Surface treatment agent

Abstract

The surface treatment agent of the present application contains: (A) a compound represented by the following formula (A1) or formula (A2); and (B) a compound represented by the following formula (B1) or formula (B2), the above-mentioned surface treatment agent containing at least one of the above-mentioned compound represented by formula (A2) or the above-mentioned compound represented by formula (B2).

Description

Technical Field

[0001] The present invention relates to surface treatment agents and articles having a layer formed by the surface treatment agent. Background Technology

[0002] It is known that by coating a solution containing a certain organosilanes and metal alkoxides onto a solid surface, an organic-inorganic hybrid coating with properties such as hydrophobicity, oiliness, or syringe can be obtained (Patent Document 1).

[0003] Existing technical documents

[0004] Patent documents

[0005] Patent Document 1: Japanese Patent Application Publication No. 2013-213181 Summary of the Invention

[0006] The technical problem that the invention aims to solve

[0007] The inventors of this invention noted that although the organic-inorganic mixed coating described in Patent Document 1 has lubricating properties, its UV durability is insufficient.

[0008] The purpose of this invention is to provide a surface treatment agent capable of forming a surface treatment layer with both lubricating properties and UV durability.

[0009] Technical solutions for solving technical problems

[0010] The present invention includes the following methods.

[0011] [1] A surface treatment agent comprising: (A) a compound represented by formula (A1) or a compound represented by formula (A2); and (B) a compound represented by formula (B1) or a compound represented by formula (B2).

[0012] The surface treatment agent described above contains at least one of the compounds shown in formula (A2) or formula (B2).

[0013]

[0014] [In the formula:]

[0015] M is Al, Ca, Fe, Ge, Hf, In, Si, Ta, Ti, Sn or Zr;

[0016] R 1 Each can be independently a hydrogen atom or a carbon atom. 1－6 alkyl;

[0017] R 4 C, each independently 1－3 Alkyl or C 1－3Alkoxy;

[0018] m is the valence of M above;

[0019] [n is 0 or higher and the valence of M is lower than the above.]

[0020]

[0021] [In the formula:]

[0022] R 2a Each time it appears, it is independently either a hydroxyl group or a hydrolyzable group;

[0023] R 3a Each time it appears, it is either a hydrogen atom or a monovalent organic group;

[0024] na in each SiR 2a na R 3a 3－na Each unit contains an independent integer from 1 to 3;

[0025] R 9a Each group can be independently a single bond or a divalent group.

[0026] M b (OR 1b ) q (R 4b ) p－q (B1)

[0027] [In the formula:]

[0028] M b is Al, Ca, Fe, Ge, Hf, In, Si, Ta, Ti, Sn or Zr;

[0029] R 1b Each can be independently a hydrogen atom or a carbon atom. 1－6 alkyl;

[0030] R 4b C 1－30 Alkyl, C 1－30 oxyalkyl, C 1－30 Fluoroalkyl or siloxane; p is the M mentioned above b The price;

[0031] q is 1 or higher and (M) b The price is less than 1.

[0032]

[0033] [In the formula:]

[0034] R 2bEach time it appears, it is independently either a hydroxyl group or a hydrolyzable group;

[0035] R 3b Each time it appears, it is either a hydrogen atom or a monovalent organic group;

[0036] nb in each SiR 2b nb R 3b 3－nb Each unit contains an independent integer from 1 to 3;

[0037] R 9b Each group is independently a single bond or a divalent group;

[0038] R 8 C 1－30 Alkyl, C 1－30 oxyalkyl, C 1－30 Fluoroalkyl groups, siloxane-containing groups, or groups containing perfluoropolyethers.

[0039] [2] The surface treatment agent as described in [1] above, wherein the compound represented by the above formula (A1) is a metal alkoxide represented by formula (A1-1).

[0040] M(OR 1 ) n (A1-1)

[0041] [In the formula:]

[0042] M is Al, Ca, Fe, Ge, Hf, In, Si, Ta, Ti, Sn or Zr;

[0043] R 1 Each can be independently a hydrogen atom or a carbon atom. 1－6 alkyl;

[0044] [n is the valence of M mentioned above.]

[0045] [3] The surface treatment agent as described in [1] or [2] above, wherein the compound represented by formula (A1) is a metal alkoxide represented by formula (A1-2).

[0046] Si(OR 1 )4(A1-2)

[0047] [In the formula, R] 1 Each can be independently a hydrogen atom or a carbon atom. 1－6 alkyl.]

[0048] [4] The surface treatment agent as described in any one of [1] to [3] above contains the compound shown in formula (A2) above.

[0049] [5] The surface treatment agent as described in any one of [1] to [4] above contains the compound shown in formula (B2) above.

[0050] [6] The surface treatment agent as described in any one of [1] to [5] above contains the compound shown in formula (A2) and the compound shown in formula (B2).

[0051] [7] The surface treatment agent as described in any one of [1] to [6] above contains the compound shown in formula (A2), the compound shown in formula (B1) above and the compound shown in formula (B2) above.

[0052] [8] The surface treatment agent as described in any one of [1] to [7] above, wherein na and nb are 3.

[0053] [9] The surface treatment agent as described in any one of [1] to [8] above, R 4b C 1－30 alkyl.

[0054]

[10] The surface treatment agent as described in any one of [1] to [9] above, wherein R 8 C 1－30 alkyl.

[0055]

[11] The surface treatment agent as described in any one of [1] to

[10] above, wherein R 9a C 1－6 Alkylene.

[0056]

[12] The surface treatment agent as described in any one of [1] to

[11] above, wherein R 9b C 1－6 Alkylene.

[0057]

[13] The surface treatment agent as described in any one of [1] to

[12] above, wherein the molar ratio of component (A) to component (B) is 0.01 to 100:1.

[0058]

[14] The surface treatment agent as described in any one of [1] to

[13] above further contains one or more other components selected from organic solvents, water and catalysts.

[0059]

[15] An article comprising a substrate and a layer formed on the substrate by any of the surface treatment agents described in any one of [1] to

[14] .

[0060] Invention Effects

[0061] Using the present invention, it is possible to provide a surface treatment agent capable of forming a surface treatment layer having both lubricating properties and UV durability. Detailed Implementation

[0062] In this specification, "monovalent organic group" refers to a monovalent group containing carbon. There is no particular limitation on what constitutes a monovalent organic group; it 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, carbonyloxy, etc., at the end of a hydrocarbon group or in the molecular chain. It should be noted that when simply referred to as "organic group," it refers to a monovalent organic group. Furthermore, "divalent organic group" refers to a divalent group containing carbon. There is no particular limitation on what constitutes a divalent organic group; examples include divalent groups that have had one hydrogen atom removed from an organic group.

[0063] In this specification, "hydrocarbon group" refers to a group containing carbon and hydrogen, specifically a group that has lost one hydrogen atom from a hydrocarbon. There are no particular limitations on what constitutes such a hydrocarbon group; examples include C groups that can be substituted by one or more substituents. 1－20 Hydrocarbon 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 structure, and can also be any type of saturated or unsaturated structure. In addition, hydrocarbon groups can contain one or more ring structures.

[0064] In the context of this specification, the substituents used as "hydrocarbon group" are not particularly limited, and examples include: halogen atoms; C atoms selected from those that can be substituted by one or more halogen atoms. 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.

