Compound for surface treatment, surface treatment agent, and article

Abstract

Provided are: a hydrocarbon terminal group-containing compound capable of forming a cured film excellent in water repellency, slipperiness, ease of soil removal, and abrasion resistance; a surface treatment agent containing the compound; and an article surface treated with the surface treatment agent.　This hydrocarbon terminal group-containing compound has at least one C3-32 linear, branched, or cyclic monovalent hydrocarbon terminal group and has at least one reactive phosphonic acid group or phosphonic acid ester group at the other molecular terminal through a divalent or higher linking group bonded to the hydrocarbon terminal group.

Description

Surface treatment compounds, surface treatment agents, and articles

[0001] The present invention relates to a compound for surface treatment, and more particularly to a hydrocarbon-terminated compound, especially an alkyl-terminated compound, that forms a film with excellent water repellency, abrasion resistance, and rapid curing properties, as well as a surface treatment agent containing the compound, and an article surface-treated with the surface treatment agent.

[0002] In recent years, the use of touch panels in displays such as smartphones and in-car displays has accelerated. However, because touch panels have exposed screens, they are frequently in direct contact with fingers and cheeks, making them prone to dirt and sebum buildup. Therefore, there is a growing demand for technologies that make the display surface less prone to fingerprints and easier to clean, in order to improve appearance and visibility. The development of materials that can meet these demands is highly desirable. In particular, since the surface of touch panel displays is prone to fingerprint smudges, there is a desire to provide a water- and oil-repellent layer. However, while conventional water- and oil-repellent layers have high water and oil repellency and are excellent at wiping away dirt, they lack sufficient abrasion resistance and have the problem of fingerprints being very noticeable when they do adhere to the surface.

[0003] Generally, fluoropolyether group-containing compounds have very low surface free energy, resulting in properties such as water and oil repellency, chemical resistance, lubricity, mold release, and antifouling. These properties are utilized industrially in a wide range of applications, including water, oil, and stain repellents for paper and textiles, lubricants for magnetic recording media, oil inhibitors and mold release agents for precision equipment, cosmetics, and protective films. However, these properties also mean non-stickiness and poor adhesion to other substrates; while they can be applied to substrate surfaces, achieving a strong bond between the film and the substrate is difficult.

[0004] Silane coupling agents are well-known for bonding organic compounds to substrate surfaces such as glass and cloth, and are widely used as coating agents for various substrate surfaces. A silane coupling agent has an organic functional group and a reactive silyl group (generally a hydrolyzable silyl group such as an alkoxysilyl group) in one molecule. The hydrolyzable silyl group undergoes a self-condensation reaction with moisture in the air to form a film. This film becomes a strong and durable coating because the hydrolyzable silyl group chemically and physically bonds with the surface of glass, metal, etc.

[0005] Therefore, compositions have been disclosed that use a fluoropolyether group-containing polymer obtained by introducing a hydrolyzable silyl group into a fluoropolyether group-containing compound, which can easily adhere to the substrate surface and form a coating on the substrate surface that has water-repellent and oil-repellent properties, chemical resistance, lubricity, mold release properties, and antifouling properties (Patent Documents 1 to 6: Japanese Patent Publication No. 2008-534696, Japanese Patent Publication No. 2008-537557, Japanese Unexamined Patent Publication No. 2012-072272, Japanese Unexamined Patent Publication No. 2012-157856, Japanese Unexamined Patent Publication No. 2013-136833, Japanese Unexamined Patent Publication No. 2015-199906).

[0006] Japanese Patent Publication No. 2008-534696, Japanese Patent Publication No. 2008-537557, Japanese Unexamined Patent Publication No. 2012-072272, Japanese Unexamined Patent Publication No. 2012-157856, Japanese Unexamined Patent Publication No. 2013-136833, Japanese Unexamined Patent Publication No. 2015-199906

[0007] However, fluorine-containing compounds, such as those containing fluoropolyether groups, are difficult to decompose in nature and tend to accumulate in the environment. Therefore, there is a growing need for the development of surface treatment agents for non-fluorine-based materials.

[0008] Furthermore, while hydrolyzable silyl groups have been widely used as substrate adhesion groups introduced into fluoropolyether group-containing compounds, they exhibit excellent adhesion to glass and SiO2, but it is difficult to directly adhere them to surfaces other than glass and SiO2, such as metal oxides and resins.

[0009] Recently, there has been a growing demand for technologies that make fingerprints less likely to adhere to the surface of displays and the casings of electronic devices, as well as technologies that make it easier to remove dirt, in order to improve appearance and visibility. As a result, there is a need for the development of materials that can adhere to various surfaces other than glass and SiO2.

[0010] The present invention has been made in view of the above circumstances, and aims to provide a non-fluorine-based (i.e., one that does not contain fluorine atoms in its molecule) surface treatment compound that can form a cured film with excellent water repellency, slipperiness, dirt-wiping properties, and abrasion resistance on various substrate surfaces, particularly metal oxide surfaces, a substantially non-fluorine-based surface treatment agent containing the compound, and an article surface-treated with the surface treatment agent.

[0011] As a result of diligent research to solve the above objectives, the present inventors have discovered that by using a hydrocarbon end group-containing compound having at least one linear, branched, or cyclic monovalent hydrocarbon end group having 3 to 32 carbon atoms, and having at least one phosphonic acid group or phosphonic acid ester group in the molecule, a surface treatment agent containing the compound can form a hardened film on the metal oxide surface that is excellent in water repellency, slipperiness, dirt wiping properties, and abrasion resistance, thus leading to the present invention.

[0012] Accordingly, the present invention provides the following hydrocarbon end group-containing compounds, surface treatment agents and articles: [1] A hydrocarbon end group-containing compound having at least one linear, branched, or cyclic monovalent hydrocarbon end group having 3 to 32 carbon atoms, and having at least one reactive phosphonic acid group or phosphonic acid ester group at the other molecular end via a divalent or higher linking group bonded to the hydrocarbon end group. [2] The hydrocarbon end group-containing compound according to [1], wherein the hydrocarbon end group is a group selected from alkyl groups having 6 to 28 carbon atoms and aryl groups having 6 to 32 carbon atoms. [3] The hydrocarbon end group-containing compound according to [1] or [2], having two or more hydrocarbon end groups, wherein the linking group bonded to the hydrocarbon end group is trivalent or higher. [4] The hydrocarbon end group-containing compound is of the following general formula (1) (In the formula, R 1R may contain at least one atom selected from oxygen, sulfur, nitrogen, and silicon, and may be linear, branched, cyclic, or a combination thereof, and is a monovalent hydrocarbon group having 3 to 32 carbon atoms. 2 These are independently a hydrogen atom, a halogen atom, a hydroxyl group, a siloxy group, an amino group, a thiol group, a monovalent hydrocarbon group having 1 or 2 carbon atoms, R 1 , or -Y-A, where U is a carbon atom, a silicon atom, a nitrogen atom, or a trivalent or tetravalent organic group, V is a single bond, or a divalent hydrocarbon group which may contain at least one selected from an oxygen atom, a nitrogen atom, and a sulfur atom, Z is a single bond, a carbon atom, a silicon atom, a nitrogen atom, a sulfur atom, or a trivalent to octavalent organic group, Y is independently a divalent hydrocarbon group which may contain at least one selected from an oxygen atom, a nitrogen atom, a sulfur atom, and a silicon atom, and A is independently the following general formula (2) (wherein R is independently a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a phenyl group.) A hydrocarbon terminal group-containing compound according to any one of the following [1] to [3], represented by (1) above, where k is 1 or 2, and m is an integer from 1 to 7. [5] In formula (1) above, R 1 A hydrocarbon terminal group-containing compound according to [4], wherein R is a monovalent hydrocarbon group having 13 to 32 carbon atoms, which may be linear, branched, cyclic, or a combination thereof. [6] In formula (1), at least one R 2 R 1 A hydrocarbon terminal group-containing compound as described in [4] or [5]. [7] In formula (1), R 1 However, the following formula (In the formula, R Ais a monovalent hydrocarbon group having 3 to 32 carbon atoms, which may be independently linear, branched, cyclic or a combination thereof; Q is independently an oxygen atom, a sulfur atom, a divalent cyclic hydrocarbon group having 6 to 8 carbon atoms, a diorganosilylene group, a silyalkylene structure or a silyarylene structure, a linear organopolysiloxane residue having 2 to 10 silicon atoms or a branched or cyclic divalent organopolysiloxane residue having 3 to 10 silicon atoms, a carbonyl (ketone) group, an ester group, a carbonate group, a sulfinyl group, a sulfonyl group, a thioester group, a thiocarbonate group, a thiocarbamate group, an amino group, an amide group, a carbamate group, a urea group, and a divalent nitrogen-containing heterocyclic group; Q' is independently a trivalent group selected from the group consisting of a nitrogen atom, a trivalent cyclic hydrocarbon group having 6 to 8 carbon atoms, a linear organopolysiloxane residue having 2 to 10 silicon atoms or a branched or cyclic trivalent organopolysiloxane residue having 3 to 10 silicon atoms, a trivalent amide group, and a trivalent nitrogen-containing heterocyclic group; Q'' is independently a tetravalent group selected from the group consisting of a carbon atom, a silicon atom, a tetravalent cyclic hydrocarbon group having 6 to 8 carbon atoms, and a linear organopolysiloxane residue having 2 to 10 silicon atoms or a branched or cyclic tetravalent organopolysiloxane residue having 3 to 10 silicon atoms; R<> B is independently a single bond or a divalent hydrocarbon group having 1 to 32 carbon atoms, which may be linear, branched or cyclic; R<> C is independently R<> AA hydrocarbon terminal group-containing compound according to any one of the following items [4] to [6], which is any group represented by (or a hydrogen atom, where p is an integer from 0 to 10, provided that the total number of carbon atoms in each structure is 32 or less). [8] A hydrocarbon terminal group-containing compound according to any one of [4] to [7], wherein in formula (1), Y is a group selected from the group consisting of an alkylene group having 1 to 20 carbon atoms which may contain at least one selected from an oxygen atom, a nitrogen atom, and a sulfur atom, an alkylene group having 1 to 10 carbon atoms which may contain an arylene group having 6 to 8 carbon atoms, a divalent group in which alkylene groups having 1 to 8 carbon atoms are bonded to each other via a diorganosilylene group, a sylalkylene structure, a sylarylene structure, or a nitrogen-containing heterocyclic group, and a divalent group in which an alkylene group having 1 to 10 carbon atoms is bonded to the bond of a linear or branched or cyclic organopolysiloxane residue having 2 to 10 silicon atoms. [9] In formula (1), Z is a single bond, or a carbon atom, a silicon atom, a nitrogen atom, a trivalent or tetravalent cyclic hydrocarbon group having 6 to 8 carbon atoms, -SiR 3 = (R 3 (A trivalent group represented by a hydroxyl group, an alkyl group having 1 to 3 carbon atoms, or an alkoxy group having 1 to 3 carbon atoms), -CR 4 = (R 4A hydrocarbon terminal group-containing compound according to any one of the following items [4] to [8]: a trivalent group represented by a hydrogen atom, a hydroxyl group, or an alkyl group having 1 to 3 carbon atoms; a linear or branched or cyclic tri- to octavalent organopolysiloxane residue having 2 to 10 silicon atoms or 3 to 10 silicon atoms; a trivalent amide group; a trivalent carbamate group; a trivalent or tetravalent urea group; and a tri- to octavalent nitrogen-containing heterocyclic group.

[10] A hydrocarbon terminal group-containing compound according to any one of the claims [4] to [9], wherein in formula (1), U is a trivalent or tetravalent group selected from the group consisting of a carbon atom, a silicon atom, a nitrogen atom, a trivalent or tetravalent cyclic hydrocarbon group having 6 to 8 carbon atoms, a linear or branched or cyclic trivalent or tetravalent organopolysiloxane residue having 2 to 10 silicon atoms, a trivalent amide group, a trivalent carbamate group, a trivalent or tetravalent urea group, and a trivalent or tetravalent nitrogen-containing heterocyclic group.

