Se, Te, P, As, Sb, Bi, O, N, and halogens. R) 1 R 2 R 3 and R 4 The same or different indicates an organic group. a, b, c, and d are 0 or positive numbers, and the sum of a, b, c, and d equals the valence of Z. Cation (R) 1 a R 2 b R 3 c R 4 d Z) +m This indicates an onium salt. A represents the metallic or metalloid element as the central atom in the halide complex, selected from at least one of B, P, As, Al, Ca, In, Ti, Zn, Sc, V, Cr, Mn, and Co. X represents a halide element. m is the pure charge of the halide complex ion. n is the number of halide elements in the halide complex ion.

[0582] As the anion (AX) of the above general formula (a) n ) －m For specific examples, tetrafluoroborate (BF4) can be cited. － ), hexafluorophosphate (PF6) － ), hexafluoroantimonate (SbF6) － ), hexafluoroarsenate (AsF6) － ), hexachloroantimonate (SbCl6) － ), etc. It can also use the general formula AXn(OH). － The anion shown is shown. Other anions that can be listed include perchlorate ion (ClO4). － ), trifluoromethyl sulfite ions (CF3SO3) － ), fluorosulfonate ions (FSO3) －), toluenesulfonate ion, trinitrobenzenesulfonate ion, etc.

[0583] Specific products of the aforementioned hot acid generators include, for example, diazonium salts such as the AMERICURE series (manufactured by American Can), ULTRASET series (manufactured by ADEKA), and WPAG series (manufactured by Wako Pure Chemical Industries); iodonium salts such as the UVE series (manufactured by General Electric), FC series (manufactured by 3M), UV9310C (manufactured by GE Toshiba Silicones), Photoinitiator 2074 (manufactured by Rhona-Planck), and WPI series (manufactured by Wako Pure Chemical Industries); and sulfonium salts such as the CYRACURE series (manufactured by Union Carbide), UVI series (manufactured by General Electric), FC series (manufactured by 3M), CD series (manufactured by SARTOMER), OPTOMER SP series / OPTOMER CP series (manufactured by ADEKA), SAN-AID SI series (manufactured by Sanshin Chemical Industry Co., Ltd.), CI series (manufactured by Nippon Soda), WPAG series (manufactured by Wako Pure Chemical Industries), and CPI series (manufactured by SAN-APRO).

[0584] These hot acid generating agents can be used alone or in combination of two or more.

[0585] The above-mentioned hot acid generating agent is not particularly limited, and the hot acid generating agent contains 0.01 to 1,000 parts by mass, preferably 0.1 to 500 parts by mass, relative to a total of 100 parts by mass of the organosilicon copolymer, the fluorinated polyether compound, and the fluorinated oil (C) in the presence.

[0586] By using the above-mentioned active energy ray cationic curing initiator, the compound containing the cationic species is photoexcited and undergoes a photodecomposition reaction, which initiates the curing (crosslinking reaction) of the curable sites of organosilicon copolymers and fluorinated polyether compounds (e.g., cyclic ethers).

[0587] Preferred active energy ray cationic curing initiators include, for example, triphenylsulfonium hexafluoroantimonate, triphenylsulfonium phosphate, p-(phenylthio)phenyl diphenylsulfonium hexafluoroantimonate, p-(phenylthio)phenyl diphenylsulfonium hexafluorophosphate, 4-chlorophenyl diphenylsulfonium hexafluorophosphate, 4-chlorophenyl diphenylsulfonium hexafluoroantimonate, bis[4-(diphenylsulfonium)phenyl]sulfide ...

[0588] Specific products of the aforementioned active energy ray cationic curing initiators are preferably, for example, UVI-6950, UVI-6970, UVI-6974, and UVI-6990 (manufactured by Union Carbide); ADEKA OPTOMER SP-150, SP-151, SP-170, and SP-172 (manufactured by ADEKA); and Irgacure 250 (CIBA). (Manufactured by JAPAN Corporation); CI-2481, CI-2624, CI-2639, CI-2064 (manufactured by Nippon Soda Corporation); CD-1010, CD-1011, CD-1012 (manufactured by SARTOMER Corporation); DTS-102, DTS-103, NAT-103, NDS-103, TPS-103, MDS-103, MPI-103, BBI-103 (manufactured by MIDORI Chemicals Corporation); PCI-061T, PCI-062T, PCI-020T, PCI-022T (manufactured by Nippon Kayaku Corporation); CPI-100P, CPT-101A, CPI-200K (manufactured by SAN-APRO Corporation); SAN-AID SI-60L, SAN-AID SI-80L, SAN-AID SI-100L, SAN-AID ST-110L, SAN-AID SI-145, SAN-AID SI-150, SAN-AID SI-160, SAN-AID SI-180L (manufactured by Sanshin Chemical Industry Co., Ltd.); WPAG series (manufactured by Wako Pure Chemical Industries Co., Ltd.), etc., are diazonium salt, iodonium salt, and sulfonium salt types.

[0589] These active energy ray cationic curing initiators can be used alone or in combination of two or more.

[0590] The above-mentioned active energy ray free radical curing initiator is not particularly limited, but contains 0.01 to 1,000 parts by mass, preferably 0.1 to 500 parts by mass, relative to a total of 100 parts by mass of the organosilicon copolymer, the fluorinated polyether compound, and the fluorinated oil (C) in the presence.

[0591] The curable composition of the present invention may contain a solvent. Fluorinated organic solvents and non-fluorinated organic solvents can be used as the solvent.