[0065] (Surface treatment agent)

[0066] The surface treatment agent of the present invention contains: (A) a compound represented by formula (A1) or a compound represented by formula (A2); and (B) a compound represented by formula (B1) or a compound represented by formula (B2), wherein the surface treatment agent contains at least one of the compounds represented by formula (A2) or the compounds represented by formula (B2).

[0067]

[0068] [In the formula:]

[0069] M is Al, Ca, Fe, Ge, Hf, In, Si, Ta, Ti, Sn or Zr;

[0070] R 1 Each can be independently a hydrogen atom or a carbon atom. 1－6 alkyl;

[0071] R 4 C independently 1－3 Alkyl or C 1－3 Alkoxy;

[0072] m is the valence of M above;

[0073] [n is 0 or higher and the valence of M is lower than the above.]

[0074]

[0075] [In the formula:]

[0076] R 2a Each time it appears, it is independently either a hydroxyl group or a hydrolyzable group;

[0077] R 3a Each time it appears, it is either a hydrogen atom or a monovalent organic group;

[0078] na in each SiR 2a na R 3a 3－na Each unit contains an independent integer from 1 to 3;

[0079] R 9a Each group can be independently a single bond or a divalent group.

[0080] M b (OR 1b ) q (R 4b ) p－q (B1)

[0081] [In the formula:]

[0082] M b is Al, Ca, Fe, Ge, Hf, In, Si, Ta, Ti, Sn or Zr;

[0083] R 1b Each can be independently a hydrogen atom or a carbon atom. 1－6 alkyl;

[0084] R 4b C 1－30 Alkyl, C 1－30 oxyalkyl, C 1－30 Fluoroalkyl or siloxane;

[0085] p is the above M b The price;

[0086] q is 1 or higher and (M) b The price is less than 1.

[0087]

[0088] [In the formula:]

[0089] R 2b Each time it appears, it is independently either a hydroxyl group or a hydrolyzable group;

[0090] R 3b Each time it appears, it is either a hydrogen atom or a monovalent organic group;

[0091] nb in each SiR 2b nb R 3b 3－nb Each unit contains an independent integer from 1 to 3;

[0092] R 9b Each group is independently a single bond or a divalent group;

[0093] R 8 C 1－30 Alkyl, C 1－30 oxyalkyl, C 1－30 Fluoroalkyl groups, siloxane-containing groups, or groups containing perfluoropolyethers.

[0094] (ingredient (A))

[0095] In the surface treatment agent of the present invention, component (A) is contained together with component (B), and component (A) contains compound (A2), or component (B) contains compound (B2), thereby enabling the formation of a surface treatment layer with excellent lubricity and UV durability.

[0096] Component (A) comprises a metal alkoxide compound of formula (A1) (hereinafter also referred to as "compound (A1)") or an isocyanurate compound of formula (A2) (hereinafter also referred to as "compound (A2)").

[0097] In a preferred embodiment, the compound (A1) is the compound (A1) shown in formula (A1).

[0098]

[0099] [In the formula:]

[0100] M is Al, Ca, Fe, Ge, Hf, In, Si, Ta, Ti, Sn or Zr;

[0101] R 1Each can be independently a hydrogen atom or a carbon atom. 1－6 alkyl;

[0102] R 4 C, each independently 1－3 Alkyl or C 1－3 Alkoxy;

[0103] m is the valence of M above;

[0104] [n is 0 or higher and the valence of M is lower than the above.]

[0105] In a further preferred embodiment, the compound (A1) is the compound represented by formula (A1-1).

[0106] M(OR 1 ) n (A1-1)

[0107] [In the formula:]

[0108] M is Al, Ca, Fe, Ge, Hf, In, Si, Ta, Ti, Sn or Zr;

[0109] R 1 Each can be independently a hydrogen atom or a carbon atom. 1－6 alkyl;

[0110] [n is the valence of M mentioned above.]

[0111] In a further preferred embodiment, the compound (A1) is a metal alkoxide of formula (A1-2).

[0112] Si(OR 1 )4(A1-2)

[0113] [In the formula, R] 1 Each can be independently a hydrogen atom or a carbon atom. 1－6 alkyl.]

[0114] In this invention, typically Al is trivalent, Ca is divalent, Fe is divalent or trivalent, preferably trivalent, Ge is divalent or tetravalent, preferably tetravalent, Hf is tetravalent, In is tetravalent, Si is tetravalent, Ta is pentavalent, Ti is tetravalent, Sn is tetravalent, and Zr is tetravalent.

[0115] The M mentioned above is preferably Si, Ti, or Zr, and more preferably Si.

[0116] The above R 1 C is preferred independently. 1－6 Alkyl, more preferably C 1－3 Alkyl, more preferably C 1－2 alkyl.

[0117] The above R4 C independently 1－3 Alkyl or C 1－3 Alkyl group.

[0118] The above R 4 The alkyl group is preferably methyl or ethyl, more preferably methyl.

[0119] The above R 4 The alkoxy group in the form is preferably methoxy or ethoxy, more preferably ethoxy.

[0120] m is the valence of M above, and n is 0 or higher and less than the valence of M above.

[0121] In one approach, n is the valence of M.

[0122] In another way, (m-n) is 1.

[0123] In a preferred embodiment, the compound (A1) is tetramethoxysilane or tetraethoxysilane.

[0124] The above compound (A2) is an isocyanurate compound with three hydrolyzable silane groups as shown in formula (A2).

[0125]

[0126] [In the formula:]

[0127] R 2a Each time it appears, it is independently either a hydroxyl group or a hydrolyzable group;

[0128] R 3a Each time it appears, it is either a hydrogen atom or a monovalent organic group;

[0129] na in each SiR 2a na R 3a 3－na Each unit contains an independent integer from 1 to 3;

[0130] R 9a Each group can be independently a single bond or a divalent group.

[0131] The surface treatment agent of the present invention contains the above-mentioned compound (A2), thereby enabling the formation of a surface treatment layer with excellent UV durability.

[0132] The above compound (A2) has three 1- to 3 functional silane groups. Here, "1- to 3 functional silane groups" refers to silane groups having 1 to 3 functional groups, typically hydroxyl or hydrolyzable groups.

[0133] In the above formula, R 2aEach time it appears, it is independently either a hydroxyl group or a hydrolyzable group.

[0134] R 2a Preferably, each occurrence is an independently hydrolyzable group.

[0135] "Hydrolytically degradable groups" refer to groups capable of undergoing hydrolysis reactions; that is, groups that can be removed from the main skeleton of a compound through hydrolysis. Examples of hydrolytically degradable groups include -OR h -OCOR h -O-N=CR h 2. -NR h 2. -NHR h , -NCO, halogens, etc. R h Examples of C that can be substituted or not substituted include: 1－4 Alkyl groups, such as methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, and other non-substituted alkyl groups; and substituted alkyl groups such as chloromethyl. Among these, alkyl groups are preferred, especially non-substituted alkyl groups, and more preferably methyl or ethyl. In one embodiment, R h For methyl, in another way, R h It is an ethyl group.

[0136] R 2a More preferably -OR h (i.e., alkoxy group).

[0137] In the above formula, R 3a Each time it appears, it is independently either a hydrogen atom or a monovalent organic group. Such a monovalent organic group is a monovalent organic group that does not include the aforementioned hydrolyzable groups.

[0138] In R 3a In this context, the monovalent organic group is preferably C. 1－20 Alkyl, more preferably C 1－6 Alkyl, more preferably C 1－3 Alkyl groups, particularly preferably methyl groups.