[11] A surface treatment agent comprising a hydrocarbon terminal group-containing compound according to any one of the claims [1] to

[10] and / or a partial (hydrolysis) condensate thereof.

[12] An article surface-treated with the surface treatment agent according to

[11] .

[0013] The hydrocarbon-end group-containing compounds of the present invention, when applied to the surface of various substrates such as glass and metal alloys, can form a cured film with high adhesion. This cured film exhibits excellent water repellency, slipperiness, dirt-wiping properties, abrasion resistance, and chemical resistance. Therefore, the hydrocarbon-end group-containing compounds of the present invention can be suitably used as surface treatment compounds in various articles such as the surfaces of displays and the casings of electronic devices.

[0014] <Hydrogen-End Group-Containing Compounds> The hydrocarbon-end group-containing compounds of the present invention are characterized by having at least one linear, branched, or cyclic monovalent hydrocarbon end group having 3 to 32 carbon atoms, and having at least one phosphonic acid group or phosphonic acid ester group in the molecule.

[0015] The hydrocarbon end group-containing compound of the present invention has at least one hydrocarbon chain end group with a predetermined number of carbon atoms, thereby improving molecular mobility. As a result, the cured film of the surface treatment agent containing the compound exhibits water repellency, as well as excellent slipperiness, dirt-wiping properties, and abrasion resistance. Furthermore, the hydrocarbon end group-containing compound of the present invention has at least one reactive phosphonic acid group or phosphonic acid ester group at the other molecular end via a divalent or higher linking group, which allows it to adhere particularly strongly to the metal oxide surface of the substrate, improving abrasion resistance.

[0016] The number of carbon atoms in the hydrocarbon chain end group of a predetermined number of carbon atoms is preferably 3 to 32, and more preferably 6 to 28. The hydrocarbon chain end group of a predetermined number of carbon atoms is preferably a group selected from alkyl groups with 6 to 28 carbon atoms and aryl groups with 6 to 32 carbon atoms. The hydrocarbon end group-containing compound of the present invention is preferably a compound having an alkyl group with 10 to 28 carbon atoms at its terminus. Furthermore, the hydrocarbon end group-containing compound of the present invention is preferably a compound having two or more hydrocarbon chain end groups of a predetermined number of carbon atoms in one molecule.

[0017] The hydrocarbon terminal group-containing compound of the present invention is preferably represented by the following general formula (1). In formula (1), R 1 R may independently contain at least one selected from oxygen, sulfur, nitrogen, and silicon atoms, and may be linear, branched, cyclic, or a combination thereof, and is a monovalent hydrocarbon group having 3 to 32 carbon atoms, 2 R is a hydrogen atom, halogen atom, hydroxyl group, siloxy group, amino group, thiol group, monovalent hydrocarbon group having 1 or 2 carbon atoms, 1, or -Y-A, where U is a carbon atom, a silicon atom, a nitrogen atom, or a trivalent or tetravalent organic group, V is a single bond, or a divalent hydrocarbon group which may contain at least one selected from an oxygen atom, a nitrogen atom, and a sulfur atom, Z is a single bond, a carbon atom, a silicon atom, a nitrogen atom, a sulfur atom, or a 3- to 8valent organic group, Y is a divalent hydrocarbon group which may independently contain at least one selected from an oxygen atom, a nitrogen atom, a sulfur atom, and a silicon atom, A is a group represented by the following general formula (2), k is 1 or 2, and m is an integer from 1 to 7. In formula (2), R is independently a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a phenyl group.

[0018] In the above formula (1), R 1 This group may independently contain at least one selected from oxygen, sulfur, nitrogen, and silicon atoms, and may be linear, branched, cyclic, or a combination thereof, and is a monovalent hydrocarbon group having 3 to 32 carbon atoms, preferably 6 to 28 carbon atoms, more preferably 8 to 28 carbon atoms. Here, when at least one selected from oxygen, sulfur, nitrogen, and silicon atoms is included, it is preferable that it be included as a group such as an ether group, carbonyl (ketone) group, ester group, carbonate group, thioether group, sulfinyl group, sulfonyl group, thioester group, thiocarbonate group, thiocarbamate group, amino group, amide group, carbamate group, urea group, oxazole group, imidazole group, triazole group, cyanurate group, isocyanurate group, diorganosilylene group, organopolysiloxane residue, sylalkylene group, or sylarylene group.

[0019] R 1 The base represented by the following formula is preferred. In the above formula, R AQ is independently a monovalent hydrocarbon group having 3 to 32 carbon atoms, which may be linear, branched, cyclic, or a combination thereof, and Q is independently an oxygen atom, a sulfur atom, a divalent cyclic hydrocarbon group having 6 to 8 carbon atoms, a diorganosilylene group, a sylalkylene structure or sylarylene structure, a linear or branched or cyclic divalent organopolysiloxane residue having 2 to 10 silicon atoms, a carbonyl (ketone) group, an ester group, a carbonate group, a sulfinyl group, a sulfonyl group, a thioester group, a thiocarbonate group, a thiocarbamate group, an amino group, an amide group, a carbamate group, a urea group, and a divalent nitrogen-containing heterocyclic group (divalent oxazole group, divalent imidazole group, 2 Q' is a divalent group selected from the group consisting of (such as a trivalent triazole group), Q' is a trivalent group selected from the group consisting of a nitrogen atom, a trivalent cyclic hydrocarbon group having 6 to 8 carbon atoms, a linear or branched or cyclic trivalent organopolysiloxane residue having 2 to 10 silicon atoms, a trivalent amide group, and a trivalent nitrogen-containing heterocyclic group (such as a trivalent cyanurate group, a trivalent isocyanurate group, or a trivalent triazole group), Q'' is a tetravalent group selected from the group consisting of a carbon atom, a silicon atom, a tetravalent cyclic hydrocarbon group having 6 to 8 carbon atoms, and a linear or branched or cyclic tetravalent organopolysiloxane residue having 2 to 10 silicon atoms, R B R is a divalent hydrocarbon group having 1 to 32 carbon atoms, which may be independently single-bonded, linear, branched, or cyclic, C R is independent A Alternatively, it is a hydrogen atom, and p is an integer between 0 and 10. However, the total number of carbon atoms in each structure is 32 or less.

[0020] In the above formula, R A R is a monovalent hydrocarbon group having 3 to 32 carbon atoms, preferably 6 to 28 carbon atoms, more preferably 8 to 28 carbon atoms, which may be independently linear, branched, cyclic, or a combination thereof. A For example, the following can be cited:

[0021] (In the formula, x is an integer between 2 and 31, preferably between 5 and 27, more preferably between 7 and 27, and y and y' are integers of 1 or more such that the sum of the number of carbon atoms in each structure is 32 or less.)

[0022] In the above formula, Q is a divalent group selected independently from the group consisting of an oxygen atom, a sulfur atom, a divalent cyclic hydrocarbon group having 6 to 8 carbon atoms, a diorganosilylene group, a sylalkylene structure or sylarylene structure, a divalent organopolysiloxane residue having 2 to 10 silicon atoms, particularly a linear structure with 2 to 8 silicon atoms, or a branched or cyclic structure with 3 to 10 silicon atoms, particularly a branched or cyclic structure with 3 to 8 silicon atoms, a carbonyl (ketone) group, an ester group, a carbonate group, a sulfinyl group, a sulfonyl group, a thioester group, a thiocarbonate group, a thiocarbamate group, an amino group, an amide group, a carbamate group, a urea group, and a divalent nitrogen-containing heterocyclic group (such as a divalent oxazole group, a divalent imidazole group, or a divalent triazole group).

[0023] Here, the groups that bond to silicon atoms in diorganosilylene groups, sylalkylene structures, sylarylene structures, and organopolysiloxane residues are preferably alkyl groups such as methyl, ethyl, propyl, and butyl groups, or phenyl groups, having 1 to 8 carbon atoms, preferably 1 to 4 carbon atoms. Furthermore, the alkylene groups in the sylalkylene structures are preferably ethylene groups, propylene groups (trimethylene groups, methylethylene groups), butylene groups (tetramethylene groups, methylpropylene groups), etc., having 2 to 6 carbon atoms, preferably 2 to 4 carbon atoms. In addition, the organopolysiloxane residue may include a sylalkylene structure in which two silicon atoms are bonded by alkylene groups such as ethylene groups and trimethylene groups.

[0024] Examples of such Q include those shown below. In the structure below, the left-hand coupling is R A It is joined to the right side, and the joining hand is R B It combines with it. (In the formula, f is an integer between 2 and 4, and e is an integer between 1 and 9.)

[0025] In the above formula, Q' is a trivalent group selected independently from the group consisting of a nitrogen atom, a trivalent cyclic hydrocarbon group having 6 to 8 carbon atoms, a trivalent organopolysiloxane residue having 2 to 10 silicon atoms, particularly a linear group having 2 to 8 silicon atoms, or a branched or cyclic group having 3 to 10 silicon atoms, particularly a branched or cyclic group having 3 to 8 silicon atoms, a trivalent amide group, and a trivalent nitrogen-containing heterocyclic group (such as a trivalent cyanurate group, a trivalent isocyanurate group, or a trivalent triazole group).

[0026] The organopolysiloxane residue may have an alkyl group such as a methyl group, ethyl group, propyl group, or butyl group, or a phenyl group, having 1 to 8 carbon atoms, more preferably 1 to 4 carbon atoms. The organopolysiloxane residue may also contain a sylalkylene structure in which two silicon atoms are linked by an alkylene group such as an ethylene group or a trimethylene group.

[0027] Examples of such Q' include those shown below. In the structure below, the left-hand coupling is R A And the coupling on the right is R B And the other bonds are R C It combines with it. (In the formula, f is an integer between 2 and 4.)

[0028] In the above formula, Q'' is a tetravalent group independently selected from the group consisting of a carbon atom, a silicon atom, a tetravalent cyclic hydrocarbon group having 6 to 8 carbon atoms, and a tetravalent organopolysiloxane residue having 2 to 10 silicon atoms, particularly a linear chain with 2 to 8 silicon atoms, or a branched or cyclic tetravalent organopolysiloxane residue having 3 to 10 silicon atoms, particularly a chain with 3 to 8 silicon atoms.

[0029] The organopolysiloxane residue may have 1 to 8 carbon atoms, more preferably 1 to 4 carbon atoms, and may contain an alkyl group such as a methyl group, ethyl group, propyl group, or butyl group, or a phenyl group. The organopolysiloxane residue may also contain a sylalkylene structure in which two silicon atoms are linked by an alkylene group such as an ethylene group or a trimethylene group.

[0030] Examples of such Q'' include those shown below. In the structure below, the left-hand coupling is R A And the coupling on the right is R B And the other bonds are R C It combines with it.

[0031] In the above formula, R B These are divalent hydrocarbon groups having 1 to 32 carbon atoms, which may be independently single-bonded, linear, branched, or cyclic, and the following are examples. (In the formula, z is an integer between 1 and 10.)

[0032] In the above formula, R C R is independent A or a hydrogen atom. C R A If so, then R A It may be the same as or different from it.

[0033] In the above formula, p is an integer between 0 and 10, and is preferably 0, 1, or 2. However, R 1 The total number of carbon atoms in each structure is 32 or less.

[0034] This kind of R 1 The following are preferred for use. (In the formulas, x, y, y', and z are the same as above, except that the total number of carbon atoms in each structure is between 3 and 32.)

[0035] In the above formula (1), R 2 R is a hydrogen atom, halogen atom, hydroxyl group, siloxy group, amino group, thiol group, monovalent hydrocarbon group having 1 or 2 carbon atoms (methyl group, ethyl group), 1 , or -Y-A. R 2 Examples include hydrogen atoms, chlorine atoms, hydroxyl groups, methyl groups, ethyl groups, and R 1 It is preferable that it be -Y-A.