[0592] Examples of such fluorinated organic solvents include perfluorohexane, perfluorooctane, perfluorodimethylcyclohexane, perfluorodecahydronaphthalene, perfluoroalkyl ethanol, perfluorobenzene, perfluorotoluene, perfluoroalkylamine (FLUORINERT, trade name, etc.), perfluoroalkyl ethers, perfluorobutyltetrahydrofuran, polyfluoroaliphatic hydrocarbons (ASAHIKLIN AC6000, trade name), and hydrochlorofluorocarbons (ASAHIKLIN...). AK-225 (trade name), etc.), hydrofluoroethers (NOVEC (trade name), HFE-7100 (trade name), etc.), 1,1,2,2,3,3,4-heptafluorocyclopentane, fluorinated alcohols, perfluoroalkyl bromides, perfluoroalkyl iodides, perfluoropolyethers (KRYTOX (trade name), DEMNUM (trade name), FOMBLIN (trade name), etc.), 1,3-bis(trifluoromethylbenzene), 2-(perfluoroalkyl)ethyl methacrylate, 2-(perfluoroalkyl)ethyl acrylate, perfluoroalkyl ethylene, Freon 134a and hexafluoropropylene oligomers.

[0593] In addition, examples of such non-fluorinated organic solvents include acetone, methyl isobutyl ketone, cyclohexanone, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether acetate, dipropylene glycol dimethyl ether pentane, hexane, heptane, octane, dichloromethane, chloroform, carbon tetrachloride, dichloroethane, carbon disulfide, benzene, toluene, xylene, nitrobenzene, diethyl ether, dimethoxyethane, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, ethyl acetate, butyl acetate, dimethylformamide, dimethyl sulfoxide, 2-butanone, acetonitrile, benzonitrile, butanol, 1-propanol, 2-propanol, ethanol, methanol, and diacetone alcohol.

[0594] The solvent used in the curable composition of the present invention is preferably methyl isobutyl ketone, propylene glycol monomethyl ether, hexadecane, butyl acetate, acetone, 2-butanone, cyclohexanone, ethyl acetate, diacetone alcohol, or 2-propanol.

[0595] These solvents can be used alone or in combination of two or more.

[0596] The solvent contains 5 to 100,000 parts by mass, preferably 5 to 50,000 parts by mass, relative to a total of 100 parts by mass of the organosilicon copolymer, the fluorinated polyether compound, and the fluorinated oil (C) in the presence.

[0597] The curable composition of the present invention may also contain antioxidants, tackifiers, leveling agents, defoamers, antistatic agents, antifogging agents, ultraviolet absorbers, pigments, dyes, inorganic particles such as silica, fillers such as aluminum paste, talc, glass frit, and metal powder, polymerization inhibitors such as butylated hydroxytoluene (BHT) and phenothiazine (PTZ).

[0598] The items of the present invention will now be described.

[0599] The present invention provides an article comprising a substrate and a layer (surface treatment layer) formed on the surface of the substrate by a curable composition of the present invention. This article can be manufactured, for example, by the following means.

[0600] First, prepare the substrate. The substrate that can be used in this invention can be made of any suitable material such as glass, resin (natural or synthetic resin, such as general plastic materials, preferably polycarbonate resin, poly(meth)acrylate resin, polyethylene terephthalate resin, triacetyl cellulose resin, polyimide resin, modified (transparent) polyimide resin, polycyclic olefin resin, polyethylene naphthalate resin, which can be in plate, film, or other form), metal (can be a composite of elemental metals such as aluminum, copper, silver, iron, etc. or alloys), ceramics, semiconductors (silicon, germanium, etc.), fibers (fabric, non-woven fabric, etc.), fur, leather, wood, ceramics, stone, building components, etc.

[0601] For example, if the desired item is an optical component, the material constituting the surface of the substrate can be a material used in optical components, such as glass or transparent plastic. Furthermore, the substrate can have insulating layers, adhesive layers, protective layers, decorative frame layers (I-CON), atomizing film layers, hard coating layers, polarizing films, retardation films, organic EL display modules, and liquid crystal display modules, depending on its specific design.

[0602] There are no particular limitations on the shape of the substrate. In addition, the surface area of ​​the substrate to which the surface treatment layer is to be formed only needs to be at least a portion of the substrate surface, and can be appropriately determined according to the intended use of the article to be manufactured and the specific design.

[0603] Next, a film of the curable composition of the present invention is formed on the surface of the substrate, and the film is post-treated as needed, thereby forming a surface treatment layer from the curable composition of the present invention.

[0604] Film formation of the curable composition of the present invention can be achieved by applying the curable composition to the surface of a substrate in a manner that coats the surface. The coating method is not particularly limited. For example, a wet coating method can be used.

[0605] Examples of wet coating methods include dip coating, spin coating, flow coating, spray coating, roller coating, gravure coating, microgravure coating, bar coating, die coating, screen printing, and similar methods.

