Hydrocarbon-end-group-containing compound, surface treatment agent, and article

Abstract

Provided is a surface treatment agent containing a hydrocarbon-terminal-group-containing compound having: at the terminal of the molecular chain, one or more substituted or unsubstituted monovalent hydrocarbon groups which each have 10 or more carbon atoms, may contain at least one selected from an oxygen atom, a sulfur atom, a nitrogen atom and a silicon atom, and may be linear, cyclic or a combination thereof; and a monovalent or divalent silacycloalkane-type reactive group. Said surface treatment agent is fast-curing and is capable of forming a cured coating having excellent water repellency, slipperiness, stain-wiping properties and abrasion resistance, in particular steel wool abrasion resistance.

Description

Hydrocarbon-terminated compounds, surface treatment agents, and articles

[0001] The present invention relates to hydrocarbon-terminated compound, and more particularly to hydrocarbon-terminated compound that has rapid curing properties and can form a coating with excellent water repellency, slipperiness, dirt-wiping properties, and abrasion resistance, 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] However, PFAS (Per- and Polyfluoroalkyl Substances) compounds, such as those containing fluoropolyether groups, have the characteristic of being difficult to decompose in nature and tend to accumulate in nature. Therefore, there has been a growing need for the development of surface protective agents for non-PFAS materials.

[0007] Therefore, as surface protective agents using non-PFAS materials, Japanese Patent Publication No. 2024-025759, International Publication No. 2023 / 181866, and International Publication No. 2023 / 181867 (Patent Documents 7-9) use compounds having alkyl groups, and all of them are described as having good abrasion resistance. However, a high temperature of 150°C is required to form the surface after coating, and high-temperature treatment is essential for adhesion to the substrate and to exhibit performance. This is due to the slow curing speed, while fluoropolyether group-containing compounds do not require high temperatures after coating and can exhibit sufficient performance even at room temperature.

[0008] Thus, surface protectants for non-PFAS materials require materials that harden relatively quickly and offer good workability.

[0009] Japanese Patent Publication No. 2008-534696, Japanese Patent Publication No. 2008-537557, Japanese Patent Publication No. 2012-072272, Japanese Patent Publication No. 2012-157856, Japanese Patent Publication No. 2013-136833, Japanese Patent Publication No. 2015-199906, Japanese Patent Publication No. 2024-025759, International Publication No. 2023 / 181866, International Publication No. 2023 / 181867