[0036] In formula (1) above, U is a carbon atom, a silicon atom, a nitrogen atom, or a trivalent or tetravalent organic group. The trivalent or tetravalent organic group represented by U is preferably a trivalent or tetravalent group selected from a trivalent or tetravalent cyclic hydrocarbon group having 5 to 8 carbon atoms, a linear trivalent or tetravalent organopolysiloxane residue having 2 to 10 silicon atoms, particularly 2 to 8 silicon atoms, or a branched or cyclic trivalent or tetravalent organopolysiloxane residue having 3 to 10 silicon atoms, particularly 3 to 8 silicon atoms, a trivalent amide group, a trivalent carbamate group, a trivalent or tetravalent urea group, and a trivalent or tetravalent nitrogen-containing heterocyclic group (such as a trivalent cyanurate group, a trivalent isocyanurate group, and a trivalent triazine ring-containing group).

[0037] The organopolysiloxane residue may have an alkyl group such as a methyl group, ethyl group, propyl group, or butyl group, or a phenyl group, having 1 to 8 carbon atoms, more preferably 1 to 4 carbon atoms. The organopolysiloxane residue may also contain a sylalkylene structure in which two silicon atoms are linked by an alkylene group such as an ethylene group or a trimethylene group.

[0038] Examples of such U are shown below. In the structure below, it is preferable that the right-hand coupling bond connects to V.

[0039] In formula (1) above, V is a single bond, or may contain at least one selected from oxygen, nitrogen, and sulfur atoms, preferably a divalent hydrocarbon group having 1 to 20 carbon atoms, and is a linking group connecting the U group and the Z group. When Z is a single bond, V is preferably a single bond. Examples of the divalent hydrocarbon group include an alkylene group having 1 to 10 carbon atoms that may contain at least one selected from oxygen, nitrogen, and sulfur atoms, an alkylene group having 1 to 10 carbon atoms that includes an arylene group having 6 to 8 carbon atoms (for example, an alkylene-arylene group having 7 to 18 carbon atoms).

[0040] Examples of such V include, in addition to single bonds, the following. In the structure below, the bond on the left is bonded to U, and the bond on the right is bonded to Z. (In the formula, q is an integer between 1 and 10, r, s, and t are each integers between 1 and 8, the sum of r and s is an integer between 2 and 10, and the sum of r, s, and t is an integer between 3 and 10.)

[0041] In formula (1) above, Z is a single bond, a carbon atom, a silicon atom, a nitrogen atom, a sulfur atom, or a 3- to 8-valent organic group. Examples of 3- to 8-valent organic groups represented by Z include a 6- to 8 carbon atom trivalent or tetravalent cyclic hydrocarbon group, -SiR 3 = (R 3 (A trivalent group represented by a hydroxyl group, an alkyl group having 1 to 3 carbon atoms, or an alkoxy group having 1 to 3 carbon atoms), -CR 4 = (R 4 Examples of 3-8 valent groups include trivalent groups represented by a hydrogen atom, a hydroxyl group, or an alkyl group having 1 to 3 carbon atoms; linear 3-8 valent organopolysiloxane residues with 2 to 10 silicon atoms, particularly 2 to 8 silicon atoms, or branched or cyclic 3-8 valent organopolysiloxane residues with 3 to 10 silicon atoms, particularly 3 to 8 silicon atoms; trivalent amide groups; trivalent carbamate groups; trivalent or tetravalent urea groups; and 3-8 valent nitrogen-containing heterocyclic groups (such as trivalent cyanurate groups, trivalent isocyanurate groups, and trivalent or tetravalent triazine ring-containing groups).

[0042] The organopolysiloxane residue may have an alkyl group such as a methyl group, ethyl group, propyl group, or butyl group, or a phenyl group, having 1 to 8 carbon atoms, more preferably 1 to 4 carbon atoms. The organopolysiloxane residue may also contain a sylalkylene structure in which two silicon atoms are linked by an alkylene group such as an ethylene group or a trimethylene group.

[0043] Examples of such Z bonds include, in addition to single bonds, those shown below. In the structure below, the bond on the left is bonded to V, and the other bonds are bonded to Y. (In the formula, f is an integer between 2 and 4.)

[0044] In formula (1) above, Y may independently contain at least one selected from oxygen, nitrogen, sulfur, and silicon atoms, preferably a divalent hydrocarbon group having 1 to 20 carbon atoms, and is a linking group connecting the Z group and the A group. Examples of the divalent hydrocarbon group include, specifically, an alkylene group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, which may contain at least one selected from oxygen, nitrogen, and sulfur atoms; an alkylene group having 1 to 10 carbon atoms including an arylene group having 6 to 8 carbon atoms (for example, an alkylene-arylene group having 7 to 18 carbon atoms); a divalent group in which alkylene groups having 1 to 8 carbon atoms are bonded to each other via a diorganosilylene group, a sylalkylene structure, a sylarylene structure, or a nitrogen-containing heterocyclic group; and a divalent group in which an alkylene group having 1 to 10 carbon atoms is bonded to the binding site of a linear organopolysiloxane residue having 2 to 10 silicon atoms, particularly 2 to 8 silicon atoms, or a branched or cyclic organopolysiloxane residue having 3 to 10 silicon atoms, particularly 3 to 8 silicon atoms.

[0045] Here, the groups that bond to silicon atoms in diorganosilylene groups, sylalkylene structures, sylarylene structures, and organopolysiloxane residues are preferably alkyl groups such as methyl, ethyl, propyl, and butyl groups, or phenyl groups, having 1 to 8 carbon atoms, preferably 1 to 4 carbon atoms. Furthermore, the alkylene groups in the sylalkylene structures are preferably ethylene groups, propylene groups (trimethylene groups, methylethylene groups), butylene groups (tetramethylene groups, methylpropylene groups), etc., having 2 to 6 carbon atoms, preferably 2 to 4 carbon atoms. In addition, the organopolysiloxane residue may include a sylalkylene structure in which two silicon atoms are bonded by alkylene groups such as ethylene groups and trimethylene groups.

[0046] Examples of such a Y group include the following. In the structure below, the left-hand bond connects to Z, and the right-hand bond connects to A. (In the formula, a is an independent integer between 1 and 10, b, c, and d are each integers between 1 and 8, the sum of b and c is an integer between 2 and 10, and the sum of b, c, and d is an integer between 3 and 10. e is an integer between 1 and 9, and f is an integer between 2 and 4.)

[0047] In the above formula (1), A is a group represented by the following general formula (2). In the formula, R is independently a hydrogen atom, a C1-C8 alkyl group, or a phenyl group. Examples of C1-C8 alkyl groups represented by R include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, and octyl groups, and may be linear or branched alkyl groups. Preferably, R is a hydrogen atom, a C1-C4 alkyl group such as a methyl, ethyl, propyl, or butyl group, and a phenyl group, with hydrogen atoms, methyl, and ethyl groups being more preferred.

[0048] In formula (1) above, k is 1 or 2, where k is 1 if U is trivalent and 2 if U is tetravalent. Also, m is an integer from 1 to 7, preferably an integer from 1 to 3.

[0049] As a hydrocarbon terminal group-containing compound represented by the above formula (1), more preferred structures include the following structures (i), (ii), (iii), or (iv).

[0050] In formula (i), R 11 A is a monovalent hydrocarbon group having 4 to 32 carbon atoms, which may contain at least one selected from oxygen, sulfur, nitrogen, and silicon atoms, and may be linear, branched, cyclic, or a combination thereof; Z is a single bond, carbon atom, silicon atom, nitrogen atom, sulfur atom, or a 3 to 8 valent organic group; Y is a divalent hydrocarbon group which may independently contain at least one selected from oxygen, nitrogen, sulfur, and silicon atoms; A is a group represented by the following general formula (2), where k is 1 or 2, and m is an integer from 1 to 7. In formula (2), R is independently a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a phenyl group.

[0051] In formula (ii), R 1R may independently contain at least one selected from oxygen, sulfur, nitrogen, and silicon atoms, and may be linear, branched, cyclic, or a combination thereof, and is a monovalent hydrocarbon group having 3 to 32 carbon atoms, 2 ' is a hydrogen atom, halogen atom, hydroxyl group, siloxy group, amino group, thiol group, or a monovalent hydrocarbon group having 1 or 2 carbon atoms; U is a carbon atom, silicon atom, or a tetravalent organic group; V is a single bond or a divalent hydrocarbon group which may contain at least one selected from oxygen, nitrogen, and sulfur atoms; Z is a single bond, carbon atom, silicon atom, nitrogen atom, sulfur atom, or a 3- to 8valent organic group; Y is a divalent hydrocarbon group which may independently contain at least one selected from oxygen, nitrogen, sulfur, and silicon atoms; A is a group represented by the following general formula (2), and m is an integer from 1 to 7. In formula (2), R is independently a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a phenyl group.

[0052] In formula (iii), R 1 A is a monovalent hydrocarbon group having 3 to 32 carbon atoms, which may independently contain at least one selected from oxygen, sulfur, nitrogen, and silicon atoms, and may be linear, branched, cyclic, or a combination thereof; U is a carbon atom, a silicon atom, or a tetravalent organic group; V is a single bond, or a divalent hydrocarbon group which may contain at least one selected from oxygen, nitrogen, and sulfur atoms; Z is a single bond, a carbon atom, a silicon atom, a nitrogen atom, a sulfur atom, or a 3 to 8valent organic group; Y is a divalent hydrocarbon group which may independently contain at least one selected from oxygen, nitrogen, sulfur, and silicon atoms; A is a group represented by the following general formula (2), and m is an integer from 1 to 7. In formula (2), R is independently a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a phenyl group.

[0053] In formula (iv), R 1R may contain at least one selected from oxygen, sulfur, nitrogen, and silicon atoms, and may be linear, branched, cyclic, or a combination thereof, and is a monovalent hydrocarbon group having 3 to 32 carbon atoms. 2 This includes hydrogen atoms, halogen atoms, hydroxyl groups, siloxy groups, amino groups, thiol groups, monovalent hydrocarbon groups having 1 or 2 carbon atoms, R 1 , or -Y-A, where U' is a nitrogen atom or a trivalent organic group, V is a single bond or a divalent hydrocarbon group which may contain at least one selected from oxygen, nitrogen, and sulfur atoms, Z is a single bond, carbon atom, silicon atom, nitrogen atom, sulfur atom, or a 3- to 8valent organic group, Y is a divalent hydrocarbon group which may independently contain at least one selected from oxygen, nitrogen, sulfur, and silicon atoms, A is a group represented by the following general formula (2), and m is an integer from 1 to 7. In formula (2), R is independently a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a phenyl group.

[0054] In the above equation (i), R 11 This group may independently contain at least one selected from oxygen, sulfur, nitrogen, and silicon atoms, and may be linear, branched, cyclic, or a combination thereof, and is a monovalent hydrocarbon group having 4 to 32 carbon atoms, preferably 6 to 28 carbon atoms, more preferably 8 to 28 carbon atoms. Here, when at least one selected from oxygen, sulfur, nitrogen, and silicon atoms is included, it is preferable that it be included as a group such as an ether group, carbonyl (ketone) group, ester group, carbonate group, thioether group, sulfinyl group, sulfonyl group, thioester group, thiocarbonate group, thiocarbamate group, amino group, amide group, carbamate group, urea group, oxazole group, imidazole group, triazole group, cyanurate group, isocyanurate group, diorganosilylene group, organopolysiloxane residue, sylalkylene group, or sylarylene group.

[0055] R 2 ' is preferably a hydrogen atom, a chlorine atom, a hydroxyl group, a methyl group, or an ethyl group.

[0056] In the above formula (iv), the trivalent organic group of U' can be the same group as the trivalent group exemplified for U above.

[0057] In the above equations (i) to (iv), R 1 U, V, Z, Y, A, and m are as described above.

[0058] The following structures are examples of hydrocarbon terminal group-containing compounds represented by the above formula (1). 1 , R 2 By changing the combination of U, V, Z, Y, A, k, and m, several different hydrocarbon end-group-containing compounds can be obtained.