[0606] When using the wet coating method, the curable composition of the present invention can be diluted with a solvent before being applied to the surface of a substrate. As this solvent, the aforementioned fluorinated organic solvents and non-fluorinated organic solvents can be used. From the viewpoint of the stability of the curable composition of the present invention and the volatility of the solvent, the following solvents are preferred: perfluoroaliphatic hydrocarbons with 5 to 12 carbon atoms (e.g., perfluorohexane, perfluoromethylcyclohexane, and perfluoro-1,3-dimethylcyclohexane); polyfluoroaromatic hydrocarbons (e.g., bis(trifluoromethyl)benzene); polyfluoroaliphatic hydrocarbons; hydrofluoroethers (HFE) (e.g., perfluoropropyl methyl ether (C3F7OCH3), perfluorobutyl methyl ether (C4F9OCH3), perfluorobutyl ethyl ether (C4F9OC2H5), perfluorohexyl methyl ether (C2F5CF(OCH3)C3F7) and other alkyl perfluoroalkyl ethers (perfluoroalkyl and alkyl groups can be straight-chain or branched)), hydrochlorofluorocarbons (ASAHIKLIN). Solvents such as AK-225 (trade name), methyl solvent, ethyl solvent, methyl solvent acetate, and ethyl solvent acetate; diethyl oxalate, ethyl pyruvate, ethyl 2-hydroxybutyrate, ethyl acetoacetate, ethyl acetate, butyl acetate, amyl acetate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 2-hydroxyisobutyrate, ethyl 2-hydroxyisobutyrate. Ester solvents such as esters; propylene glycol solvents such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether acetate, and dipropylene glycol dimethyl ether; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, 2-hexanone, cyclohexanone, methyl amino ketone, and 2-heptanone; alcohol solvents such as methanol, ethanol, propanol, isopropanol, butanol, and diacetone alcohol; and aromatic hydrocarbons such as toluene and xylene. These solvents can be used alone or in mixtures of two or more. Among them, hydrofluoroethers, glycol solvents, ester solvents, ketone solvents, and alcohol solvents are preferred, and perfluorobutyl methyl ether (C4F9OCH3) and / or perfluorobutyl ethyl ether (C4F9OC2H5), propylene glycol monomethyl ether, ethyl acetate, butyl acetate, propylene glycol monomethyl ether acetate, methyl ethyl ketone, methyl isobutyl ketone, isopropanol, butanol, and diacetone alcohol are particularly preferred.

[0607] Next, the film undergoes post-treatment. This post-treatment is not particularly limited; for example, it can be performed by irradiation with active energy rays, such as electromagnetic waves in the wavelength region below 350 nm, i.e., ultraviolet light, electron beams, X-rays, gamma rays, etc., or by heating for a specified time. By performing this post-treatment, curing is initiated in the curable sites of the organosilicon copolymer and the fluorinated polyether compound, as well as the curable sites of the matrix-forming composition, forming bonds between these compounds and between these compounds and the substrate.

[0608] As described above, a surface treatment layer derived from the curable composition of the present invention is formed on the surface of a substrate to manufacture the article of the present invention. The resulting surface treatment layer exhibits both high surface lubricity (or lubricity, such as the ability to wipe away fingerprints and excellent tactile feel on the fingers) and high friction durability. Furthermore, in addition to high friction durability and surface lubricity, depending on the composition of the curable composition used, this surface treatment layer may also possess water-repellent, oil-repellent, and stain-resistant properties (e.g., prevention of fingerprint adhesion), making it well-suited for use as a functional film.

[0609] The static friction coefficient of the film formed by the surface treatment composition of the present invention is preferably 1.3 or less, more preferably 1.1 or less, and even more preferably 1.0 or less.

[0610] The film formed from the surface treatment composition of the present invention preferably has a coefficient of kinetic friction of 0.43 or less, more preferably 0.41 or less, and even more preferably 0.39 or less.

[0611] The static and dynamic friction coefficients mentioned above can be measured using a tribometer (Tribomaster TL201Ts, manufactured by Trinity-Lab Co., Ltd.) with a tactile contact as the friction element, at a load of 20gf and a scanning speed of 10mm / sec.

[0612] The present invention also relates to optical materials having the above-described surface treatment layer as the outermost layer.

[0613] In addition to the optical materials related to displays and the like that exemplified below, a wide variety of optical materials are also preferred as optical materials, such as: displays of cathode ray tubes (CRTs, such as TVs and personal computer monitors), liquid crystal displays, plasma displays, organic EL displays, inorganic thin-film EL dot matrix displays, rear projection displays, fluorescent tubes (VFDs), field emission displays (FEDs), etc., or protective plates, films, or materials on which anti-reflective coatings have been applied.

[0614] In one embodiment, an article having the surface treatment layer obtained by the present invention can be an optical component, but is not particularly limited thereto. Examples of optical components include: lenses for eyeglasses, etc.; front protective panels, anti-spray films, anti-reflective films, polarizers, and anti-glare plates for displays such as PDPs and LCDs; touchscreen sheets for devices such as portable telephones and portable information terminals; disc surfaces for Blu-ray discs, DVD discs, CD-Rs, MO discs, etc.; optical fibers, etc.

[0615] In one embodiment, examples of articles having the surface treatment layer obtained by the present invention include LiDAR (Light Detection and Ranging) cover components, sensor components, dashboard cover components, automotive interior components, etc., particularly these components for automobiles.

[0616] The thickness of the surface treatment layer is not particularly limited. In the case of optical components, from the viewpoints of optical performance, surface lubricity, friction durability and anti-fouling properties, a thickness of 0.1 to 30 μm, preferably 0.5 to 20 μm, is preferred for the surface treatment layer.

[0617] The articles obtained using the curable composition of the present invention have been described in detail above. However, the uses, methods of use, and methods of manufacturing the articles of the curable composition of the present invention are not limited to the examples described above.

[0618] Example

[0619] The present invention will be described below by way of examples, but the present invention is not limited to the following examples. Furthermore, in these examples, the chemical formulas shown below represent average compositions, and the order in which the repeating units constituting the perfluoropolyether ((OCF2CF2CF2), (OCF2CF2), (OCF2), etc.) exist is arbitrary.

[0620] 1. Synthesis of organosilicon-containing chain transfer agents

[0621] (1) Synthesis of chain transfer agent (A-1)

[0622] In a flask, 0.895 g of 2-[(dodecylsulfanylthiocarbonyl)sulfanyl]propane acid (manufactured by Fujifilm and Koko Pure Chemical Industries, Ltd.), 0.031 g of 4-dimethylaminopyridine (DMAP) (manufactured by Tokyo Chemical Industry Co., Ltd.), 0.489 g of 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride (EDCI) (manufactured by Tokyo Chemical Industry Co., Ltd.), and 10.0 g of single-terminated methanol-modified organosilicon X-22-170DX (number average molecular weight 4,700, manufactured by Shin-Etsu Chemical Industry Co., Ltd.) were added, along with 15 mL of dichloromethane. The mixture was stirred at room temperature to allow the reaction to proceed. After stirring overnight, the reaction solution was washed with a saturated sodium bicarbonate aqueous solution and brine. After separating and concentrating the organic layer, it was dropped into methanol to obtain 9.49 g of the yellow oily target substance (A-1) by dehydration condensation of 2-[(dodecylthiothiocarbonyl)thio]propionic acid and single-terminal methanol-modified organosilicon X-22-170DX.