[0139] In the above formula, na in each (SiR 2a na R 3a 3－na Each of the units is an independent integer from 1 to 3. That is, the silane in the compound (A2) is a 1- to 3-functional silane. na is preferably 2 to 3, more preferably 3. That is, the silane in the compound (A2) is preferably a 2- to 3-functional silane, more preferably a 3-functional silane.

[0140] In one approach, R 9a Each is an organic group that is either a single bond or divalent.

[0141] In the preferred embodiment, R 9a Each group is independently a single bond or a divalent group as shown in the following formula. Such a group is bonded to a Si atom on the left and to an N atom of the isocyanurate ring on the right. Wherein, R... 9a (typically R) 9a The hydrogen atom can be selected from fluorine atoms, C atoms, etc. 1－3 Alkyl and C 1－3 One or more substituents are substituted in the fluoroalkyl group. In a preferred embodiment, R 9a It was not replaced by these groups.

[0142] -R 41 x6 -R 42 x7 -

[0143] [In the formula:]

[0144] R 41 For -(CH2) y6 - or ortho, meta, or para-phenylene, preferably -(CH2). y6 -,

[0145] y6 is an integer from 1 to 20, preferably an integer from 1 to 6, and more preferably an integer from 1 to 3.

[0146] R 42 The derivatives are selected from -O-, -S-, ortho-, meta-, or para-phenylene, -C(O)O-, -OC(O)-, and -CONR-. 45 -, -NR 45 CO-、-O-CONR 45 -, -NR 45 CO-O-、-NR 45 -, -NR 45 CONR 45 -, -SO2NR 45 -, -NR 45 SO2−, -SO2−, and -(CH2) y7 - group,

[0147] R 45 Each can be independently a hydrogen atom, a phenyl group, or a carbon atom. 1－6 Alkyl (preferably C) 1－2 Alkyl, more preferably methyl),

[0148] y7 is an integer from 1 to 20, preferably an integer from 1 to 6, and more preferably an integer from 1 to 3.

[0149] x6 is an integer between 0 and 2.

[0150] x7 is either 0 or 1.

[0151] Among them, except that at least one of x6 and x7 is 0, each repeating unit R labeled x6 and x7 41 and R 42 The order in which they exist is arbitrary.

[0152] In the preferred embodiment, R 9a For -(CH2) y6 —(In the formula, y6 is an integer from 1 to 6.)

[0153] In the preferred embodiment, R 2a It is methoxy or ethoxy, na is 3, R 9a C 1－6 Alkylene.

[0154] (Ingredient (B))

[0155] In the surface treatment agent of the present invention, component (B) is contained together with component (A), and component (B) is compound (B2), or component (A) is compound (A2), thereby enabling the formation of a surface treatment layer with excellent lubricity and UV durability.

[0156] Component (B) comprises a metal alkoxide compound of formula (B1) (hereinafter also referred to as "compound (B1)") or an isocyanurate compound of formula (B2) (hereinafter also referred to as "compound (B2)").

[0157] The above compound (B1) is a metal alkoxide represented by formula (B1).

[0158] M b (OR 1b ) q (R 4b ) p－q (B1)

[0159] [In the formula:]

[0160] M b is Al, Ca, Fe, Ge, Hf, In, Si, Ta, Ti, Sn or Zr;

[0161] R 1b Each can be independently a hydrogen atom or a carbon atom. 1－6 alkyl;

[0162] R 4b C 1－30 Alkyl, C 1－30 oxyalkyl, C 1－30 Fluoroalkyl or siloxane;

[0163] p is the above M b The price;

[0164] q is 1 or higher and (M) b The price is less than 1.

[0165] The above compound (B1) has a metal atom and an alkoxy group bonded to the metal atom, as well as a functional group that imparts lubrication properties.

[0166] The above M b Preferably, it is made of Si, Ti, or Zr, and more preferably Si.

[0167] The above R 1b C is preferred independently. 1－6 Alkyl, more preferably C 1－3 Alkyl, more preferably C 1－2 alkyl.

[0168] The above R 4b C 1－30 Alkyl, C 1－30 oxyalkyl, C 1－30 Fluoroalkyl or siloxane.

[0169] The above C 1－30 Alkyl groups can be straight-chain or branched.

[0170] The above C 1－30 Alkyl groups can preferably be C14-32 ... 3－25 Alkyl, more preferably C 6－25 Alkyl, more preferably C 8－20 Alkyl, more preferably C 8－16 alkyl.

[0171] The above C 1－30 Oxyalkyl groups can preferably be C 3－30 alkyl oxy group, more preferably C 7－25 alkyl oxy group, more preferably C 8－20 alkyl oxy group, more preferably C 8－16 oxyalkyl.

[0172] The above C 1－30 Fluorinated alkyl groups can preferably be C10-30 ... 3－25 Fluorinated alkyl groups, more preferably C10, are used. 6－25 Fluorinated alkyl groups, more preferably C10, are preferred. 8－20 Fluorinated alkyl groups, more preferably C10, are preferred. 8－16 Fluorinated alkyl groups. These fluorinated alkyl groups may be partially or completely fluorinated.

[0173] The aforementioned siloxane group is a group represented by the following formula.

[0174]

[0175] [In the formula:]

[0176] R 21 Each time it appears, it is independently represented by a hydrogen atom or a carbon atom. 1－6 alkyl;

[0177] R 22 It is a hydrogen atom or a carbon atom. 1－6 alkyl;

[0178] t is an integer from 1 to 200.

[0179] The above R 21 C in 1－6 Alkyl groups are preferably C 1－3 Alkyl, more preferably methyl.

[0180] The above R 22 C in 1－6 Alkyl groups are preferably C 1－3 Alkyl, more preferably methyl.

[0181] In the preferred embodiment, R 21 and R 22 C independently 1－6 alkyl.

[0182] t is preferably an integer from 1 to 100, and more preferably an integer from 5 to 100.

[0183] In the preferred embodiment, the aforementioned R 4b C 1－30 alkyl.

[0184] p is the above M b The valence, q is 1 or higher and (M b The price is less than 1.

[0185] In one mode, (p-q) is 1.

[0186] In the preferred embodiment, M b For Si, R 1b It is methyl or ethyl, R 4b C 1－30 Alkyl group, preferably C 8－20 Alkyl group, p = 4, q = 3.

[0187] The above compound (B2) is an isocyanurate compound with two hydrolyzable silane groups as shown in formula (B2).

[0188]

[0189] [In the formula:]

[0190] R 2bEach time it appears, it is independently either a hydroxyl group or a hydrolyzable group;

[0191] R 3b Each time it appears, it is either a hydrogen atom or a monovalent organic group;

[0192] nb in each SiR 2b nb R 3b 3－nb Each unit contains an independent integer from 1 to 3;

[0193] R 9b Each group is independently a single bond or a divalent group;

[0194] R 8 C 1－30 Alkyl, C 1－30 oxyalkyl, C 1－30 Fluoroalkyl groups, siloxane-containing groups, or groups containing perfluoropolyethers.

[0195] The surface treatment agent of the present invention contains the above-mentioned compound (B2), thereby enabling the formation of a surface treatment layer with excellent lubricity and UV durability.

[0196] The above compound (B2) has two 1- to 3-functional silane groups.

[0197] In the above formula, R 2b Each time it appears, it is independently either a hydroxyl group or a hydrolyzable group.

[0198] R 2b Preferably, each occurrence is an independently hydrolyzable group.