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[0114] (In the formula, x, y, y', z, q, r, s, a, b, c, d, e, and f are all independently the same as above.)

[0115] Examples of methods for preparing hydrocarbon terminal group-containing compounds represented by the general formula (1) of the present invention include the following: [Preparation Method 1] A hydrocarbon terminal group-containing compound having a leaving group at its terminus is mixed with a phosphorus compound (e.g., a trialkyl phosphite compound), reacted, and then the resulting compound is reacted with a halide trimethylsilane to produce a hydrocarbon terminal group-containing compound represented by formula (1) (particularly a compound having a phosphate group at its terminus).

[0116] Examples of hydrocarbon terminal group-containing compounds having a leaving group at its terminal include compounds represented by the following formulas (1G) or (1H). (In the formula, R 1 , R 2 U, V, Z, k, and m are the same as above. V 1(where X' is a divalent hydrocarbon group having 1 to 10 carbon atoms; X' is a halogen atom or a sulfonyl ester group.)

[0117] In the above equation (1H), V 1 This is a divalent hydrocarbon group having 1 to 10 carbon atoms, preferably an alkylene group, and the following are examples. (In the formula, q is the same as above.)

[0118] Examples of compounds represented by formula (1G) are listed below. (In the formula, x, z, and b are all independently the same as above.)

[0119] Examples of compounds represented by formula (1H) are listed below. (In the formula, x, z, and q are each independently the same as above.)

[0120] In preparation method 1, when reacting a hydrocarbon end group-containing compound having a leaving group at its terminal with a phosphorus compound (e.g., a trialkyl phosphite compound), examples of phosphorus compounds include trialkyl phosphite and dialkyl phosphite, with trimethyl phosphite, triethyl phosphite, triphenyl phosphite, dimethyl phosphite, and triethyl phosphite being examples. The amount of phosphorus compound used is preferably 1 to 6 moles, particularly 1.5 to 5 moles, per mole of leaving group in the hydrocarbon end group-containing compound having a leaving group at its terminal.

[0121] In preparation method 1, a solvent can be used when reacting a hydrocarbon end group-containing compound having a leaving group at its terminal with a phosphorus compound (e.g., a trialkyl phosphite compound). Examples of solvents include aromatic hydrocarbons such as toluene and xylene, aliphatic or alicyclic hydrocarbons such as n-pentane, n-hexane, and cyclohexane, ether compounds such as tetrahydrofuran, dioxane, and diethyl ether, ketones such as acetone and methyl ethyl ketone, amides such as dimethylformamide and dimethylacetamide, alcohols such as methanol, ethanol, and isopropanol, and halogenated hydrocarbons such as chloroform, dichloromethane, and dichloroethane. The amount of solvent used is preferably 0 to 1,000 parts by mass, more preferably 50 to 300 parts by mass, per 100 parts by mass of the hydrocarbon end group-containing compound having a leaving group at its terminal.

[0122] In preparation method 1, a base may be used when reacting a hydrocarbon end group-containing compound having a leaving group at its terminal with a phosphorus compound (e.g., a trialkyl phosphite compound). Examples of bases include sodium hydride and potassium hydride. The amount of base used is preferably 1 to 6 moles, particularly 1.5 to 3 moles, per mole of leaving group in the hydrocarbon end group-containing compound having a leaving group at its terminal.

[0123] In preparation method 1, the reaction conditions for reacting a hydrocarbon terminal group-containing compound having a leaving group at its terminal with a phosphorus compound (e.g., a trialkyl phosphite compound) are preferably a temperature of 25 to 180°C, particularly 25 to 140°C, for 0.5 to 72 hours, and especially 1 to 36 hours.

[0124] In preparation method 1, a hydrocarbon end group-containing compound having a leaving group at its terminal is mixed with a phosphorus compound (e.g., a trialkyl phosphite compound), reacted, and the resulting compound is then reacted with the halogenated trimethylsilane, which can be trimethylchlorosilane, trimethylbromosilane, trimethyliodosilane, etc. The amount of halogenated trimethylsilane used is preferably 1 to 10 moles, particularly 1 to 5 moles, per mole of leaving group in the hydrocarbon end group-containing compound having a leaving group at its terminal.

[0125] In preparation method 1, a solvent can be used when reacting a hydrocarbon end group-containing compound having a leaving group at its terminal with a phosphorus compound (e.g., a trialkyl phosphite compound) after mixing and reacting the resulting compound with a halogenated trimethylsilane. Examples of solvents include aromatic hydrocarbons such as toluene and xylene, aliphatic or alicyclic hydrocarbons such as n-pentane, n-hexane, and cyclohexane, ether compounds such as tetrahydrofuran, dioxane, and diethyl ether, ketones such as acetone and methyl ethyl ketone, amides such as dimethylformamide and dimethylacetamide, alcohols such as methanol, ethanol, and isopropanol, and halogenated hydrocarbons such as chloroform, dichloromethane, and dichloroethane. The amount of solvent used is preferably 0 to 1,000 parts by mass, more preferably 50 to 300 parts by mass, per 100 parts by mass of the hydrocarbon end group-containing compound having a leaving group at its terminal.

[0126] In preparation method 1, a hydrocarbon terminal group-containing compound having a leaving group at its terminal end is mixed with a phosphorus compound (e.g., a trialkyl phosphite compound), reacted, and then the resulting compound is reacted with a halogenated trimethylsilane. The reaction conditions for this reaction are preferably a temperature of 0 to 100°C, particularly 25 to 80°C, for 0.5 to 72 hours, and especially 1 to 36 hours.

[0127] Other methods for preparing hydrocarbon terminal group-containing compounds represented by the general formula (1) of the present invention include the following: [Preparation Method 2] A hydrocarbon terminal group-containing compound having an SiH group at the terminal end is mixed with a compound having an alkenyl group and a phosphate group or a phosphate ester group, and a hydrosilylation addition reaction is carried out in the presence of a hydrosilylation reaction catalyst. In some cases, the resulting compound is reacted with a halogenated trimethylsilane to produce a hydrocarbon terminal group-containing compound represented by formula (1) (particularly a compound having a phosphate group at the terminal end).

[0128] Examples of hydrocarbon terminal group-containing compounds having an SiH group at the terminal include compounds represented by the following formulas (1B) or (1C). (In the formula, R1 , R 2 U, V, Z, k, and m are the same as above. Z 1 Y is a linear or branched or cyclic organopolysiloxane residue with 2 to 10 silicon atoms, and Y 2 (It is a monovalent hydrocarbon group that independently has a silicon atom or a siloxane bond and has an SiH group at its terminal end.)

[0129] In the above formula (1B), Z 1 These are 3-8 valent organopolysiloxane residues with 2-10 silicon atoms, particularly 2-8 silicon atoms in a linear chain, or 3-10 silicon atoms, particularly 3-8 silicon atoms in a branched or cyclic structure, as shown below. In the structure below, the left-hand bond is bound to V, and the other bond is bound to H. (In the formula, f is an integer between 2 and 4.)

[0130] Examples of compounds represented by formula (1B) are listed below. (In the formula, x, q, r, and s are all independently the same as above.)

[0131] In the above formula (1C), Y 2 These are monovalent hydrocarbon groups that independently have a silicon atom or a siloxane bond and have an SiH group at their terminus, and the following are examples. (In the formula, a is an integer between 1 and 10, b is an integer between 1 and 8, e is an integer between 1 and 9, and f is an integer between 2 and 4.)

[0132] Examples of compounds represented by formula (1C) are listed below. (In the equation, x and b are independently the same as above.)

[0133] Examples of compounds having an alkenyl group and a phosphate group or a phosphate ester group include vinylphosphonic acid, allylphosphonic acid, dimethyl vinylphosphonate, dimethyl allylphosphonate, dimethyl vinylphosphonate, dimethyl allylphosphonate, and dimethyl allylphosphonate.

[0134] In preparation method 2, the amount of compound having an alkenyl group and a phosphate group or phosphate ester group used is preferably 1 to 5 moles, particularly 1 to 3 moles, per mole of SiH groups in the hydrocarbon terminal group-containing compound having an SiH group at the terminal.

[0135] In preparation method 2, examples of the hydrosilylation reaction catalyst include platinum black, chloroplatinic acid, alcohol-modified chloroplatinic acid, complexes of chloroplatinic acid with olefins, aldehydes, vinylsiloxanes, acetylene alcohols, etc., and platinum group metal catalysts such as tetrakis(triphenylphosphine)palladium and chlorotris(triphenylphosphine)rhodium. Preferably, it is a platinum-based compound such as a vinylsiloxane coordination compound. It is preferable to dissolve the platinum-based compound in a solvent such as toluene, lower alcohol, higher alcohol, or silicone-based solvent before use. The amount of hydrosilylation reaction catalyst used is preferably 0.001 to 1,000 ppm, more preferably 0.01 to 100 ppm, in terms of transition metal (mass), relative to the mass of the hydrocarbon-terminal group-containing compound having an alkenyl group at the terminal end.

[0136] In preparation method 2, a solvent can be used when carrying out the reaction. Examples of solvents are the same as those used in preparation method 1. The amount of solvent used is preferably 0 to 1,000 parts by mass, more preferably 50 to 200 parts by mass, per 100 parts by mass of the hydrocarbon terminal group-containing compound having an SiH group at the terminal end.

[0137] In preparation method 2, the reaction conditions are preferably a temperature of 20 to 120°C, particularly 60 to 100°C, for 0.5 to 72 hours, and especially 1 to 36 hours.

[0138] In preparation method 2, if a compound having an alkenyl group and a phosphate ester group is used, the reaction product of a hydrocarbon-terminal group-containing compound having a terminal SiH group and a compound having an alkenyl group and a phosphate ester group may be reacted with a halide trimethylsilane. The conditions for reacting with the halide trimethylsilane are the same as in preparation example 1.

[0139] <Surface Treatment Agent> The present invention further provides a substantially non-fluorine surface treatment agent that contains a hydrocarbon terminal group-containing compound represented by formula (1) as a main component. The surface treatment agent only needs to contain the hydrocarbon terminal group-containing compound represented by formula (1) as a main component, and may also contain unreacted raw materials and reaction intermediates before the introduction of the reactive group of the hydrocarbon terminal group-containing compound represented by formula (1). Furthermore, it is preferable that the reactive group of the hydrocarbon terminal group-containing compound used in the surface treatment agent is a hydrolyzable silyl group, and in this case, the surface treatment agent may also contain a partially (hydrolyzed) condensate obtained by partially hydrolyzing the hydrolyzable silyl group by a known method.

[0140] The surface treatment agent may optionally contain hydrolysis condensation catalysts, such as organotin compounds (e.g., dibutyltin dimethoxide, dibutyltin dilaurate), organotitanium compounds (e.g., tetra-n-butyl titanate, tetra-n-propyl titanate), organozirconium compounds (e.g., tetra-n-butyl zirconate, tetra-n-propyl zirconate), organic acids (e.g., acetic acid, methanesulfonic acid, carboxylic acid), inorganic acids (e.g., hydrochloric acid, sulfuric acid), and organic bases (e.g., amines, trialkylamines, nitrogen-containing cyclic compounds). Among these, acetic acid, tetra-n-butyl titanate, and dibutyltin dilaurate are particularly desirable. The amount of hydrolysis condensation catalyst added is a catalytic amount, usually 0.001 to 5 parts by mass, particularly 0.1 to 1 part by mass, per 100 parts by mass of the hydrocarbon-terminal group-containing compound (and / or its partial (hydrolysis) condensate).