[0623] Synthesis of Organosilicon Chain Transfer Agent (A-2)

[0624] Except for replacing X-22-170DX with 21.3g of single-terminal methanol-modified organosilicon FM-0425 (number average molecular weight 10,000 (manufactured by JNC), the same synthesis as (A-1) yielded 19.5g of the yellow oily target compound (A-2).

[0625] 2. Synthesis of organosilicon copolymers with epoxy groups (S-1) to (S-3)

[0626] 1.0 g of chain transfer agent (A-1), 0.16 g of 4-hydroxybutyl acrylate glycidyl ether (4HBAGE) (manufactured by Mitsubishi Chemical Corporation), and 11 mg of N,N′-azobisisobutyronitrile (AIBN) (manufactured by Fujifilm and Kazumitsu Chemical Co., Ltd.) were added to a reaction vessel and dissolved in 2.3 mL of toluene. The mixture was heated at 75°C for 16 hours. The reaction solution was then added dropwise to methanol to precipitate and recover the block polymer (S-1). 1 The degree of polymerization of 4HBAGE was calculated to be 3 by ¹H-NMR determination.

[0627] Similar to the synthesis of (S-1) above, the amount of 4HBAGE added was changed to 0.27 g and 1.07 g, thereby synthesizing block polymers (S-2) and (S-3) with degrees of polymerization of 5 and 20, respectively.

[0628] Synthesis of epoxy-containing organosilicon copolymers (S-4)

[0629] Except for changing the chain transfer agent (A-1) 1.0g to (A-2), the 4HBAGE 0.16g to 0.2g, and the AIBN to 5.5mg, the same operation as (S-1) was performed to obtain a block polymer (S-4) with a degree of polymerization of 10 of 4HBAGE.

[0630] 3. Synthesis of organosilicon copolymers with (meth)acrylic acid groups

[0631] (1) Synthesis of acrylic silicone copolymers (S-8) to (S-10)

[0632] 1.0 g of chain transfer agent (A-1), 0.08 g of 2-hydroxyethyl acrylate (HEA) (manufactured by Tokyo Chemical Industry Co., Ltd.), and 10 mg of AIBN were added to the reaction vessel and dissolved in 2.9 mL of toluene. The mixture was heated at 70 °C for 22.5 hours to polymerize, yielding a solution of block polymer (S-5). 1 H-NMR analysis determined the degree of polymerization of HEA to be 3.

[0633] The same procedure was followed, but the amount of HEA added was changed to 0.14 g and 0.53 g, thereby synthesizing block polymers (S-6) and (S-7) with degrees of polymerization of 5 and 20, respectively.

[0634] Add 1.1 equivalents of 2-isocyanate ethyl acrylate (trade name: KARENZ AOI, manufactured by Showa Denko Co., Ltd.) and 0.01 equivalents of dibutyltin dilaurate (DBTDL) (manufactured by Tokyo Chemical Industry Co., Ltd.) relative to the HEA units in the polymer (S-5) to the above-obtained block polymer (S-5) solution, and stir at 40°C for 2 hours. 1 After confirming 100% hydroxyl group reaction by H-NMR determination, the reaction solution was added dropwise to methanol to precipitate and recover the acrylic block polymer (S-8). The same reaction was performed on block polymers (S-6) and (S-7) to synthesize block polymers (S-9) and (S-10) with degrees of polymerization of 5 and 20, respectively.

[0635] (2) Synthesis of organosilicon copolymers (S-11) to (S-13) with methacrylic acid groups

[0636] Except for replacing KARENZ AOI with ethyl methacrylate-2-isocyanate (trade name: KARENZ MOI, manufactured by Showa Denko Corporation), the same procedure was followed as in the synthesis of (S-8) to (S-10) above to synthesize block polymers (S-11) to (S-13) with degrees of polymerization of 3, 5 and 20, respectively.

[0637] 4. Synthesis of chain transfer agents containing perfluorinated polyethers

[0638] (1) Synthesis of chain transfer agent (B-1)

[0639] In a flask, take 0.505 g of 2-[(dodecylthiothiocarbonyl)thio]propionic acid (manufactured by Fujifilm and Kagaku Pure Chemical Industries Co., Ltd.), 0.019 g of 4-dimethylaminopyridine (DMAP) (manufactured by Tokyo Chemical Industry Co., Ltd.), 0.293 g of 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride (EDCI) (manufactured by Tokyo Chemical Industry Co., Ltd.), and CF3CF2CF2(OCF2CF2CF2). n5.0 g of an alcohol containing perfluoropolyether (manufactured by Daikin Industries, Ltd.) as shown in OCF2CF2CH2OH (average n ≈ 25) was added to 13 mL of ASAHIKLIN AK-225 (manufactured by AGC), and the reaction was carried out with stirring at room temperature. After stirring overnight, the reaction solution was washed with saturated sodium bicarbonate aqueous solution and brine. The organic layer was separated and concentrated, and then added dropwise to methanol to obtain 4.56 g of a yellow oily target compound (B-1) by dehydration condensation of 2-[(dodecylthiothiocarbonyl)thio]propionic acid and the alcohol containing perfluoropolyether. The structure of the compound is shown in the figure. 1 H and 19 This was confirmed by F-NMR determination.