[0199] "Hydrolytically degradable groups" refer to groups capable of undergoing hydrolysis reactions; that is, groups that can be removed from the main skeleton of a compound through hydrolysis. Examples of hydrolytically degradable groups include -OR h -OCOR h -O-N=CR h 2. -NR h 2. -NHR h , -NCO, halogens, etc. R h Examples of C that can be substituted or not substituted include: 1－4 Alkyl groups, such as methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, and other non-substituted alkyl groups; and substituted alkyl groups such as chloromethyl. Among these, alkyl groups are preferred, especially non-substituted alkyl groups, and more preferably methyl or ethyl. In one embodiment, R h For methyl, in another way, R h It is an ethyl group.

[0200] R 2bMore preferably -OR h (i.e., alkoxy group).

[0201] In the above formula, R 3b Each time it appears, it is independently either a hydrogen atom or a monovalent organic group. Such a monovalent organic group is a monovalent organic group that does not include the aforementioned hydrolyzable groups.

[0202] In R 3b In this context, the monovalent organic group is preferably C. 1－20 Alkyl, more preferably C 1－6 Alkyl, more preferably C 1－3 Alkyl groups, particularly preferably methyl groups.

[0203] In the above formula, nb is in each (SiR) 2b nb R 3b 3－nb Each of the units is an independent integer from 1 to 3. That is, the silane in the compound (B2) is a 1- to 3 functional silane. nb is preferably 2 to 3, more preferably 3. That is, the silane in the compound (B2) is preferably a 2- to 3 functional silane, more preferably a 3 functional silane.

[0204] In one approach, R 9b Each group is independently a single bond or a divalent group as shown in the following formula. Such a group is bonded to a Si atom on the left and to an N atom of the isocyanurate ring on the right. Wherein, R... 9b (typically R) 9b The hydrogen atom can be selected from fluorine atoms, C atoms, etc. 1－3 Alkyl and C 1－3 One or more substituents are substituted in the fluoroalkyl group. In a preferred embodiment, R 9b It was not replaced by these groups.

[0205] -R 41 x6 -R 42 x7 -

[0206] [In the formula:]

[0207] R 41 For -(CH2) y6 - or ortho, meta, or para-phenylene, preferably -(CH2). y6 -,

[0208] y6 is an integer from 1 to 20, preferably an integer from 1 to 6, and more preferably an integer from 1 to 3.

[0209] R 42The derivatives are selected from -O-, -S-, ortho-, meta-, or para-phenylene, -C(O)O-, -OC(O)-, and -CONR-. 45 -, -NR 45 CO-、-O-CONR 45 -, -NR 45 CO-O-、-NR 45 -, -NR 45 CONR 45 -, -SO2NR 45 -, -NR 45 SO2−, -SO2−, and -(CH2) y7 - group,

[0210] R 45 Each can be independently a hydrogen atom, a phenyl group, or a carbon atom. 1－6 Alkyl (preferably C) 1－2 Alkyl, more preferably methyl),

[0211] y7 is an integer from 1 to 20, preferably an integer from 1 to 6, and more preferably an integer from 1 to 3.

[0212] x6 is an integer between 0 and 2.

[0213] x7 is either 0 or 1.

[0214] Among them, except that at least one of x6 and x7 is 0, each repeating unit R labeled x6 and x7 41 and R 42 The order in which they exist is arbitrary.

[0215] In the preferred embodiment, R 9b For -(CH2) y6 —(In the formula, y6 is an integer from 1 to 6.)

[0216] The above R 8 C 1－30 Alkyl, C 1－30 oxyalkyl, C 1－30 Fluoroalkyl, siloxane-containing groups, or perfluoropolyether-containing groups.

[0217] The above C 1－30 Alkyl, C 1－30 oxyalkyl and C 1－30 The significance of fluoroalkyl groups is the same as that of R mentioned above. 4b C in 1－30 Alkyl, C 1－30 oxyalkyl and C 1－30 The same applies to fluoroalkyl groups.

[0218] The aforementioned siloxane-containing groups are siloxane-containing groups, preferably -X. S -RS (where X) S R is an organic group that is either a single bond or divalent. S It is a siloxane group. )

[0219] In one manner, X S It is a single key.

[0220] In another way, X S It is a divalent organic group.

[0221] The divalent organic group mentioned above is preferably C. 1－6 Alkylene, -(CH2) z1 -O-(CH2) z2 - (where z1 is an integer from 0 to 6, for example, an integer from 1 to 6, and z2 is an integer from 0 to 6, for example, an integer from 1 to 6), or - (CH2). z3 -Phenylidene-(CH2) z4 —(In the formula, z3 is an integer from 0 to 6, for example, an integer from 1 to 6; z4 is an integer from 0 to 6, for example, an integer from 1 to 6). Such a C 1－6 The alkylene group can be straight-chain or branched, preferably straight-chain. These groups can be selected, for example, from fluorine atoms, C atoms, etc. 1－6 Alkyl, C 2－6 alkenyl and C 2－6 One or more substituents in the alkynyl group are substituted, preferably unsubstituted. The divalent organic group is preferably C. 1－6 Alkylene.

[0222] The meaning of the above-mentioned siloxane group is the same as that of the above-mentioned R. 4b The same siloxane group is present in it.

[0223] The aforementioned groups containing perfluoropolyethers are groups containing perfluoropolyether groups, preferably -X. PF -R PF (where X) PF R is an organic group that is either a single bond or divalent. PF It is a perfluoropolyether group. (The group is shown in the image.)

[0224] In one manner, X PF It is a single key.

[0225] In another way, X PF It is a divalent organic group.

[0226] The divalent organic group mentioned above is preferably C. 1－6 Alkylene, -(CH2) z5 -O-(CH2) z6- (where z5 is an integer from 0 to 6, for example, an integer from 1 to 6, and z6 is an integer from 0 to 6, for example, an integer from 1 to 6), or - (CH2) z7 -Phenylidene-(CH2) z8 —(In the formula, z7 is an integer from 0 to 6, for example, an integer from 1 to 6; z8 is an integer from 0 to 6, for example, an integer from 1 to 6). Such a C 1－6 The alkylene group can be straight-chain or branched, preferably straight-chain. These groups can be selected, for example, from fluorine atoms, C atoms, etc. 1－6 Alkyl, C 2－6 alkenyl and C 2－6 One or more substituents in the alkynyl group are substituted, preferably unsubstituted. The divalent organic group is preferably C. 1－6 Alkylene.

[0227] The above-mentioned perfluoropolyether group is preferably Rf 1 -R F -O q - [where Rf] 1 Each occurrence is independently assigned the number C. 1－16 Perfluoroalkyl, R F Each time it appears, it is independently a divalent fluorinated polyether group, with q being 0 or 1. ] as shown in the group.

[0228] 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.

[0229] In the above formula, q is either 0 or 1 independently each time it appears. In one case, q is 0. In another case, q is 1.

[0230] In the above formula, R F Each time it appears, it is independently a divalent perfluoropolyether group.

[0231] R F Preferred formula: -(OC6F 12 ) a -(OC5F) 10 ) b -(OC4F8) c -(OC3F6) d -(OC2F4) e -(OCF2) f—[In the formula: 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 the repeating units labeled a, b, c, d, e, or f and enclosed in parentheses is arbitrary in the formula. Wherein, in all R...] Fa In the case where the atom is a hydrogen atom or a chlorine atom, at least one of a, b, c, e, and f is 1 or more. [The group shown is missing in the original text.]

[0232] a, b, c, d, e, and f can preferably be independent integers from 0 to 100.