[0141] The surface treatment agent may contain a suitable solvent. Such solvents are preferably non-fluorinated solvents, and examples include hydrocarbon solvents (petroleum benzine, toluene, xylene, hexane, cyclohexane, methylcyclohexane, ethylcyclohexane, heptane, octane (n-octane, isooctane, etc.), nonane (n-nonane, isononane, etc.)), ketone solvents (acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, etc.), ether solvents (tetrahydrofuran (THF), dipropyl ether, dibutyl ether, methylcyclopentyl ether, methyl t-butyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, propylene glycol dimethyl ether, etc.), alcohol solvents (propylene glycol monomethyl ether, butanol, isopropanol, etc.), and ester solvents (ethyl acetate, propyl acetate, butyl acetate, pentyl acetate, propylene glycol monomethyl ether acetate). Among these, toluene, hexane, heptane, isooctane, isononane, cyclopentanone, dipropyl ether, dibutyl ether, methylcyclopentyl ether, methyl t-butyl ether, ethylene glycol dimethyl ether, propyl acetate, butyl acetate, and propylene glycol monomethyl ether acetate are preferred in terms of solubility, wettability, etc.

[0142] The above solvents may be mixed in two or more forms, and it is preferable to uniformly dissolve the hydrocarbon end group-containing compound (and its partial (hydrolysis) condensate). The optimal concentration of the hydrocarbon end group-containing compound (and its partial (hydrolysis) condensate) to be dissolved in the solvent varies depending on the processing method, and any amount that is easy to weigh is acceptable. However, in the case of direct coating, it is preferable to use 0.01 to 100 parts by mass, particularly 0.05 to 30 parts by mass, per 100 parts by mass of the total of the solvent and the hydrocarbon end group-containing compound (and its partial (hydrolysis) condensate). In the case of vapor deposition, it is preferable to use 1 to 100 parts by mass, particularly 3 to 30 parts by mass, per 100 parts by mass of the total of the solvent and the hydrocarbon end group-containing compound (and its partial (hydrolysis) condensate). In either coating case, 100 parts by mass refers to the case where no solvent is used and the coating is performed directly.

[0143] The surface treatment agent of the present invention can be applied to a substrate by known methods such as brush application, dipping, spraying, and vapor deposition. The heating method during vapor deposition can be either resistance heating or electron beam heating, and is not particularly limited. The curing temperature varies depending on the curing method, but for example, in the case of direct coating (brush application, dipping, spraying, etc.), it is preferable to set the temperature at 25 to 200°C, particularly 25 to 150°C, for 30 minutes to 36 hours, and especially 1 to 24 hours. When applied by vapor deposition, it is desirable to set the temperature in the range of 20 to 200°C for 1 to 24 hours. Curing may also be performed under humid conditions. Furthermore, for example, when using a hydrocarbon terminal group-containing compound having a hydrolyzable silyl group, in spray coating, diluting it in an organic solvent with water added beforehand and allowing hydrolysis, i.e., generating Si-OH, before spray coating will result in faster curing after coating.

[0144] The thickness of the cured film is appropriately selected depending on the type of substrate, but is usually 0.1 to 100 nm, and particularly 1 to 20 nm. The film thickness can be measured by methods such as spectral reflectance measurement, X-ray reflectance measurement, spectral ellipsometry measurement, and X-ray fluorescence measurement.

[0145] The substrate treated with the surface treatment agent of the present invention is not particularly limited and may be made of various materials such as paper, cloth, metals and their oxides, glass, plastics, ceramics, and quartz. The surface treatment agent of the present invention can impart water-repellent and oil-repellent properties to the substrate. In particular, it has good adhesion to metal and metal oxide surfaces and can be suitably used as a surface treatment agent for metals such as SUS304, SUS403, and duralumin, as well as metals, glass, and films having a ZnO2, TiO2, ZrO2, or Al2O3 treated layer on their surface.

[0146] The surface treatment agent of the present invention can form a hardened film with excellent water repellency, slipperiness, dirt-wiping properties, and abrasion resistance at a high level.

[0147] <Articles> Articles treated with the surface treatment agent of the present invention include car navigation systems, mobile phones, smartphones, digital cameras, digital video cameras, PDAs, portable audio players, car audio systems, game consoles, eyeglass lenses, camera lenses, lens filters, sunglasses, medical devices such as endoscopes, photocopiers, PCs, liquid crystal displays, organic EL displays, plasma displays, touch panel displays, protective films, anti-reflective films, and other optical articles and electronic components. The surface treatment agent of the present invention can impart scratch resistance to the aforementioned articles, and is therefore particularly useful as a water-repellent layer for touch panel displays, anti-reflective films, eyeglass lenses, and the like.

[0148] Furthermore, the surface treatment agent of the present invention is also useful as an antifouling coating for sanitary products such as bathtubs and washbasins, an antifouling coating for windows or tempered glass of automobiles, trains, and aircraft, an antifouling coating for headlamp covers, a water-repellent coating for exterior building materials, a stain-preventing coating for kitchen building materials, an antifouling and anti-sticker / graffiti coating for telephone booths, a coating to prevent dirt from adhering to works of art, a stain-preventing coating for compact discs and DVDs, a mold release agent or paint additive for molds, a resin modifier, a fluidity modifier or dispersibility modifier for inorganic fillers, and a lubricity enhancer for tapes, films, etc.

[0149] The present invention will be described in more detail below with reference to synthesis examples, examples, and comparative examples, but the present invention is not limited to the following examples. In the following examples, the mol amount of the compound is, with respect to the measured mass of the target compound, 1 The value was calculated by dividing by the molecular weight of the polymer identified by 1H-NMR analysis. Furthermore, the film thickness was measured using spectroscopic ellipsometry with a spectroscopic ellipsometer. The room temperature was 23°C.

[0150] [Synthesis Example 1] In the reaction vessel, the following formula (A) 1.00 g (1.23 × 10) of the compound represented by -3 mol), triethyl phosphite 0.615 g (3.70 x 10 -3 The mixture was combined with 3.00 g of toluene and 0.944 g of bromotrimethylsilane (6.17 × 10⁻¹⁰). -3 The mixture (mol) was aged at room temperature for 24 hours. Then, the solvent and unreacted materials were removed by reduced pressure distillation to obtain 0.887 g of the product.

[0151] The resulting compound was 1 ¹H-NMR confirmed that the structure is represented by the following formula (B).

[0152] [Synthesis Example 2] In the reaction vessel, the following formula (C) 1.00 g (1.71 × 10) of the compound represented by -3 mol), triethyl phosphite 0.850 g (5.12 x 10 -3 The mixture (mol) was mixed and aged at 130°C for 24 hours. After that, the solvent and unreacted products were removed by vacuum distillation. The obtained product was mixed with 3.00 g of toluene and 1.31 g of bromotrimethylsilane (8.53 × 10⁻¹⁰). -3 The mixture (mol) was aged at room temperature for 24 hours. Then, the solvent and unreacted materials were removed by distillation under reduced pressure to obtain 0.943 g of the product.

[0153] The resulting compound was 1 ¹H-NMR confirmed that the structure is represented by the following formula (D).

[0154] [Synthesis Example 3] In a reaction vessel, 1.00 g (1.17×10 mol) of the compound represented by the following formula (E), 0.437 g (3.52×10 -3 mol) of trimethyl phosphite were mixed and aged at 150 °C for 24 hours. Then, the solvent and unreacted substances were distilled off under reduced pressure. The obtained product was mixed with 3.00 g of toluene and 0.898 g (5.86×10 -3 mol) of bromotrimethylsilane and aged at room temperature for 24 hours. Then, the solvent and unreacted substances were distilled off under reduced pressure to obtain 0.917 g of a product.

[0155] The obtained compound was 1 confirmed by 1H-NMR to have a structure represented by the following formula (F).

[0156] [Synthesis Example 4] In a reaction vessel, 1.00 g (1.59×10 mol) of the compound represented by the following formula (G), 0.793 g (4.77×10 -3 mol) of triethyl phosphite were mixed and aged at 140 °C for 24 hours. Then, the solvent and unreacted substances were distilled off under reduced pressure. The obtained product was mixed with 3.00 g of toluene and 1.22 g (7.96×10 -3 mol) of bromotrimethylsilane and aged at room temperature for 24 hours. Then, the solvent and unreacted substances were distilled off under reduced pressure to obtain 0.929 g of a product. -3 mol) of bromotrimethylsilane and aged at room temperature for 24 hours. Then, the solvent and unreacted substances were distilled off under reduced pressure to obtain a product of 0.929 g.

[0157] The obtained compound was 1 confirmed by 1H-NMR to have a structure represented by the following formula (H).

[0158] [Synthesis Example 5] In a reaction vessel, 1.00 g (1.26×10 mol) of the compound represented by the following formula (I), 1.26 g (7.59×10 -3 mol) of triethyl phosphite were mixed and aged at 160 °C for 24 hours. Then, the solvent and unreacted substances were distilled off under reduced pressure. The obtained product was mixed with 3.00 g of toluene and 1.94 g (1.26×10 -3 mol) of bromotrimethylsilane and aged at 160 °C for 24 hours. Then, the solvent and unreacted substances were distilled off under reduced pressure. The obtained product was mixed with 3.00 g of toluene and 1.94 g (1.26×10 -2 ​​(mol) were mixed and aged at room temperature for 24 hours. Then, the solvent and unreacted substances were distilled off under reduced pressure to obtain 0.950 g of the product.

[0159] The obtained compound 1 was confirmed to have a structure represented by the following formula (J) by 1H-NMR.

[0160] [Synthesis Example 6] In a reaction vessel, 1.00 g (1.27×10 mol) of the compound represented by the following formula (K), 0.632 g (3.80×10 -3 mol) of triethyl phosphite were mixed and aged at 120 °C for 24 hours. Then, the solvent and unreacted substances were distilled off under reduced pressure. The obtained product was mixed with 3.00 g of toluene and 0.971 g (6.34×10 -3 mol) of bromotrimethylsilane and aged at room temperature for 24 hours. Then, the solvent and unreacted substances were distilled off under reduced pressure to obtain 0.911 g of the product. -3 mol) were mixed and aged at room temperature for 24 hours. Then, the solvent and unreacted substances were distilled off under reduced pressure to obtain 0.911 g of the product.

[0161] The obtained compound 1 was confirmed to have a structure represented by the following formula (L) by 1H-NMR.

[0162] [Synthesis Example 7] In a reaction vessel, 1.00 g (1.99×10 mol) of the compound represented by the following formula (M), 2.00 g of toluene, 0.736 g (4.13×10 -3 mol) of diethyl allylphosphonate, and 5.26×10 -3 g of a toluene solution of chloroplatinic acid / vinylsiloxane complex (containing 1.62×10 -3 mol of elemental Pt) were mixed and aged at 90 °C for 24 hours. Then, the solvent and unreacted substances were distilled off under reduced pressure. The obtained product was mixed with 3.00 g of toluene and 1.05 g (6.88×10 -8 mol) of bromotrimethylsilane and aged at room temperature for 24 hours. Then, the solvent and unreacted substances were distilled off under reduced pressure to obtain 1.12 g of the product. -3 mol) were mixed and aged at room temperature for 24 hours. Then, the solvent and unreacted substances were distilled off under reduced pressure to obtain 1.12 g of the product.

[0163] The obtained compound 1¹H-NMR confirmed that the structure is represented by the following formula (N).

[0164] [Synthesis Example 8] In the reaction vessel, the following formula (O) 1.00 g (1.29 × 10) of the compound represented by -3 mol), toluene 2.00 g, diethyl vinylphosphonate 1.90 g (1.16 x 10 -2 mol), and 4.92 × 10¹³ toluene solution of chloroplatinate / vinylsiloxane complex -3 g (as Pt alone, 1.52 × 10) -8 The mixture (containing mol) was aged at 90°C for 24 hours, after which the solvent and unreacted products were removed by vacuum distillation. The resulting product was mixed with 3.00 g of toluene and 2.96 g of bromotrimethylsilane (1.93 × 10⁻¹⁰). -2 The mixture (mol) was aged at room temperature for 24 hours. Then, the solvent and unreacted materials were removed by vacuum distillation to obtain 1.30 g of the product.

[0165] The resulting compound was 1 ¹H-NMR confirmed that the structure is represented by the following formula (P).