[0640] (2) Synthesis of chain transfer agent (B-2)

[0641] Except for changing 2-[(dodecylthiothiocarbonyl)thio]propionic acid to 0.421g, DMAP to 0.015g, EDCI to 0.230g, and using CF3CF2(OCF2) as an alcohol containing perfluoropolyether. m (OCF2CF2) n Apart from 4.2 g of OCF2CH2OH (number average molecular weight 4200, n / m = 1.1), the same procedure as the synthesis of (B-1) above was followed to obtain 4.27 g of the target compound (B-2).

[0642] (3) Synthesis of chain transfer agent (B-3)

[0643] In addition to being used as an alcohol containing perfluoropolyethers, CF3CF2CF2[OCF(CF3)CF2] n Apart from 5.0 g of OCF(CF3)CH2OH(n≈25), the same procedure as the synthesis of (B-1) above was followed to obtain 4.68 g of the target compound (B-3).

[0644] 5. Synthesis of PFPE copolymers with epoxy groups

[0645] (1) Synthesis of PFPE copolymer with epoxy groups (F-1)

[0646] 1.0 g of chain transfer agent (B-1), 0.23 g of 4-hydroxybutyl acrylate glycidyl ether (4HBAGE) (manufactured by Mitsubishi Chemical Corporation), and 12 mg of N,N′-azobisisobutyronitrile (AIBN) (manufactured by Fujifilm and Wako Pure Chemical Industries, Ltd.) were added to the reaction vessel and dissolved in 2.9 mL of 1,3-bis(trifluoromethyl)benzene (manufactured by Tokyo Chemical Industry Co., Ltd.). The mixture was heated at 75°C for 17 hours. The reaction solution was then added dropwise to hexane to precipitate the block polymer (F-1), which was then recovered. 1The degree of polymerization of 4HBAGE was determined to be 5 by ¹H-NMR analysis.

[0647] (2) Synthesis of PFPE copolymer with epoxy groups (F-2)

[0648] Except for replacing 1.0 g of chain transfer agent (B-1) with 1.0 g of chain transfer agent (B-2), the synthesis was carried out in the same manner as that of (F-1) to obtain the block polymer (F-2). 1 The degree of polymerization of 4HBAGE was determined to be 5 by ¹H-NMR analysis.

[0649] (3) Synthesis of PFPE copolymer with epoxy groups (F-3)

[0650] Except for replacing 1.0 g of chain transfer agent (B-1) with 1.0 g of chain transfer agent (B-3), the synthesis was carried out in the same manner as that of (F-1) to obtain the block polymer (F-3). 1 The degree of polymerization of 4HBAGE was determined to be 5 by ¹H-NMR analysis.

[0651] 6. Synthesis of PFPE copolymers with (meth)acrylic acid groups

[0652] (1) Synthesis of PFPE copolymer with acrylic groups (F-5)

[0653] 1.3 g of chain transfer agent (B-1), 0.18 g of 2-hydroxyethyl acrylate (HEA) (manufactured by Tokyo Chemical Industry Co., Ltd.), and 15.5 mg of AIBN were added to the reaction vessel and dissolved in 2.1 mL of 1,3-bis(trifluoromethyl)benzene. The mixture was heated at 70°C for 22.5 hours to polymerize, yielding a solution of block polymer (F-4). 1 The degree of polymerization of HEA was determined to be 5 by H-NMR analysis.

[0654] Next, 1.1 equivalents of KARENZ AOI (manufactured by Showa Denko) and 0.01 equivalents of dibutyltin dilaurate (DBTDL) (manufactured by Tokyo Chemical Industry Co., Ltd.) relative to the HEA units in the polymer (F-4) were added to the obtained block polymer (F-4), and the mixture was stirred at 40°C for 2 hours. 1 After confirming 100% hydroxyl group reaction by H-NMR determination, the reaction solution was added dropwise to hexane to precipitate and recover the block polymer (F-5) with acrylic acid groups.

[0655] (2) Synthesis of PFPE copolymer with methacrylic acid group (F-6)

[0656] Except for changing KARENZ AOI to KARENZ MOI (manufactured by Showa Denko Corporation), the same procedure as described above (F-5) was followed to synthesize a block polymer with methacrylic acid groups (F-6).

[0657] (3) Synthesis of PFPE compounds with acrylic groups (F-7)

[0658] In a 1L four-necked flask equipped with a dropping funnel, condenser, thermometer, and stirrer, Sumidur N3300 (manufactured by Sumika Bayer Urethane, NCO group content 21.8%, 36.6g) was dissolved in HCFC225 (219.4g), and dibutyltin dilaurate (manufactured by Fujifilm and Kazumitsu Chemical Co., Ltd., 0.30g) was added. While stirring under a nitrogen stream at 40°C, the solution was added dropwise to achieve an average composition of CF3CF2CF2O (CF2CF2CF2O). 14 An alcohol (60.0 g) containing a perfluoropolyether, as shown in CF2CF2CH2OH, was dissolved in a solution of HCFC225 (60.0 g) and stirred. Hydroxyethyl acrylate (19.6 g) was added dropwise and stirred. The complete disappearance of NCO absorption was confirmed by IR spectroscopy. 0.05 g of butylated hydroxytoluene was added to completely remove HCFC225, synthesizing a PFPE compound (F-7) with acrylate groups.