[0233] The sum of a, b, c, d, e, and f is preferably 5 or more, more preferably 10 or more, for example, it can be 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, it can be 50 or less or 30 or less.

[0234] These repeating units can be linear or branched. For example, -(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 the following: -(OCF2CF2CF2CF2CF2)-, -(OCF(CF3)CF2CF2CF2)-, -(OCF2CF(CF3)CF2CF2)-, -(OCF2CF2CF(CF3)CF2)-, -(OCF2CF2CF2CF(CF3))-, etc. -(OC4F8)- can be any of the following: -(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, in the above formula, R FaThe fluorine atom can be any of the following: -(OCF2CF2CF2)-, -(OCF(CF3)CF2)-, and -(OCF2CF(CF3))-. -(OC2F4)- can be any of the following: -(OCF2CF2)- and -(OCF(CF3))-.

[0235] In one approach, R F Each time it appears, it is independently represented by any of the groups shown in the following formulas (f1) to (f5).

[0236] -(OC3F6) d -(OC2F4) e -(f1)

[0237] [In the formula, d is an integer from 1 to 200, and e is 0 or 1.]

[0238] -(OC4F8) c -(OC3F6) d -(OC2F4) e -(OCF2) f -(f2)

[0239] 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.

[0240] The sum of c, d, e, and f is 2 or more.

[0241] The order of repeated units marked with subscripts c, d, e, or f and enclosed in parentheses is arbitrary in the formula.

[0242] -(R) 6 -R 7 ) g -(f3)

[0243] [In the formula, R] 6 It is either OCF2 or OC2F4.

[0244] R 7 Selected from OC2F4, OC3F6, OC4F8, OC5F 10 and OC6F 12 The groups in the group, or combinations of two or three groups independently selected from these groups,

[0245] g is an integer from 2 to 100.

[0246] -(OC6F 12 ) a -(OC5F) 10 ) b -(OC4F8)c -(OC3F6) d -(OC2F4) e -(OCF2) f -(f4)

[0247] [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, and the order of the repeated units marked a, b, c, d, e, or f and enclosed in parentheses is arbitrary in the formula.]

[0248] -(OC6F 12 ) a -(OC5F) 10 ) b -(OC4F8) c -(OC3F6) d -(OC2F4) e -(OCF2) f -(f5)

[0249] [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, and the order of the repeated units marked a, b, c, d, e, or f and enclosed in parentheses is arbitrary in the formula.]

[0250] In the above formula (f1), d is preferably 5 to 200, more preferably 10 to 100, and even more preferably an integer of 15 to 50, for example, 25 to 35. In one embodiment, e is 1. In another embodiment, e is 0. In the above formula (f1), -(OC3F6) d - Preferably - (OCF2CF2CF2) d -、-(OCF(CF3)CF2) d - or - (OCF2CF(CF3)) d The group shown is more preferably -(OCF2CF2CF2). d - The group shown.

[0251] In the above formula (f2), e and f are each independently an integer, preferably 5 to 200, 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.

[0252] 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-, -OC2F 4OC2F4OC3F6-、-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 an integer of 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 any type of chain, either straight or branched, but preferably straight. In this configuration, the above formula (f3) is preferably -(OC2F4-OC3F6). g - or - (OC2F4 - OC4F8) g -.

[0253] In the above formula (f4), e is preferably an integer of 1 to 100, more preferably an integer of 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.

[0254] In the above formula (f5), f is preferably an integer of 1 to 100, more preferably an integer of 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.

[0255] In one approach, the aforementioned RF The group is represented by the formula (f1) above.

[0256] In one approach, the aforementioned R F The group is shown in the above formula (f2).

[0257] In one approach, the aforementioned R F The group is represented by the formula (f3) above.

[0258] In one approach, the aforementioned R F The group is represented by the formula (f4) above.

[0259] In one approach, the aforementioned R F The group is represented by the formula (f5) above.

[0260] In the preferred embodiment, the aforementioned R 8 C 1－30 Alkyl group, preferably C 8－20 alkyl.

[0261] In the preferred embodiment, R 2b and R 3b It is methoxy or ethoxy, nb is 3, R 9b C 1－6 Alkylene, R 8 C 1－30 Alkyl group, preferably C 8－20 alkyl.

[0262] The surface treatment agent of the present invention contains at least one of the compounds shown in formula (A2) or the compounds shown in formula (B2) above. UV durability is further improved by containing the compound shown in formula (A2) or the compound shown in formula (B2) above.

[0263] In one embodiment, the surface treatment agent of the present invention contains a compound represented by formula (B2). By containing the compound represented by formula (B2), UV durability and lubricity are further improved.

[0264] In one embodiment, the molar ratio of component (A) to component (B) (component (A): component (B)) is preferably 0.01 to 100:1, more preferably 1 to 100:1, further preferably 4 to 50:1, and even more preferably 5 to 20:1. By setting the molar ratio of component (A) to component (B) within the above range, lubricating properties and UV resistance can be imparted more effectively. Wherein, when component (A) and component (B) each contain two or more compounds, the above molar ratio is calculated based on their total amount.

[0265] In one manner, component (A) is compound (A1).

[0266] In another embodiment, component (A) is compound (A2).

[0267] In another embodiment, component (A) consists of compound (A1) and compound (A2).

[0268] In one embodiment, component (B) is compound (B1).

[0269] In another embodiment, component (B) is compound (B2).

[0270] In another embodiment, component (B) consists of compounds (B1) and (B2).

[0271] In one embodiment, component (A) is compound (A1) and component (B) is compound (B2).

[0272] In another embodiment, component (A) is compound (A1), and component (B) is compound (B1) and compound (B2).

[0273] In one embodiment, component (A) is compound (A2) and component (B) is compound (B1).

[0274] In another embodiment, component (A) is compound (A2) and component (B) is compound (B2).

[0275] In another embodiment, component (A) consists of compounds (A1) and (A2), and component (B) consists of compound (B1).

[0276] In another embodiment, component (A) consists of compounds (A1) and (A2), and component (B) consists of compound (B2).

[0277] In one embodiment, component (A) consists of compounds (A1) and (A2), and component (B) consists of compounds (B1) and (B2).

[0278] In one embodiment, the surface treatment agent of the present invention does not contain vinyl polymers, particularly vinyl polymers containing silanes.

[0279] When component (A) includes compound (A1) and compound (A2), the ratio of compound (A1) to compound (A2) is preferably 1:10 to 10:1, more preferably 1:5 to 5:1, and even more preferably 1:3 to 3:1.

[0280] When component (A) contains compound (A1) and component (B) contains compound (B2), the ratio of compound (A1):compound (B2) is preferably 1:10 to 10:1, more preferably 1:5 to 5:1, and even more preferably 1:3 to 3:1. By setting the ratio of compound (A1) to compound (B2) within the above range, the slip properties and UV durability of the surface treatment layer are further improved.

[0281] When component (B) comprises compounds (B1) and (B2), the ratio of compound (B1):compound (B2) is preferably 1:10 to 10:1, more preferably 1:5 to 5:1, and even more preferably 1:3 to 3:1. By setting the ratio of compound (B1) to compound (B2) within the above range, the slip properties and UV durability of the surface treatment layer are further improved.

[0282] When component (A) contains compound (A1) and component (B) contains compounds (B1) and (B2), the ratio of the total of compounds (A1) and (B1) to compound (B2) ({compound (A1) + compound (B1)} : compound (B2)) is preferably 1:10 to 10:1, more preferably 1:5 to 5:1, and even more preferably 1:3 to 3:1. By setting the ratio of compound (A1) to compound (B2) within the above range, the slipperiness and UV durability of the surface treatment layer are further improved.