[0166] [Synthesis Example 9] In the reaction vessel, the following formula (Q) 1.00 g (1.24 × 10) of the compound represented by -3 mol), 1.24 g of triethyl phosphite (7.47 x 10) -3 The mixture (mol) was mixed and aged at 150°C for 24 hours. After that, the solvent and unreacted products were removed by vacuum distillation. The obtained product was mixed with 3.00 g of toluene and 1.90 g of bromotrimethylsilane (1.24 × 10⁻¹⁴). -2 The mixture (mol) was aged at room temperature for 24 hours. Then, the solvent and unreacted materials were removed by distillation under reduced pressure to obtain 0.942 g of the product.

[0167] The resulting compound was 1 ¹H-NMR confirmed that the structure is represented by the following formula (R).

[0168] [Synthesis Example 10] In the reaction vessel, the following formula (S) 1.00 g (9.00 x 10) of the compound represented by-4 mol), triethyl phosphite 0.446 g (2.69 x 10) -3 The mixture (mol) was heated and aged at 140°C for 24 hours. After that, the solvent and unreacted materials were removed by vacuum distillation. The obtained product was mixed with 3.00 g of toluene and 0.685 g of bromotrimethylsilane (4.48 × 10⁻¹⁰). -3 The mixture (mol) was aged at room temperature for 24 hours. Then, the solvent and unreacted materials were removed by distillation under reduced pressure to obtain 0.906 g of the product.

[0169] The resulting compound was 1 ¹H-NMR confirmed that the structure is represented by the following formula (T).

[0170] [Synthesis Example 11] In the reaction vessel, the following formula (U) 1.00 g (1.33 × 10) of the compound represented by -3 mol),), Triethyl phosphite 0.662 g (3.98 x 10 -3 The mixture (mol) was mixed and aged at 150°C for 24 hours. After that, the solvent and unreacted products were removed by vacuum distillation. The obtained product was mixed with 3.00 g of toluene and 1.02 g of bromotrimethylsilane (6.64 × 10⁻⁶). -3 The mixture (mol) was allowed to mature at room temperature for 24 hours. Then, the solvent and unreacted materials were removed by reduced pressure distillation to obtain 0.946 g of the product.

[0171] The resulting compound was 1 ¹H-NMR confirmed that the structure is represented by the following formula (V).

[0172] [Synthesis Example 12] In the reaction vessel, the following formula (W) 1.00 g (1.25 × 10) of the compound represented by -3 mol),), Triethyl phosphite 0.622 g (3.75 x 10 -3 The mixture (mol) was mixed and aged at 160°C for 24 hours. After that, the solvent and unreacted products were removed by vacuum distillation. The obtained product was mixed with 3.00 g of toluene and 0.956 g of bromotrimethylsilane (6.25 × 10⁻⁶). -3 The mixture (mol) was aged at room temperature for 24 hours. Then, the solvent and unreacted materials were removed by distillation under reduced pressure to obtain 0.938 g of the product.

[0173] The resulting compound was 1 ¹H-NMR confirmed that the structure is represented by the following formula (X).

[0174] [Synthesis Example 13] In the reaction vessel, the following formula (Y) 1.00 g (1.38 × 10) of the compound represented by -3 mol), triethyl phosphite 2.06 g (1.24 x 10 -2 The mixture (mol) was mixed and aged at 140°C for 24 hours. After that, the solvent and unreacted products were removed by vacuum distillation. The obtained product was mixed with 3.00 g of toluene and 3.16 g of bromotrimethylsilane (2.07 × 10⁻⁶). -2 The mixture (mol) was aged at room temperature for 24 hours. Then, the solvent and unreacted materials were removed by reduced pressure distillation to obtain 0.964 g of the product.

[0175] The resulting compound was 1 H-NMR confirmed that the structure is represented by the following formula (Z).

[0176] [Synthesis Example 14] In the reaction vessel, the following formula (AA) 1.00 g (2.00 × 10) of the compound represented by -3 mol), triethyl phosphite 0.996 g (6.00 x 10 -3 The mixture (mol) was heated and aged at 150°C for 24 hours. After that, the solvent and unreacted materials were removed by vacuum distillation. The obtained product was mixed with 3.00 g of toluene and 1.53 g of bromotrimethylsilane (9.99 × 10⁻¹⁰). -3 The mixture (mol) was aged at room temperature for 24 hours. Then, the solvent and unreacted materials were removed by reduced pressure distillation to obtain 0.925 g of the product.

[0177] The resulting compound was 1 ¹H-NMR confirmed that the structure is represented by the following formula (AB).

[0178] [Synthesis Example 15] In the reaction vessel, the following formula (AC) 1.00 g (2.56 × 10) of the compound represented by -3mol), 1.28 g of triethyl phosphite (7.69 x 10) -3 The mixture (mol) was mixed and aged at 140°C for 24 hours. After that, the solvent and unreacted products were removed by vacuum distillation. The obtained product was mixed with 3.00 g of toluene and 1.96 g of bromotrimethylsilane (1.28 × 10⁻¹⁰). -2 The mixture (mol) was aged at room temperature for 24 hours. Then, the solvent and unreacted materials were removed by distillation under reduced pressure to obtain 0.947 g of the product.

[0179] The resulting compound was 1 ¹H-NMR confirmed that the structure is represented by the following formula (AD).

[0180] [Synthesis Example 16] In the reaction vessel, the following formula (AE) 1.00 g (1.46 × 10) of the compound represented by -3 mol), 2.18 g of triethyl phosphite (1.31 x 10) -2 The mixture (mol) was mixed and aged at 150°C for 24 hours. After that, the solvent and unreacted products were removed by vacuum distillation. The obtained product was mixed with 3.00 g of toluene and 3.35 g of bromotrimethylsilane (2.19 × 10⁻⁶). -2 The mixture (mol) was aged at room temperature for 24 hours. Then, the solvent and unreacted materials were removed by distillation under reduced pressure to obtain 0.916 g of the product.

[0181] The resulting compound was 1 ¹H-NMR confirmed that the structure is represented by the following formula (AF).

[0182] [Example 1] The compound obtained in Synthesis Example 1 was dissolved in toluene to a concentration of 10% by mass to prepare a surface treatment agent.

[0183] [Example 2] The compound obtained in Synthesis Example 2 was dissolved in dibutyl ether to a concentration of 20% by mass to prepare a surface treatment agent.

[0184] [Example 3] The compound obtained in Synthesis Example 3 was dissolved in butyl acetate to a concentration of 10% by mass to prepare a surface treatment agent.

[0185] [Example 4] The compound obtained in Synthesis Example 4 was dissolved in dibutyl ether to a concentration of 30% by mass to prepare a surface treatment agent.

[0186] [Example 5] The compound obtained in Synthesis Example 7 was dissolved in isononane / isooctane 50 / 50 to a concentration of 50% by mass to prepare a surface treatment agent.

[0187] [Example 6] The compound obtained in Synthesis Example 11 was dissolved in butyl acetate to a concentration of 70% by mass to prepare a surface treatment agent.

[0188] [Example 7] The compound obtained in Synthesis Example 14 was dissolved in toluene to a concentration of 10% by mass to prepare a surface treatment agent.

[0189] [Comparative Example 1] The following formula (A') A surface treatment agent was prepared by dissolving the compound represented by [formula] in toluene to a concentration of 20% by mass.

[0190] [Comparative Example 2] The following formula (B') A surface treatment agent was prepared by dissolving the compound represented by [formula] in toluene to a concentration of 20% by mass.

[0191] [Comparative Example 3] The following formula (C') A surface treatment agent was prepared by dissolving the compound represented by [formula] in toluene to a concentration of 20% by mass.

[0192] [Comparative Example 4] No surface treatment agent used.

[0193] <Preparation of Surface Treatment Agents and Formation of Cured Films> Surface treatment agents were prepared as in the above examples and comparative examples. Each surface treatment agent was vacuum deposited (equipment: ULVAC KIKO, product number: VTR-350M) onto glass (Corning Goilla Glass (product number: Gorilla III, size: 100 mm x 50 mm x 0.7 mm)) whose outermost surface was coated with ZrO2 to a thickness of 20 nm under the following conditions (processing conditions: pressure: 2.0 x 10 -2A cured film with a thickness of 3-5 nm was formed by curing in an atmosphere of Pa, heating temperature: 700°C, 80°C, and 80% relative humidity for 1 hour, and then in an atmosphere of 25°C and 50% relative humidity for 12 hours. [ZrO 2-layer film formation conditions] Film formation apparatus: OTFC-1300 (Optolan Co., Ltd.) Film formation material: ZrO2 Film formation chamber pressure: 0.015 Pa Film formation rate: 0.8 nm / s Film thickness: 20 nm

[0194] The water repellency, slipperiness, dirt-wiping properties, abrasion resistance, and chemical resistance of the glass with a hardened coating were evaluated using the method described below. For Comparative Example 4, a glass (Corning Gorilla) with no surface treatment, but coated with a 10 nm thick layer of ZrO2 on its outermost surface, was used and evaluated in the same manner.

[0195] Evaluation of Water Repellency The contact angle (water repellency) of the hardened film formed on the glass prepared as described above was measured using a Drop Master contact angle meter (DMo-701SA, manufactured by Kyowa Interface Science Co., Ltd.) (droplet: 2 μl, temperature: 25°C, relative humidity: 40%). The measurement was performed by photographing the droplet 1 second after dropping with a CCD camera connected to the contact angle meter, and then analyzing the droplet image using FAMAS, the contact angle analysis software attached to the contact angle meter, to measure the contact angle between the glass substrate and the droplet. The contact angle was calculated using the θ / 2 method. The analysis conditions are as follows. The results (initial water contact angle) are shown in Table 1. In this invention, a good (water-repellent) water contact angle was defined as 90° or higher (the same applies hereinafter). [Analysis Conditions] Method: Droplet method (θ / 2 method) Droplet recognition: Automatic Droplet recognition line (distance from needle tip): 50 dots Algorithm: Automatic Image mode: Frame threshold level: Automatic

[0196] Evaluation of Slipperiness The slipperiness of the glass with the hardened coating prepared as described above was evaluated by assessing the coefficient of dynamic friction with the nonwoven fabric using the method described below. The coefficient of dynamic friction of the glass with the hardened coating with the nonwoven fabric was measured in accordance with ASTM D1894 using a surface properties measuring instrument TYPE: 14FW (manufactured by Shinto Kagaku Co., Ltd.) under the conditions of a load of 100 gf and a tensile speed of 500 mm / min. The results (coefficient of dynamic friction) are shown in Table 1. [Slipperiness Evaluation Conditions] Load: 100 gf Stroke: 100 mm Contact area: 1 × 3 cm 2 Nonwoven fabric: BEMCOT (manufactured by Asahi Kasei Corporation)

[0197] Evaluation of stain removal properties A 2 cm straight line was drawn on the glass with the hardened film prepared as described above using a Hi-Mackie (manufactured by Zebra Co., Ltd.), the ink was dried, and then the surface was wiped with tissue paper. The number of rubbings required to remove the ink was evaluated according to the following criteria. The results are shown in Table 1. [Stain Removal Evaluation Criteria] A: 4 or fewer rubbings B: 5 or more rubbings C: Ink cannot be wiped off

[0198] Abrasion Resistance Evaluation The glass with the hardened coating prepared as described above was rubbed every 1000 times using a rubbing tester (manufactured by Shinto Kagaku Co., Ltd.) under the following conditions. The contact angle (water repellency) of the hardened coating with water was measured in the same manner as described above, and the number of times it fell below 80° was counted to evaluate abrasion resistance. The test environment conditions were 25°C and 40% relative humidity. The results (water contact angle after abrasion) are shown in Table 1. [Fabric abrasion resistance test conditions] Nonwoven fabric: BEMCOT (manufactured by Asahi Kasei Corporation) Contact area: 1 cm 2 Distance traveled (one way): 40 mm; Speed: 4,800 mm / min; Load: 1,000 gf / cm 2 Measure the number of times the water contact angle falls below 80°.