[0659] 7. Coating preparation

[0660] (1) Epoxy coating

[0661] As the epoxy compound forming matrix, CELLOXIDE 2021P (manufactured by Daicel) was dissolved in MIBK. The following combination of compounds was added to this solution, such that the PFPE copolymers (F-1) to (F-3) each reached 1% of the epoxy compound solids concentration relative to the epoxy compound solids concentration, and the silicone copolymers (S-1) to (S-4) each reached 0.1% of the epoxy compound solids concentration relative to the epoxy compound solids concentration, thus preparing a 50% by mass epoxy compound solution. Then, SAN-AID SI-60L (manufactured by Sanshin Chemical Co., Ltd.) as a hot acid generator was added at 3% by mass relative to the epoxy compound solids concentration to obtain a coating agent. The coating agent was applied to a PET substrate using a rod coater and heated at 90°C for 2 hours to obtain a cured film.

[0662] (2) Acrylic coating

[0663] As the acrylic-containing composition forming the matrix, BEAMSET 575CB (manufactured by Arakawa Chemical Industry Co., Ltd.) was dissolved in MIBK. The following combination was then added to the solution, such that the PFPE copolymer (F-5) or (F-6) reached 1% of the resin solids relative to BEAMSET 575CB (converted by solids concentration), and the silicone copolymers (S-8) to (S-13) reached 0.1% of the resin solids relative to BEAMSET 575CB (converted by solids concentration), resulting in a 50% by mass coating composition. The coating composition was applied to a PET substrate using a rod coater, dried at 70°C for 10 minutes, and then subjected to ultraviolet irradiation to obtain a cured film. Ultraviolet irradiation was performed using a conveyor belt type ultraviolet irradiation device, with the irradiation dose set to 600 mJ / cm². 2 Alternatively, when used as a PFPE compound (F-7), the solvent is replaced with MIBK, and the same treatment is performed using propylene glycol monomethyl ether to obtain a cured coating.

[0664] (3) Acrylic coating (containing terminal methanol-modified organosilicon)

[0665] Except for adding single-terminal methanol-modified organosilicon X-22-170DX to replace the organosilicon copolymer, the same operation as in (2) above was performed to obtain the cured coating.

[0666] (4) Epoxy and acrylic coatings (without silicone copolymers and PFPE copolymers)

[0667] Except for the absence of silicone copolymer and PFPE copolymer, the same procedure as described in (1) or (2) above is followed to obtain a cured coating.

[0668] 8. Are there any exudates from the cured coating?

[0669] After touching the cured film prepared in step 7 above with your finger, visually confirm whether whitening caused by exudated components can be seen on the film surface. The evaluation criteria are as follows.

[0670] ○: No albinism.

[0671] ×: Albinism has occurred.

[0672] 9. Evaluation of surface sliding properties

[0673] For the cured coatings obtained in step 7 above, the static and dynamic coefficients of friction were measured using a tribomaster TL201Ts tribomaster TL201Ts trinity-Lab Co., Ltd. as friction elements, with a tactile contact as the friction element and a load of 20 gf and a scanning speed of 10 mm / sec.

[0674] 10. Contact Angle Evaluation

[0675] For the cured coatings prepared in step 7 above, the static contact angle of water was measured using a contact angle tester (DropMaster, manufactured by Kyowa Interface Science Co., Ltd.) with a liquid volume of 2 μL.

[0676] The evaluation results are shown in Table 1 below.

[0677] [Table 1]

[0678]

[0679] Based on the above results, it can be confirmed that the coatings in Examples 1 to 15, which are included within the scope of this invention, have low static and dynamic friction coefficients, high water contact angles, and no leakage occurs. On the other hand, it can be confirmed that at least one of the results for static friction coefficient, dynamic friction coefficient, water contact angle, and permeability in Comparative Examples 1 to 5, which are not included within the scope of this invention, is poor.

[0680] Industrial availability

[0681] The curable compositions of the present invention are well used to form surface treatment layers on a wide variety of substrates.

Claims

1. A curable composition, characterized in that, Compositions containing organosilicon copolymers, fluorinated polyether compounds, and matrix-forming compounds. The organosilicon copolymer has two or more crosslinking groups. The crosslinking groups include carbon-carbon double bonds, carbon-carbon triple bonds, cyclic ether groups, hydroxyl groups, mercapto groups, amino groups, azide groups, nitrogen-containing heterocyclic groups, isocyanate groups, halogen atoms, groups containing phosphate groups or silane coupling groups. The organosilicon copolymer is an organosilicon copolymer represented by formula (1) or (2) below. In the formula, R 1 It is a hydrogen atom or a carbon atom. 1－6 alkyl; R 2 Each time it appears, it is independently represented by a hydrogen atom or a carbon atom. 1－6 alkyl; m is an integer from 1 to 300; R 4 Each occurrence is independently assigned the value R. 4a Or R 4b ; R 4 n In the middle, R 4a The number is 2 or more; R 4a Each time it appears, it is independently a divalent organic group with cross-linking properties; R 4b Each time it appears, it is an independent divalent organic group that does not have a cross-linking group; n is an integer from 2 to 90; X a Each is an organic group that is independently divalent; X b Each is an organic group that is independently divalent; R a Each is independently an alkyl, phenyl, or -SR a1 -OR a2 、-NR a3 2. ； R a1 R a2 R a3 R a4 R a5 and R a6 Each can be independently an alkyl or phenyl group; R a7 It can be a hydrogen atom or a halogen atom.

2. The curable composition according to claim 1, characterized in that, R in the organosilicon copolymer 4a The number is 3 or more.

3. The curable composition according to claim 1 or 2, characterized in that, The organosilicon copolymer is a block copolymer.

4. The curable composition according to claim 1 or 2, characterized in that, The organosilicon copolymer has more than three crosslinking groups at its ends.