[0283] In the surface treatment agent of the present invention, components (A) and (B) are preferably combined to a total of 0.1 to 80% by mass, more preferably 1 to 50% by mass, and even more preferably 2 to 30% by mass.

[0284] The surface treatment agent of the present invention may also contain one or more other components selected from organic solvents, water and catalysts.

[0285] Examples of organic solvents mentioned above include fluorinated organic solvents and non-fluorinated organic solvents.

[0286] Examples of fluorinated organic solvents mentioned above include perfluorohexane, perfluorooctane, perfluorodimethylcyclohexane, perfluorodecahydronaphthalene, perfluoroalkyl ethanol, perfluorobenzene, perfluorotoluene, perfluoroalkylamines (Fluorinert, etc.), perfluoroalkyl ethers, perfluorobutyltetrahydrofuran, polyfluoroaliphatic hydrocarbons (ASAHIKLIN AC6000, etc.), and hydrochlorofluorocarbons (ASAHIKLIN). AK-225 (trade name), hydrofluoroethers (Novec (trade name), HFE-7100 (trade name), HFE-7300 (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), methyl methacrylate-2-(perfluoroalkyl) ethyl acrylate, acrylate-2-(perfluoroalkyl) ethyl acrylate, perfluoroalkyl ethylene, Freon 134a and hexafluoropropylene oligomers.

[0287] Examples of the aforementioned fluorine-free 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, benzyl nitrile, butanol, 1-propanol, 2-propanol, ethanol, methanol, and diacetone alcohol.

[0288] The preferred organic solvents are methyl isobutyl ketone, propylene glycol monomethyl ether, hexadecane, butyl acetate, acetone, 2-butanone, cyclohexanone, ethyl acetate, diacetone alcohol, ethanol, or 2-propanol.

[0289] The above-mentioned organic solvents can be used alone or in combination of two or more.

[0290] The organic solvent is preferably used in the surface treatment agent in the range of 10-99% by mass, more preferably 30-95% by mass, and even more preferably 50-95% by mass.

[0291] Examples of catalysts mentioned above include acids (such as hydrochloric acid, acetic acid, trifluoroacetic acid, etc.), bases (such as ammonia, triethylamine, diethylamine, etc.), and transition metals (such as Ti, Ni, Sn, etc.).

[0292] The catalyst described above promotes the hydrolysis and dehydration condensation of the surface treatment agent of the present invention, thereby promoting the surface treatment reaction.

[0293] The surface treatment agent of the present invention may also contain a compound of formula (B2') formed by ring opening of the isocyanuric acid ring of compound (B2).

[0294]

[0295] [In the formula, R] 10 Two of them are -R 9b -SiR 2b nb R 3b 3－nb R 10 One of them is R 8 . ]

[0296] These silane compounds may or may not be present in the surface treatment agent. When present, they are preferably 0.01 to 20 mol parts, more preferably 0.1 to 15 mol parts, relative to a total of 100 mol parts of compound (B2), for example, 1 to 10 mol parts or 3 to 5 mol parts.

[0297] The surface treatment agent of the present invention may also contain cationic silane compounds. By containing cationic silane compounds, the surface treatment agent of the present invention can form a surface treatment layer with excellent lubricity, UV durability, and excellent antibacterial properties.

[0298] The aforementioned cationic compound is preferably an ammonium salt type cationic silane compound, such as the cationic silane compound shown in formula (C1).

[0299] R 13 3－m R 12 m Si-R 15 -N + R 11 3 X － (C1)

[0300] [In the formula:]

[0301] R 12 Each time it appears, it is independently either a hydroxyl group or a hydrolyzable group;

[0302] R 13 Each time it appears, it is either a hydrogen atom or a monovalent organic group;

[0303] m is an integer from 1 to 3;

[0304] R 11 C independently 1－22 alkyl;

[0305] R 15It is an organic group that is either a single bond or divalent;

[0306] X － For F － Cl － or Br － . ]

[0307] The items of the present invention will now be described.

[0308] The article of the present invention comprises a substrate and a layer (hereinafter also referred to as "surface treatment layer") formed on the surface of the substrate by the surface treatment agent of the present invention.

[0309] The substrates that can be used in this invention can be made of, for example, glass, resin (natural or synthetic resin, such as general plastic materials), metal, ceramics, semiconductors (silicon, germanium, etc.), fibers (fabric, non-woven fabric, etc.), fur, leather, wood, ceramics, stone, building materials, hygiene products, or any suitable material.

[0310] For example, if the article to be manufactured is an optical component, the material constituting the surface of the substrate can be a material used for optical components, such as glass or transparent plastic. Alternatively, if the article to be manufactured is an optical component, a layer (or film), such as a hard coating or an anti-reflective layer, can be formed on the surface of the substrate (outermost layer). The anti-reflective layer can be any type of single-layer or multi-layer anti-reflective layer. Examples of inorganic materials that can be used for anti-reflective layers include SiO2, SiO, ZrO2, TiO2, TiO, Ti2O3, Ti2O5, Al2O3, Ta2O5, Ta3O5, Nb2O5, HfO2, Si3N4, CeO2, MgO, Y2O3, SnO2, MgF2, WO3, etc. These inorganic materials can be used alone or in combination of two or more (e.g., forming a mixture). When forming a multi-layer anti-reflective layer, it is preferable to use SiO2 and / or SiO in its outermost layer. When the item to be manufactured is an optical glass component for a touch panel, a transparent electrode can be formed on a portion of the substrate (glass) surface, for example, using a thin film made of indium tin oxide (ITO) or indium zinc oxide. Furthermore, depending on its specific specifications, the substrate may also include insulating layers, adhesive layers, protective layers, decorative frame layers (I-CON), atomizing film layers, hard coating layers, polarizing films, retardation films, and liquid crystal display modules.

[0311] The shape of the substrate is not particularly limited; for example, it can be a plate, a film, or other forms. Furthermore, 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 and specific specifications of the article to be manufactured.

[0312] In one approach, the substrate can be a material whose surface portion is formed from a material that inherently possesses hydroxyl groups. Examples of such materials include glass, as well as metals (especially base metals), ceramics, semiconductors, etc., on which a natural or thermal oxide film forms. Alternatively, in the case of resins, where hydroxyl groups are present but not sufficiently, or where hydroxyl groups are not present to begin with, hydroxyl groups can be introduced or added to the surface of the substrate through some pretreatment. Examples of such pretreatments include plasma treatment (e.g., corona discharge) and ion beam irradiation. Plasma treatment can also be appropriately utilized to introduce or add hydroxyl groups to the substrate surface and to clean the substrate surface (removing foreign matter, etc.). Other examples of such pretreatments include methods such as forming a surface adsorbent with carbon-carbon unsaturated bond groups in the form of a monolayer on the substrate surface using the LB method (Langmuir-Blodgett method), chemical adsorption, etc., and then breaking the unsaturated bonds in an atmosphere containing oxygen, nitrogen, etc.

[0313] In another approach, such a substrate may also be a substrate whose surface portion is formed of at least one other reactive group, such as an organosilicon compound with a Si-H group or a material containing an alkoxysilane.

[0314] In a preferred embodiment, the substrate is glass. Preferred types of glass include sapphire glass, soda-lime glass, alkali aluminosilicate glass, borosilicate glass, alkali-free glass, crystal glass, and quartz glass. Particularly preferred are chemically strengthened soda-lime glass, chemically strengthened alkali aluminosilicate glass, and chemically bonded borosilicate glass.