[0199] Evaluation of Chemical Resistance The glass with the hardened film prepared as described above was immersed in a container of alkaline solution and left standing in a constant-temperature oven. The glass immersed in the container was removed every hour, the entire surface of the glass was washed with pure water, and then dried with dry air. After that, the contact angle (water repellency) of the hardened film with respect to water was measured in the same manner as described above for the area immersed in the alkaline solution. This operation was repeated, and the immersion time at which the water contact angle became less than 80° was confirmed. The results (chemical resistance (immersion time at which the water contact angle became less than 80°)) are shown in Table 1. The chemical resistance test conditions are as follows. Furthermore, good chemical resistance in this invention means that in the chemical resistance test described above, the immersion time at which the water contact angle of the formed hardened film becomes less than 80° is 2 hours or more, more preferably 4 hours or more, and most preferably 5 hours or more. [Chemical Resistance Test Conditions] Chemical: 30% by mass sodium hydroxide aqueous solution Temperature: 55°C

[0200] The cured coatings of the surface treatment agents in Examples 1 to 7 exhibited improved adhesion to the substrate due to the presence of phosphonic acid groups or phosphonic acid ester groups at the molecular chain ends of the compounds used. Furthermore, the presence of hydrocarbon chains with a predetermined number of carbon atoms resulted in water repellency and improved molecular mobility, leading to good slipperiness, dirt-wiping properties, abrasion resistance, and chemical resistance. Comparative Examples 1 and 3 had poor substrate adhesion because their ends were alkoxysilyl groups. The cured coating of the surface treatment agent in Comparative Example 2, although the compound used had fluorinated hydrocarbon chains, exhibited poor durability. Comparative Example 4 was a glass substrate without a surface treatment agent, but since it was not surface-treated, it lacked all of the properties, confirming the effects of the Examples. As described above, the surface treatment agents in the Examples made it possible to obtain a cured coating that achieved a high level of water repellency, slipperiness, dirt-wiping properties, abrasion resistance, and chemical resistance in vapor deposition coating.

[0201]

[0202] [Example 8] The compound obtained in Synthesis Example 2 was dissolved in dibutyl ether to a concentration of 0.2% by mass to prepare a surface treatment agent.

[0203] [Example 9] The compound obtained in Synthesis Example 5 was dissolved in toluene to a concentration of 0.2% by mass to prepare a surface treatment agent.

[0204] [Example 10] The compound obtained in Synthesis Example 8 was dissolved in hexane / isooctane 50 / 50 to a concentration of 0.2% by mass to prepare a surface treatment agent.

[0205] [Example 11] The compound obtained in Synthesis Example 10 was dissolved in butyl acetate to a concentration of 0.2% by mass to prepare a surface treatment agent.

[0206] [Example 12] The compound obtained in Synthesis Example 12 was dissolved in toluene to a concentration of 0.2% by mass to prepare a surface treatment agent.

[0207] [Example 13] The compound obtained in Synthesis Example 14 was dissolved in toluene to a concentration of 0.2% by mass to prepare a surface treatment agent.

[0208] [Example 14] The compound obtained in Synthesis Example 15 was dissolved in ethylcyclohexane to a concentration of 0.2% by mass to prepare a surface treatment agent.

[0209] [Comparative Example 5] A surface treatment agent was prepared by dissolving the compound represented by the above formula (A') in dibutyl ether to a concentration of 0.2% by mass.

[0210] [Comparative Example 6] A surface treatment agent was prepared by dissolving the compound represented by the above formula (B') in toluene to a concentration of 0.2% by mass.

[0211] [Comparative Example 7] A surface treatment agent was prepared by dissolving the compound represented by the above formula (C') in dibutyl ether to a concentration of 0.2% by mass.

[0212] [Comparative Example 8] No surface treatment agent used.

[0213] <Preparation of Surface Treatment Agents and Formation of Cured Films> Surface treatment agents were prepared as in the above examples and comparative examples. Each surface treatment agent was spray-coated onto glass (Corning Goilla Glass (product code: Gorilla III, size: 100 mm x 50 mm x 0.7 mm)) that had been coated with ZrO2 to a thickness of 10 nm on its outermost surface by dip coating under the following conditions. The coating was then cured for 1 hour at 80°C and 80% relative humidity, and then for 12 hours at 25°C and 50% relative humidity to form a cured film with a thickness of 3 to 5 nm. [ZrO 2-layer film deposition conditions] Film deposition apparatus: ND0407-N1 (manufactured by SDI) Film deposition material: ZrO2 dispersion aqueous solution Pulling speed: 3 mm / s Film thickness: 10 nm [Spray coating conditions] Atmosphere: 25°C / 50% Nozzle distance: 50 mm Air pressure: 150 kPa Speed: 300 mm / min Pitch: 5 mm

[0214] The water repellency, slipperiness, dirt-wiping properties, abrasion resistance, and chemical resistance of the glass with the hardened coating were evaluated using the method described below. For Comparative Example 8, a glass (Gorilla, manufactured by Corning) with no surface treatment, but with a 10 nm thick ZrO2 coating applied to the outermost surface by the above-described dip-coating method, was used and evaluated in the same manner.

[0215] Evaluation of Water Repellency The contact angle (water repellency) of the hardened film formed on the glass prepared as described above was measured using a Drop Master contact angle meter (Kyowa Interface Science Co., Ltd., DMo-701SA) (droplet: 2 μl, temperature: 25°C, relative humidity: 40%). The measurement was performed by photographing the droplet 1 second after dropping with a CCD camera connected to the contact angle meter, and then analyzing the droplet image using FAMAS, the contact angle analysis software attached to the contact angle meter, to measure the contact angle between the glass substrate and the droplet. The contact angle was calculated using the θ / 2 method. The analysis conditions are as follows. The results (initial water contact angle) are shown in Table 2. [Analysis Conditions] Method: Droplet method (θ / 2 method) Droplet recognition: Automatic Droplet recognition line (distance from needle tip): 50 dots Algorithm: Automatic Image mode: Frame Threshold level: Automatic

[0216] Evaluation of Slipperiness The slipperiness of the glass with the hardened coating prepared as described above was evaluated by assessing the coefficient of dynamic friction with the nonwoven fabric using the method described below. The coefficient of dynamic friction of the glass with the hardened coating with the nonwoven fabric was measured in accordance with ASTM D1894 using a surface properties measuring instrument TYPE: 14FW (manufactured by Shinto Kagaku Co., Ltd.) under the conditions of a load of 100 gf and a tensile speed of 500 mm / min. The results (coefficient of dynamic friction) are shown in Table 2. [Slipperiness Evaluation Conditions] Load: 100 gf Stroke: 100 mm Contact area: 1 × 3 cm 2 Nonwoven fabric: BEMCOT (manufactured by Asahi Kasei Corporation)

[0217] Evaluation of stain removal properties A 2 cm straight line was drawn on the glass with the hardened film prepared as described above using a Hi-Mackie (manufactured by Zebra Co., Ltd.), the ink was dried, and then the area was wiped with tissue paper. The number of rubbings required to remove the ink was evaluated according to the following criteria. The results are shown in Table 2. [Stain Removal Evaluation Criteria] A: 4 or fewer rubbings B: 5 or more rubbings C: Ink cannot be wiped off

[0218] Abrasion Resistance Evaluation The glass with the hardened coating prepared as described above was rubbed every 1000 times using a rubbing tester (manufactured by Shinto Kagaku Co., Ltd.) under the following conditions. The contact angle (water repellency) of the hardened coating with water was measured in the same manner as described above, and the number of times it fell below 80° was recorded to evaluate abrasion resistance. The test environment conditions were 25°C and 40% relative humidity. The results (water contact angle after abrasion) are shown in Table 2. [Fabric abrasion resistance test conditions] Nonwoven fabric: BEMCOT (manufactured by Asahi Kasei Corporation) Contact area: 1 cm 2 Distance traveled (one way): 40 mm; Speed: 4,800 mm / min; Load: 1,000 gf / cm 2 Measure the number of times the water contact angle falls below 80°.

[0219] Evaluation of Chemical Resistance The glass with the hardened film prepared as described above was immersed in a container of alkaline solution and left standing in a constant-temperature oven. The glass immersed in the container was removed every hour, the entire surface of the glass was washed with pure water, and then dried with dry air. After that, the contact angle (water repellency) of the hardened film with respect to water was measured in the same manner as described above for the area immersed in the alkaline solution. This operation was repeated, and the immersion time at which the water contact angle became less than 80° was confirmed. The results (chemical resistance (immersion time at which the water contact angle became less than 80°)) are shown in Table 1. The chemical resistance test conditions are as follows. Furthermore, good chemical resistance in this invention means that in the chemical resistance test described above, the immersion time at which the water contact angle of the formed hardened film becomes less than 80° is 2 hours or more, more preferably 4 hours or more, and most preferably 5 hours or more. [Chemical Resistance Test Conditions] Chemical: 30% by mass sodium hydroxide aqueous solution Temperature: 55°C

[0220] The cured coatings of the surface treatment agents in Examples 8 to 14 exhibited improved adhesion to the substrate due to the presence of phosphonic acid groups or phosphonic acid ester groups at the molecular chain ends of the compounds used. Furthermore, the presence of hydrocarbon chains with a predetermined number of carbon atoms resulted in water repellency and improved molecular mobility, leading to good slipperiness, dirt-wiping properties, abrasion resistance, and chemical resistance. Comparative Examples 5 and 7 exhibited poor substrate adhesion because their terminals were alkoxysilyl groups. The cured coating of the surface treatment agent in Comparative Example 6, although the compound used had fluorinated hydrocarbon chains, showed poor durability. Comparative Example 8 was a glass substrate without a surface treatment agent, but since it was not surface-treated, it lacked all of the properties, confirming the effects observed in the Examples. As described above, the surface treatment agents in the Examples made it possible to obtain a cured coating in a spray coat that achieved a high level of water repellency, slipperiness, dirt-wiping properties, abrasion resistance, and chemical resistance.

[0221]

[0222] [Example 15] The compound obtained in Synthesis Example 2 was dissolved in toluene to a concentration of 0.2% by mass to prepare a surface treatment agent.

[0223] [Example 16] The compound obtained in Synthesis Example 6 was dissolved in butyl acetate to a concentration of 0.2% by mass to prepare a surface treatment agent.

[0224] [Example 17] The compound obtained in Synthesis Example 9 was dissolved in propylene glycol monomethyl ether acetate to a concentration of 0.2% by mass to prepare a surface treatment agent.

[0225] [Example 18] The compound obtained in Synthesis Example 11 was dissolved in dibutyl ether to a concentration of 0.2% by mass to prepare a surface treatment agent.

[0226] [Example 19] The compound obtained in Synthesis Example 13 was dissolved in toluene to a concentration of 0.2% by mass to prepare a surface treatment agent.

[0227] [Example 20] The compound obtained in Synthesis Example 16 was dissolved in toluene to a concentration of 0.2% by mass to prepare a surface treatment agent.

[0228] [Comparative Example 9] A surface treatment agent was prepared by dissolving the compound represented by the above formula (A') in dibutyl ether to a concentration of 0.2% by mass.

[0229] [Comparative Example 10] A surface treatment agent was prepared by dissolving the compound represented by the above formula (B') in toluene to a concentration of 0.2% by mass.

[0230] [Comparative Example 11] A surface treatment agent was prepared by dissolving the compound represented by the above formula (C') in dibutyl ether to a concentration of 0.2% by mass.

[0231] [Comparative Example 12] No surface treatment agent used.

[0232] <Preparation of Surface Treatment Agents and Formation of Cured Films> Surface treatment agents were prepared as in the above examples and comparative examples. SUS304 (a test specimen substrate manufactured by Standard Test Piece Co., Ltd., 1 mm thick, 50 mm wide, and 100 mm long) and each surface treatment agent were spray-coated under the following conditions, and cured for 1 hour at 80°C and 80% relative humidity, and then for 12 hours at 25°C and 50% relative humidity to form a cured film with a thickness of 3-5 nm. [Spray Coating Conditions] Atmosphere: 25°C / 50% Nozzle distance: 50 mm Air pressure: 150 kPa Speed: 300 mm / min Pitch: 5 mm

[0233] The substrates on which the cured coating was formed were evaluated for water repellency, slipperiness, dirt wipeability, abrasion resistance, and chemical resistance using the method described below.