5. The curable composition according to claim 1 or 2, characterized in that, The organosilicon copolymer is hydrophobic.

6. The curable composition according to claim 1 or 2, characterized in that, R 4 For R 4a .

7. The curable composition according to claim 1 or 2, characterized in that, R 4a For groups represented by the following formula: In the formula, R 31 Each time it appears, it is independently represented by a hydrogen atom or an alkyl group; R 32 Each time it appears, it is independently a hydrogen atom, a chlorine atom, a fluorine atom, or an alkyl group that is substituted with fluorine or not substituted; R 33 Each time it appears, it is an independent cross-linking group; Y 1 For single bonds, -C(=O)O-, -C(=O)NH-, -OC(=O)-, -NHC(=O)-, -O-, -N(R) c ) - Aromatic ring, aromatic ring with substituents, or carbazoyl group; R c It is an organic group. Y 2 It is a linker group consisting of single bonds or 1 to 16 atoms in the main chain.

8. The curable composition according to claim 1 or 2, characterized in that, The crosslinking groups are epoxy, vinyl, allyl, substituted or unsubstituted acryloyl, cinnamoyl, 2,4-hexadienoyl, vinyl ether (vinyloxy) group, hydroxy, oxetyl, isocyanate group, catechol group, mercapto, amino, monoalkylamino, dialkylamino, azide, phosphate group, carboxyl, imidazole, triazolyl, benzotriazolyl, tetrazolyl, halogen atom or silane coupling group.

9. The curable composition according to claim 1 or 2, characterized in that, The crosslinking group is an epoxy group, an acryloyl group, or a methacryloyl group.

10. The curable composition according to claim 1 or 2, characterized in that, The crosslinking group is at least one selected from glycidyl groups and alicyclic epoxy groups.

11. The curable composition according to claim 1 or 2, characterized in that, n is an integer from 2 to 50.

12. The curable composition according to claim 1 or 2, characterized in that, n is an integer from 3 to 30.

13. The curable composition according to claim 1 or 2, characterized in that, R 2 Each occurrence is independently assigned the number C. 1－6 alkyl.

14. The curable composition according to claim 1 or 2, characterized in that, m is an integer from 2 to 250.

15. The curable composition according to claim 1 or 2, characterized in that, The fluorine content in the fluorinated polyether compound is in the range of 2 to 70% by weight.

16. The curable composition according to claim 1 or 2, characterized in that, The fluorine content in the fluorinated polyether compound is in the range of 10 to 60% by weight.

17. The curable composition according to claim 1 or 2, characterized in that, The fluorinated polyether-based compound is a chain copolymer.

18. The curable composition according to claim 17, characterized in that, The chain copolymer is an addition copolymer.

19. The curable composition as claimed in claim 18, characterized in that, The addition copolymer is a free radical copolymer or an ionic copolymer.

20. The curable composition as claimed in claim 18, characterized in that, The addition copolymer is a free radical copolymer.

21. The curable composition according to claim 1 or 2, characterized in that, The fluorinated polyether-based compound is a block copolymer.

22. The curable composition according to claim 1 or 2, characterized in that, The fluorinated polyether compound is a fluorinated polyether compound represented by formula (3) or (4). In the formula, R F1 is Rf 1 -R F -O q -; R F2 is -Rf 2 p -R F -O q -; Rf 1 C atoms that are substituted or unsubstituted by one or more fluorine atoms 1－16 alkyl; Rf 2 C atoms that are substituted or unsubstituted by one or more fluorine atoms 1－6 Alkylene; R F Each is independently a divalent fluorinated polyether group; p is 0 or 1; q can be 0 or 1 independently; R 4′ Each occurrence is independently assigned the value R. 4a′ or R 4b′ ; R 4′ n′ In the middle, R 4a′ The number is 2 or more; R 4a′ Each time it appears, it is independently an organic group with a divalent functional group selected from substituent group A; R 4b′ Each time it appears, it is independently a divalent organic group that does not have a functional group selected from substituent group A; The substituent group A is a group containing carbon-carbon double bonds, carbon-carbon triple bonds, cyclic ether groups, hydroxyl groups, mercapto groups, amino groups, azide groups, nitrogen-containing heterocyclic groups, isocyanate groups, halogen atoms, phosphate groups, and silane coupling groups; n ′ Integers from 1 to 100; X a′ Each is an independent divalent organic group; X b′ Each is an independent divalent organic group; R a′ Each is independently an alkyl, phenyl, or -SR a1 -OR a2 、-NR a3 2. ； R a1 R a2 R a3 R a4 R a5 and R a6 Each can be independently an alkyl or phenyl group; R a7 It can be a hydrogen atom or a halogen atom.

23. The curable composition according to claim 22, characterized in that, R 4′ For R 4a′ .

24. The curable composition according to claim 22, characterized in that, R 4a′ For groups represented by the following formula: In the formula, R 31′ Each time it appears, it is independently represented by a hydrogen atom or an alkyl group; R 32′ Each time it appears, it is independently a hydrogen atom, a chlorine atom, a fluorine atom, or an alkyl group that is substituted with fluorine or not substituted; R 33′ Each time it appears, it is an organic group having a functional group selected from substituent group A; Y 1′ For single bonds, -C(=O)O-, -C(=O)NH-, -OC(=O)-, -NHC(=O)-, -O-, -N(R) c )-, phenylene or carbazoyl group; R c It is an organic group. Y 2′ It is a linker group consisting of single bonds or 1 to 16 atoms in the main chain.

25. The curable composition according to claim 22, characterized in that, The functional group selected from substituent group A is an epoxy group or CH2=CX. 1′ -C(O)-, where X 1′ Alkyl groups having 1 to 10 carbon atoms, including hydrogen, chlorine, fluorine, or carbon atoms substituted or unsubstituted with fluorine.

26. The curable composition according to claim 22, characterized in that, The functional group selected from substituent group A is at least one selected from glycidyl group and alicyclic epoxy group.