[0315] By forming a layer of the surface treatment agent of the present invention on the surface of the above-mentioned substrate, and performing post-treatment on the layer as needed, a layer is formed by the surface treatment agent of the present invention, thereby enabling the manufacture of articles of the present invention.

[0316] The formation of the surface treatment agent layer of the present invention can be achieved by applying the surface treatment agent to the surface of the substrate in a manner that covers the substrate surface. The covering method is not particularly limited. For example, a wet covering method and a dry covering method can be used.

[0317] Examples of wet coating methods include dip coating, spin coating, flow coating, spray coating, roller coating, gravure coating, and similar methods.

[0318] Examples of dry coating methods include vapor deposition (usually vacuum vapor deposition), sputtering, CVD, and similar methods. Specific examples of vapor deposition methods (usually vacuum vapor deposition) include resistance heating, electron beam, high-frequency heating using microwaves, ion beam, and similar methods. Specific examples of CVD methods include plasma-CVD, optical CVD, thermal CVD, and similar methods.

[0319] Alternatively, atmospheric pressure plasma can be used for coverage.

[0320] When using the dry coating method, the surface treatment agent of the present invention can be supplied directly to the dry coating method, or it can be supplied to the dry coating method after being diluted with the above-mentioned organic solvent.

[0321] The formation of the surface treatment agent layer is preferably carried out in such a manner that the surface treatment agent of the present invention coexists with a catalyst for hydrolysis and dehydration condensation in the layer. In short, when using the wet coating method, the catalyst can be added to the diluted solution of the surface treatment agent of the present invention after diluting it with a solvent, just before it is applied to the substrate surface. When using the dry coating method, the surface treatment agent of the present invention with the catalyst added can be directly subjected to vapor deposition (usually vacuum vapor deposition), or the surface treatment agent of the present invention with the catalyst added can be impregnated in a porous metal such as iron or copper to obtain particulate matter, and the obtained particulate matter can be subjected to vapor deposition (usually vacuum vapor deposition).

[0322] The catalyst can be any suitable acid or base. Examples of acid catalysts include hydrochloric acid, acetic acid, formic acid, and trifluoroacetic acid. Examples of base catalysts include ammonia and organic amines.

[0323] The surface treatment layer contained in the article of the present invention has lubricating properties. In addition to high lubricating properties, the surface treatment layer can also have antibacterial, water-repellent, oil-repellent, stain-resistant (e.g., preventing the adhesion of fingerprints and other stains), waterproof (preventing water from penetrating electronic components, etc.), and surface smoothness (or lubricity, such as the ability to wipe away fingerprints and other stains, and excellent finger feel) depending on the composition of the surface treatment agent used, and can be suitable for use as a functional film.

[0324] The articles of the present invention are useful in applications where it is necessary to maintain lubricity even during prolonged use in harsh outdoor environments.

[0325] In a preferred embodiment, the articles of the present invention are useful in glass or mirror glass for vehicles, ships, or aircraft, such as automotive glass, automotive door rearview mirrors, or automotive fender rearview mirrors, or glass used in vehicle cameras. Furthermore, they are useful in substrates for outdoor applications such as glass used in surveillance cameras and curved mirrors.

[0326] Therefore, the present invention also relates to optical materials having the above-described surface treatment layer as the outermost layer.

[0327] In addition to optical materials such as displays exemplified below, a variety of other optical materials can be preferred as optical materials, such as cathode ray tubes (CRTs; for example, computer monitors), liquid crystal displays, plasma displays, organic EL displays, inorganic thin-film EL dot matrix displays, rear projection displays, fluorescent display tubes (VFDs), field emission displays (FEDs), and protective plates for these displays, or materials obtained by treating their surfaces with anti-reflective coatings.

[0328] The items of this invention are not particularly limited and can be optical components. Examples of optical components include: lenses for eyeglasses, etc.; front protective plates, anti-reflective plates, polarizing plates, and anti-glare plates for displays such as PDPs and LCDs; touch panel sheets for devices such as mobile phones and portable information terminals; disc surfaces for Blu-ray (registered trademark) discs, DVD discs, CD-Rs, MO discs, etc.; optical fibers; and the display surface of clocks, etc.

[0329] In addition, the articles of the present invention can also be medical devices or medical materials.

[0330] The thickness of the aforementioned layer is not particularly limited. In the case of automotive glass or rearview mirrors, considering long-term weather resistance, a thickness of the aforementioned layer is preferably in the range of, for example, 1–1000 nm, 1–500 nm, or 1–100 nm. In the case of optical components, considering optical performance and lubrication, a thickness of the aforementioned layer is preferably in the range of 1–50 nm, more preferably 1–30 nm, and even more preferably 1–15 nm.

[0331] The surface treatment agent and article of the present invention have been described in detail above. However, the surface treatment agent and article of the present invention are not limited to the examples illustrated above.

[0332] Example

[0333] The surface treatment agent of the present invention will be described in the following embodiments, but the present invention is not limited to the following embodiments.

[0334] Prepare the following compounds as components (A) and (B).

[0335] Compound (A1)

[0336]

[0337] Compound (A2)

[0338]

[0339] Compound (B1)

[0340]

[0341] Compound (B2)

[0342]

[0343] Preparation of surface treatment agent 1

[0344] Compounds (A1), (A2), (B1), and (B2) were dissolved in ethanol in a specified ratio to a total weight of 20 wt%. 0.01 N hydrochloric acid (0.15 by mass) was then added to this solution to prepare surface treatment agents 1–10. The proportions (molar ratios) of each compound are shown in Table 1 below.

[0345] [Table 1]

[0346]

[0347] Preparation of surface-treated samples 1

[0348] The surface treatment agents 1-10 prepared above were spin-coated onto a soda-lime glass substrate (at 2000 rpm for 10 seconds) to form a surface treatment layer, resulting in surface treatment samples 1-10. It should be noted that surface treatment samples 1-9 are Examples 1-9, and surface treatment sample 10 is Comparative Example 1. The initial roll-off angle and the roll-off angle after UV irradiation were evaluated for the obtained surface treatment samples 1-10. The results are shown in Table 2 below.

[0349] Method for determining the roll angle

[0350] A water droplet was applied to the surface treatment layer of a horizontally placed surface-treated sample using a micro-syringe. The sample was tilted to 90° at a speed of 2° per second, and the droplet's shape was observed. The angle at which the droplet moved 5 mm was defined as the roll-off angle. The droplet volume was set to 20 μL for measurement.

[0351] Promoting UV resistance test

[0352] For surface-treated samples 1 to 10, UV resistance enhancement tests were performed as described below. A UVB-313 lamp (manufactured by Q-Lab, with an irradiance of 0.63 W / m² at 310 nm) was used. 2 The distance between the lamp and the surface treatment layer of the surface-treated sample was set to 5 cm, and the temperature of the plate on which the surface-treated sample was placed was 63°C. Continuous UVB irradiation was performed, but the surface-treated sample was temporarily removed before measuring the roll-off angle. Changes were confirmed after 480 hours of irradiation.

[0353] [Table 2]

[0354]

[0355] Preparation of surface treatment agents 2

[0356] Compounds (A2) and (B1) were dissolved in ethanol in a specified ratio to a total weight of 30 wt%. 0.01 N hydrochloric acid (0.15 by mass) was added to each solution to prepare surface treatment agents 11–17. The molar ratios of the compounds are shown in Table 3 below. It should be noted that the (A2) / (B1) molar ratio of surface treatment agent 11 is 0, meaning it contains only compound (B1).