[0234] Evaluation of Water Repellency The contact angle (water repellency) of the cured film with respect to water was measured on the substrate on which the cured film prepared as described above was formed, using a Drop Master contact angle meter (Kyowa Interface Science Co., Ltd., DMo-701SA) (droplet: 2 μl, temperature: 25°C, relative humidity: 40%). The measurement was performed by photographing the (stable) droplet 1 second after dropping with a CCD camera connected to the above contact angle meter, and then analyzing the droplet image with the contact angle analysis software FAMAS attached to the above contact angle meter to measure the contact angle between the substrate and the droplet. The contact angle was calculated using the θ / 2 method. The analysis conditions are as follows. The results (initial water contact angle) are shown in Table 3. Initially, both the example and comparative example showed good water repellency. [Analysis Conditions] Method: Droplet method (θ / 2 method) Droplet recognition: Automatic Droplet recognition line (distance from needle tip): 50 dots Algorithm: Automatic Image mode: Frame Threshold level: Automatic

[0235] Evaluation of Slipperiness The slipperiness of the substrate on which the cured film was formed as described above was evaluated by assessing the coefficient of dynamic friction with respect to the nonwoven fabric using the method described below. The coefficient of dynamic friction with respect to the nonwoven fabric of the substrate on which the cured film was formed was measured in accordance with ASTM D1894 using a surface properties measuring instrument TYPE: 14FW (manufactured by Shinto Kagaku Co., Ltd.) under the conditions of a load of 100 gf and a tensile speed of 500 mm / min. The results (coefficient of dynamic friction) are shown in Table 3. [Slipperiness Evaluation Conditions] Load: 100 gf Stroke: 100 mm Contact area: 1 × 3 cm 2 Nonwoven fabric: BEMCOT (manufactured by Asahi Kasei Corporation)

[0236] Evaluation of Dirt Removal Properties A 2 cm straight line was drawn on the substrate with the cured film prepared as described above using a Hi-Mackie (manufactured by Zebra Co., Ltd.), the ink was dried, and then the surface was wiped with tissue paper. The number of rubs required to remove the ink was evaluated according to the following criteria. The results are shown in Table 3. [Criteria for Evaluating Dirt Removal Properties] A: 4 rubs or less B: 5 rubs or more C: Ink cannot be wiped off

[0237] Abrasion Resistance Evaluation The substrates on which the cured film prepared as described above were formed were rubbed every 100 times using a rubbing tester (manufactured by Shinto Kagaku Co., Ltd.) under the following conditions. The contact angle (water repellency) of the cured film with respect to water was measured in the same manner as described above, and the number of times the contact angle fell below 80° was counted to evaluate abrasion resistance. The test environment conditions were 25°C and 40% relative humidity. The results (water contact angle after abrasion) are shown in Table 3. [Fabric Abrasion Resistance Test Conditions] Nonwoven fabric: BEMCOT (manufactured by Asahi Kasei Corporation) Contact area: 1 cm 2 Distance traveled (one way): 40 mm; Speed: 4,800 mm / min; Load: 1,000 gf / cm 2 Measure the number of times the water contact angle falls below 80°.

[0238] Evaluation of Chemical Resistance A substrate with the cured film prepared as described above was immersed in a container of alkaline solution and left standing in a constant-temperature oven. The substrate was removed from the container every hour, the entire surface of the substrate was washed with pure water, and then dried with dry air. After that, the contact angle (water repellency) of the cured film with respect to water was measured in the same manner as described above for the area immersed in the alkaline solution. This operation was repeated, and the immersion time at which the water contact angle became less than 80° was confirmed. The results (chemical resistance (immersion time at which the water contact angle became less than 80°)) are shown in Table 3. The chemical resistance test conditions are as follows. Furthermore, good chemical resistance in this invention means that in the chemical resistance test described above, the immersion time at which the water contact angle of the formed cured film becomes less than 80° is 2 hours or more, more preferably 4 hours or more, and most preferably 5 hours or more. [Chemical Resistance Test Conditions] Chemical: 30% by mass sodium hydroxide aqueous solution Temperature: 55°C

[0239] The cured coatings of the surface treatment agents in Examples 15 to 20 exhibited improved adhesion to the substrate due to the presence of phosphonic acid groups or phosphonic acid ester groups at the molecular chain ends of the compounds used. Furthermore, the presence of hydrocarbon chains with a predetermined number of carbon atoms resulted in water repellency and improved molecular mobility, leading to good slipperiness, dirt-wiping properties, abrasion resistance, and chemical resistance. Comparative Examples 9 and 11 exhibited poor substrate adhesion because their terminals were alkoxysilyl groups. The cured coating of the surface treatment agent in Comparative Example 10, although the compound used had fluorinated hydrocarbon chains, showed poor durability. Comparative Example 12 was a SUS substrate without a surface treatment agent, and since it was not surface-treated, it lacked all of the properties, confirming the effects observed in the Examples. As described above, the surface treatment agents in the Examples made it possible to obtain a cured coating in a spray coat that achieved a high level of water repellency, slipperiness, dirt-wiping properties, abrasion resistance, and chemical resistance.

[0240]

Claims

1. A hydrocarbon-end group-containing compound having at least one linear, branched, or cyclic monovalent hydrocarbon end group having 3 to 32 carbon atoms, and having at least one reactive phosphonic acid group or phosphonic acid ester group at the other molecular end via a divalent or higher linking group bonded to the hydrocarbon end group.

2. The hydrocarbon terminal group-containing compound according to claim 1, wherein the hydrocarbon terminal group is a group selected from alkyl groups having 6 to 28 carbon atoms and aryl groups having 6 to 32 carbon atoms.

3. The hydrocarbon terminal group-containing compound according to claim 1, having two or more hydrocarbon terminal groups, wherein the linking group bonded to the hydrocarbon terminal groups is trivalent or greater.

4. The hydrocarbon terminal group-containing compound is of the following general formula (1) (In the formula, R 1 R may contain at least one atom selected from oxygen, sulfur, nitrogen, and silicon, and may be linear, branched, cyclic, or a combination thereof, and is a monovalent hydrocarbon group having 3 to 32 carbon atoms. 2 These are independently a hydrogen atom, a halogen atom, a hydroxyl group, a siloxy group, an amino group, a thiol group, a monovalent hydrocarbon group having 1 or 2 carbon atoms, R 1 , or -Y-A, where U is a carbon atom, a silicon atom, a nitrogen atom, or a trivalent or tetravalent organic group, V is a single bond, or a divalent hydrocarbon group which may contain at least one selected from an oxygen atom, a nitrogen atom, and a sulfur atom, Z is a single bond, a carbon atom, a silicon atom, a nitrogen atom, a sulfur atom, or a trivalent to octavalent organic group, Y is independently a divalent hydrocarbon group which may contain at least one selected from an oxygen atom, a nitrogen atom, a sulfur atom, and a silicon atom, and A is independently the following general formula (2) A hydrocarbon terminal group-containing compound according to claim 1, represented by the formula (wherein R is independently a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a phenyl group, k is 1 or 2, and m is an integer from 1 to 7).

5. In the above formula (1), R 1 The hydrocarbon terminal group-containing compound according to claim 4, wherein the terminal group is a monovalent hydrocarbon group having 13 to 32 carbon atoms, which may be linear, branched, cyclic, or a combination thereof.

6. In formula (1) above, at least one R 2 R 1 The hydrocarbon terminal group-containing compound according to claim 4.

7. In the above formula (1), R 1 is any one of the following formulas (wherein R A is independently a monovalent hydrocarbon group having 3 to 32 carbon atoms which may be linear, branched or cyclic or a combination thereof, Q is independently an oxygen atom, a sulfur atom, a divalent cyclic hydrocarbon group having 6 to 8 carbon atoms, a diorganosilylene group, a silaalkylene structure or a silaarylene structure, a linear organopolysiloxane residue having 2 to 10 silicon atoms or a branched or cyclic divalent organopolysiloxane residue having 3 to 10 silicon atoms, a carbonyl (ketone) group, an ester group, a carbonate group, a sulfinyl group, a sulfonyl group, a thioester group, a thiocarbonate group, a thiocarbamate group, an amino group, an amide group, a carbamate group, a urea group, and a divalent nitrogen-containing heterocyclic group, Q' is independently a trivalent group selected from the group consisting of a nitrogen atom, a trivalent cyclic hydrocarbon group having 6 to 8 carbon atoms, a linear organopolysiloxane residue having 2 to 10 silicon atoms or a branched or cyclic trivalent organopolysiloxane residue having 3 to 10 silicon atoms, a trivalent amide group, and a trivalent nitrogen-containing heterocyclic group, Q'' is independently a tetravalent group selected from the group consisting of a carbon atom, a silicon atom, a tetravalent cyclic hydrocarbon group having 6 to 8 carbon atoms, and a linear organopolysiloxane residue having 2 to 10 silicon atoms or a branched or cyclic tetravalent organopolysiloxane residue having 3 to 10 silicon atoms, R B is independently a single bond or a divalent hydrocarbon group having 1 to 32 carbon atoms which may be linear, branched or cyclic, R C is independently R A or a hydrogen atom, and p is an integer of 0 to 10. However, the total number of carbon atoms in each structure is 32 or less.) and is a hydrocarbon terminal group-containing compound according to claim 4.

8. The hydrocarbon terminal group-containing compound according to claim 4, wherein in formula (1), Y is a group selected from the group consisting of an alkylene group having 1 to 20 carbon atoms which may contain at least one selected from an oxygen atom, a nitrogen atom, and a sulfur atom; an alkylene group having 1 to 10 carbon atoms which contains an arylene group having 6 to 8 carbon atoms; a divalent group in which alkylene groups having 1 to 8 carbon atoms are bonded to each other via a diorganosilylene group, a sylalkylene structure, a sylarylene structure, or a nitrogen-containing heterocyclic group; and a divalent group in which an alkylene group having 1 to 10 carbon atoms is bonded to the binding site of a linear or branched or cyclic organopolysiloxane residue having 2 to 10 silicon atoms.

9. In formula (1) above, Z is a single bond, or a carbon atom, a silicon atom, a nitrogen atom, a trivalent or tetravalent cyclic hydrocarbon group having 6 to 8 carbon atoms, -SiR 3 = (R 3 (A trivalent group represented by a hydroxyl group, an alkyl group having 1 to 3 carbon atoms, or an alkoxy group having 1 to 3 carbon atoms), -CR 4 = (R 4 The hydrocarbon terminal group-containing compound according to claim 4, wherein the group is a trivalent group represented by a hydrogen atom, a hydroxyl group, or an alkyl group having 1 to 3 carbon atoms; a linear or branched or cyclic trivalent to octavalent organopolysiloxane residue having 2 to 10 silicon atoms; a trivalent amide group; a trivalent carbamate group; a trivalent or tetravalent urea group; and a trivalent to octavalent nitrogen-containing heterocyclic group.

10. The hydrocarbon terminal group-containing compound according to claim 4, wherein in formula (1), U is a trivalent or tetravalent group selected from the group consisting of a carbon atom, a silicon atom, a nitrogen atom, a trivalent or tetravalent cyclic hydrocarbon group having 6 to 8 carbon atoms, a linear or branched or cyclic trivalent or tetravalent organopolysiloxane residue having 2 to 10 silicon atoms, a trivalent amide group, a trivalent carbamate group, a trivalent or tetravalent urea group, and a trivalent or tetravalent nitrogen-containing heterocyclic group.

11. A surface treatment agent comprising a hydrocarbon terminal group-containing compound and / or a partial (hydrolysis) condensate thereof according to any one of claims 1 to 10.

12. An article surface-treated with the surface treatment agent described in claim 11.

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