27. The curable composition according to claim 22, characterized in that, n′ is an integer from 2 to 50.

28. The curable composition according to claim 22, characterized in that, n′ is an integer from 3 to 30.

29. The curable composition according to claim 1 or 2, characterized in that, The fluorinated polyether compound is a fluorinated polyether compound represented by the following formula (5). In equation (5), R F1 is Rf 1 -R F -O q -; Rf 1 C atoms that are substituted or unsubstituted by one or more fluorine atoms 1－16 alkyl; R F Each is independently a divalent fluorinated polyether group; q is 0 or 1; X c The following expression is represented: -(Q) d - (CFZ) e - (CH2) f - The group shown, Formula – (Q) d - (CFZ) e - (CH2) f In the symbol - Q represents oxygen atom, phenylene, carbazolyl group, and -NR. a - or divalent polar group, formula -NR a - In the middle, R a Indicates a hydrogen atom or an organic group. Z represents a hydrogen atom, a fluorine atom, or a lower fluorinated alkyl group. d, e, and f are independent integers from 0 to 50, the sum of d, e, and f is at least 1, and the order of the repeating units enclosed in parentheses is arbitrary in the formula. R 10 This refers to an organic group with (n2+n3) valence that may or may not have a ring structure, heteroatoms, and / or functional groups. R 8 Represents a divalent organic group. R 9 Alkyl groups having 1 to 10 carbon atoms, including hydrogen, chlorine, fluorine, or fluorine-substituted or unsubstituted atoms. n2 is an integer from 1 to 3. n3 is an integer from 1 to 3.

30. The curable composition according to claim 22, characterized in that, R F Separately, the formula is: - (OC6F 12 ) a - (OC5F) 10 ) b - (OC4F8) c - (OC3R) Fa 6) d - (OC2F4) e - (OCF2) f - The group shown, In the formula, R Fa Each time it appears, it is independently represented by a hydrogen atom, a fluorine atom, or a chlorine atom. a, b, c, d, e, and f are each independent integers from 0 to 200. The sum of a, b, c, d, e, and f is 1 or more. The order of the repeating units marked a, b, c, d, e, or f and enclosed in parentheses is arbitrary in the formula.

31. The curable composition according to claim 30, characterized in that, R Fa It is a fluorine atom.

32. The curable composition according to claim 22, characterized in that, R F Each of these groups can be independently represented by one of the following formulas (f1), (f2), (f3), (f4), or (f5). -(OC3F6) d -(OC2F4) e - (f1) In equation (f1), d is an integer from 1 to 200, and e is 0 or 1. -(OC4F8) c -(OC3F6) d -(OC2F4) e - (OCF2) f - (f2) In equation (f2), c and d are independent integers from 0 to 30; e and f are independent integers from 1 to 200; The sum of c, d, e, and f is an integer between 10 and 200; The order of repeated units marked with subscripts c, d, e, or f and enclosed in parentheses is arbitrary in the formula. -(R 6 -R 7 ) g - (f3) In equation (f3), R 6 It is either OCF2 or OC2F4; R 7 Selected from OC2F4, OC3F6, OC4F8, OC5F 10 and OC6F 12 The group, or a combination of two or three groups selected from these groups; g is an integer from 2 to 100. -(OC6F 12 ) a -(OC5F 10 ) b -(OC4F8) c -(OC3F6) d -(OC2F4) e -(OCF2) f - (f4) In equation (f4), e is an integer greater than 1 and less than 200, a, b, c, d, and f are each an independent integer greater than 0 and less than 200, the sum of a, b, c, d, e, and f is at least 1, and the order of the repeated units labeled a, b, c, d, e, or f and enclosed in parentheses is arbitrary in the equation. -(OC6F 12 ) a -(OC5F 10 ) b -(OC4F8) c -(OC3F6) d -(OC2F4) e -(OCF2) f - (f5) In equation (f5), f is an integer greater than 1 and less than 200, a, b, c, d and e are each an integer greater than 0 and less than 200, the sum of a, b, c, d, e and f is at least 1, and the order of the repeated units marked a, b, c, d, e or f and enclosed in parentheses is arbitrary in the equation.

33. The curable composition according to claim 22, characterized in that, It also contains at least one of the fluorinated oils represented by the following general formula (C), In the formula, Rf 2 An alkyl group having 1 to 16 carbon atoms, which may or may not be substituted by one or more fluorine atoms; Rf 3 It is an alkyl group having 1 to 16 carbon atoms, consisting of hydrogen atoms, fluorine atoms, or alkyl groups having one or more fluorine atoms substituted or unsubstituted; In formula (C), a′, b′, c′, and d′ represent the number of three repeating units of the perfluoro(poly)ether constituting the main framework of the polymer, and are independent integers between 0 and 300. The sum of a′, b′, c′, and d′ is at least 1. The order of repeated units marked with subscripts a′, b′, c′, or d′ and enclosed in parentheses is arbitrary in the formula.

34. The curable composition according to claim 1 or 2, characterized in that, The mass ratio of the organosilicon copolymer to the fluorinated polyether compound in the curable composition is in the range of 0.1:100 to 100:0.

1.

35. The curable composition according to claim 1 or 2, characterized in that, The mass ratio of the organosilicon copolymer to the fluorinated polyether compound in the curable composition is in the range of 0.5:100 to 100:

100.

36. A film formed from any one of the curable compositions according to claims 1 to 35.

37. An article comprising a substrate and a layer formed on the surface of the substrate by any one of claims 1 to 35 of a curable composition.

38. The article as claimed in claim 37, characterized in that, The item in question is an optical component.

39. The article as claimed in claim 37, characterized in that, The item in question is a LiDAR cover component.

40. The article as claimed in claim 37, characterized in that, The item in question is a sensor component.

41. The article as claimed in claim 37, characterized in that, The item in question is a dashboard cover component.

42. The article as claimed in claim 37, characterized in that, The item in question is an interior component for automobiles.

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