[0357] Preparation and evaluation of surface-treated samples

[0358] Using the surface treatment agents 11-17 prepared above, surface treatment samples 11-17 were prepared according to the method described in Preparation 1 of the surface treatment sample above. For the obtained surface treatment samples 11-17, the roll-off angle was measured and the UV resistance enhancement test was performed in the same manner as described above. The results are shown in Table 3 below. It should be noted that surface treatment sample 11 is Comparative Example 2, and surface treatment samples 12-17 are Examples 10-15.

[0359] [Table 3]

[0360]

[0361] Fit test

[0362] The adhesion of various surface treatment agents to glass was evaluated using a cross-cut test. Specifically, 11 cuts extending to the substrate were made on the test surface using a cutter, creating a checkerboard pattern of 100 cuts spaced 1 mm apart. Cellotape was then strongly pressed and bonded to this pattern, and the end of the tape was peeled off in one go at a 45° angle. Regarding coating peeling, a multi-purpose pen was used to apply ink to the peeled checkerboard pattern, and the areas completely coated were considered defects. Adhesion was scored according to the following criteria.

[0363] 10 points: No square was stripped.

[0364] 8 points: There is a small amount of peeling at the intersection of the cuts, and the area of ​​the defect is less than 5% of the area of ​​the entire square.

[0365] 6 points: There is peeling on both sides and at the intersection of the cut, and the area of ​​the defect is more than 5% and less than 15% of the area of ​​the whole square.

[0366] 4 points: Partial or complete peeling along the cut line, with the area of ​​the defect being more than 15% and less than 35% of the area of ​​the entire square.

[0367] 2 points: Partial or complete peeling along the cut line, with the area of ​​the defect being more than 35% and less than 65% of the area of ​​the entire square.

[0368] 0 points: The area of ​​the missing part of the cut is more than 65% of the entire square.

[0369] [Table 4]

[0370] Compound (A1) Compound (A2) Compound (B1) Compound (B2) Number of missing parts Fraction Example 4 0 10 1 0 5 / 100 8 points Example 9 0 10 0 1 0 / 100 10 points Comparative Example 1 10 0 1 0 70 / 100 0 points

[0371] Evaluation of surface hardness

[0372] The surface hardness of each surface-treated sample was determined using the ERICHSEN Hardness Test Pencil Model 318S (ISO 1518). The results of this test are compared with approximate pencil hardness values ​​in the following table.

[0373] [Table 5]

[0374] 318 test bar Approximate value of pencil hardness 0.5N 2H-3H 1.0N 3H 2.0N 3H-4H 4.0N 6H-7H

[0375] [Table 6]

[0376]

[0377] ○: Unharmed; ×: Injured.

[0378] Industrial availability

[0379] The surface treatment agent of the present invention can be suitably used in a wide variety of applications.

Claims

1. A surface treatment agent characterized by comprising: (A) a compound represented by the following formula (Al) or a compound represented by the following formula (A2); and (B) a compound represented by the following formula (B2), ###0001### (Al) ###0002### (A2) ###0003### (B2) In formula (Al): M is Si; m is the valence of the M; R 1 are each independently a hydrogen atom or a C 1－6 alkyl group; R 4 are each independently C 1－3 alkyl or C 1－3 alkoxy; n is 0 or more and the valence of the M or less; In formula (A2): In formula (B2): R 2a independently at each occurrence, is hydroxyl or a hydrolyzable group; R 3a independently at each occurrence, is a hydrogen atom or a monovalent organic group; na is an integer from 1 to 3 at each SiR 2a na R 3a 3－na each independently an integer from 1 to 3; R 9a are each independently a single or 2-valent group; 2. The surface treatment agent according to claim 1, characterized in that: the compound represented by the formula (Al) is a metal alkoxide represented by the following formula (Al-1), ###0004### (Al-1) in the formula: M is Si; and n is the valence of the M. R 2b independently at each occurrence, is hydroxyl or a hydrolyzable group; R 3b independently at each occurrence, a hydrogen atom or a monovalent organic group; nb is an integer from 1 to 3 at each SiR 2b nb R 3b 3－nb is an integer from 1 to 3 in each unit, respectively; R 9b are each independently a single or 2-valent group; R 8 is C 1－30 alkyl, C 1－30 oxyalkyl, C 1－30 fluoroalkyl, -X S -R S or a perfluoropolyether-containing group, wherein X S is a single bond or a divalent organic group, and R S is a siloxane group.

3. The surface treatment agent according to claim 1 or 2, characterized in that: the compound represented by the formula (Al) is a metal alkoxide represented by the following formula (Al-2), ###0005### (Al-2) in the formula: M is Si; and n is the valence of the M.

4. The surface treatment agent according to claim 1 or 2, characterized by comprising the compound represented by the formula (A2). M(OR 1 ) n (A1-1) 5. The surface treatment agent according to claim 1 or 2, characterized by comprising the compound represented by the formula (A2), a compound represented by the following formula (Bl), and the compound represented by the formula (B2), ###0006### (Bl) in formula (Bl): na and nb are each an integer of 1 or more and 3 or less; and M is Si.

6. The surface treatment agent according to claim 1 or 2, characterized in that: na and nb are 3. R 1 are each independently a hydrogen atom or a C 1－6 alkyl group; 7. The surface treatment agent according to claim 5, characterized in that: the compound represented by the formula (Bl) is a compound represented by the following formula (Bl-1), ###0007### (Bl-1) in the formula: M is Si; and n is the valence of the M.

8. The surface treatment agent according to claim 1 or 2, characterized in that: the compound represented by the formula (A2) is a compound represented by the following formula (A2-1), ###0008### (A2-1) in the formula: M is Si; and n is the valence of the M.

9. The surface treatment agent according to claim 1 or 2, characterized in that: the compound represented by the formula (A2) is a compound represented by the following formula (A2-2), ###0009### (A2-2) in the formula: M is Si; and n is the valence of the M. Si(OR 1 )4 (A1-2) wherein R 1 are each independently a hydrogen atom or a C 1－6 alkyl group.

10. The surface treatment agent according to claim 1 or 2, characterized in that: the compound represented by the formula (A2) is a compound represented by the following formula (A2-3), ###0010### (A2-3) in the formula: M is Si; and n is the valence of the M.

11. The surface treatment agent according to claim 1 or 2, characterized in that: the molar ratio of component (A) to component (B) is 0.01 to 100:

1.

12. The surface treatment agent according to claim 1 or 2, characterized by further comprising one or more other components selected from the group consisting of an organic solvent, water, and a catalyst.

13. A surface-treated product comprising a substrate and a layer formed on the substrate from the surface treatment agent according to claim 1 or 2. M b (OR 1b ) q (R 4b ) p－q (B1) ​ M b Si; R 1b are each independently a hydrogen atom or a C 1－6 alkyl group; R 4b is C 1－30 alkyl, C 1－30 fluoroalkyl or siloxanyl; p is the valence of said M b ; q is 1 or more and M b of valence -1 or less. ​ ​ ​ R 4b is C 1－30 alkyl. ​ R 8 is C 1－30 alkyl. ​ R 9a is C 1－6 alkylene. ​ R 9b is C 1－6 alkylene. ​ ​ ​ ​ 13. An article characterized by: ​

Images