[0010] The present invention has been made in view of the above circumstances, and aims to provide a fast-curing non-PFAS (i.e., a hydrocarbon-terminated compound that does not have a PFAS-corresponding structure in its molecule) that can form a cured film with excellent water repellency, slipperiness, dirt-wiping properties, and abrasion resistance, a non-PFAS 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 found that a surface treatment agent containing a novel hydrocarbon end group-containing compound, which has a monovalent unsubstituted or substituted hydrocarbon group having 10 or more carbon atoms, and which may contain at least one selected from oxygen, sulfur, nitrogen, and silicon atoms at the end of the molecular chain, and which may be linear, cyclic, or a combination thereof, and a monovalent or divalent silacycloalkane-type reactive group, exhibits rapid curing properties. Furthermore, the inventors have found that a cured film with excellent water repellency, slipperiness, dirt-wiping properties, abrasion resistance, and especially resistance to steel wool abrasion can be formed in a short time, 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 a monovalent unsubstituted or substituted hydrocarbon group having 10 or more carbon atoms, which may contain at least one selected from oxygen, sulfur, nitrogen, and silicon atoms at the end of the molecular chain, and which may be linear, cyclic, or a combination thereof, and a monovalent or divalent silacycloalkane-type reactive group. [2] The hydrocarbon end group-containing compound according to [1], wherein the monovalent hydrocarbon group and the monovalent or divalent silacycloalkane-type reactive group are bonded directly or via a polyvalent linking group. [3] The hydrocarbon end group-containing compound according to [1] or [2], wherein the monovalent hydrocarbon group has 10 to 60 carbon atoms. [4] The hydrocarbon end group-containing compound according to any one of [1] to [3], wherein the monovalent hydrocarbon group is linear. [5] A hydrocarbon terminal group-containing compound according to any one of [1] to [4], wherein the ring member number of the monovalent or divalent silacycloalkane-type reactive group is 3 to 20. [6] The monovalent or divalent silacycloalkane-type reactive group is the following general formula (1) to (3) (In the formula, U 1 is a nitrogen atom or a trivalent organic group, U 2A hydrocarbon terminal group-containing compound according to any one of [1] to [5], wherein the group is any of the groups represented by [1] to [5]. [7] A hydrocarbon terminal group-containing compound according to [6], wherein the total number of atoms forming a cyclic structure in formulas (1) to (3) above is 3 to 20. [8] A in formulas (1) to (3) above is the following general formula (4) A hydrocarbon-terminal group-containing compound as described in [6] or [7], which is represented by the following formula: (wherein R is an alkyl group having 1 to 4 carbon atoms or a phenyl group, X is independently a hydroxyl group or a hydrolyzable group, and n is 1 or 2.) [9] The following general formula (5) or (6) (In the formula, R 1is an unsubstituted or substituted monovalent hydrocarbon group having 10 to 60 carbon atoms, which may independently contain at least one selected from oxygen, sulfur, nitrogen, and silicon atoms, and may be linear, cyclic, or a combination thereof; U and U' are each a carbon atom, silicon atom, nitrogen atom, or a trivalent or tetravalent organic group; V and V' are single bonds or divalent hydrocarbon groups which may contain at least one selected from oxygen, nitrogen, and sulfur atoms; Z is a carbon atom, silicon atom, nitrogen atom, or a trivalent or tetravalent organic group; and W is an acid which may have a single bond or a divalent hydrocarbon group. A hydrocarbon terminal group-containing compound according to any one of [1] to [8], which is represented by the formula (5) or (6) above, where A is a divalent reactive silylene group, T is a divalent hydrocarbon group which may contain at least one selected from oxygen, nitrogen, sulfur, and silicon atoms, Y is a divalent hydrocarbon group which may independently contain at least one selected from oxygen, nitrogen, sulfur, and silicon atoms, A' is a monovalent reactive silyl group, k1 is 1 or 2, k2 is 0 or 1, k1 + k2 is 1 or 2, k3 is an integer from 1 to 3, k4 is 0 or 1, k3 + k4 is an integer from 1 to 3, k5 is 0 or 1, j is 0 or 1, and m is 1 or 2. 1 However, the following formula (In the formula, R AQ is an unsubstituted or substituted monovalent hydrocarbon group having 10 to 60 carbon atoms, which may be linear, cyclic, or a combination thereof, and Q is an oxygen atom, a sulfur atom, a diorganosilylene group, a sylalkylene structure or sylarylene structure, and a linear or branched or cyclic divalent organopolysiloxane residue having 2 to 10 silicon atoms, or 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, 2 Q' is a divalent group selected from the group consisting of valence nitrogen-containing heterocyclic groups, 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 or branched or cyclic trivalent organopolysiloxane residue having 2 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, a linear or branched or cyclic tetravalent organopolysiloxane residue having 2 to 10 silicon atoms, and R B R is a divalent hydrocarbon group having 1 to 50 carbon atoms, which may be independently single-bonded, linear, or cyclic, and C (where is a hydrogen atom and p is an integer from 0 to 10, provided that the total number of carbon atoms in each structure is 60 or less.) A hydrocarbon terminal group-containing compound as described in [9], which is any of the groups represented by [1] to

[10] .

[11] A surface treatment agent containing a hydrocarbon terminal group-containing compound as described in any of [1] to

[10] .

[12] An article surface-treated with the surface treatment agent described in

[11] .

[0013] The hydrocarbon-terminated compound of the present invention, when used as a surface treatment agent, can form a cured film that is fast-curing and has excellent water repellency, slipperiness, dirt-wiping properties, and abrasion resistance. Articles surface-treated with this surface treatment agent exhibit excellent water repellency, slipperiness, dirt-wiping properties, and abrasion resistance.

[0014] The hydrocarbon-terminated compound of the present invention may contain at least one atom selected from oxygen, sulfur, nitrogen, and silicon atoms at the end of its molecular chain, and may have a monovalent unsubstituted or substituted hydrocarbon group having 10 or more carbon atoms, which may be linear, cyclic, or a combination thereof, and a monovalent or divalent silacycloalkane-type reactive group. Preferably, the monovalent hydrocarbon group and the monovalent or divalent silacycloalkane-type reactive group are bonded directly or via a polyvalent linking group. The surface treatment agent containing the hydrocarbon-terminated compound is characterized by its rapid curing properties and the formation of a cured film that is excellent in water repellency, slipperiness, dirt wiping properties, abrasion resistance, and especially resistance to steel wool abrasion.

[0015] In the present invention, a "monovalent or divalent silacycloalkane-type reactive group" is a monovalent or divalent group having a cyclic structure, and the cyclic structure is a group having a silicon atom (reactive silylene group) to which a hydrolyzable group such as a hydroxyl group or an alkoxy group is bonded. Furthermore, in the cyclic structure, examples of atoms bonded to the monovalent hydrocarbon group or linking group include monovalent carbon atoms ("-CH=(cyclic structure)"), divalent carbon atoms ("=C=(cyclic structure)"), nitrogen atoms, and monovalent or divalent silicon atoms.

[0016] The hydrocarbon-terminated group-containing compound of the present invention, when cured using a surface treatment agent containing the hydrocarbon-terminated group-containing compound, exhibits water repellency due to having at least one monovalent hydrocarbon group with a predetermined number of carbon atoms, and improves molecular mobility when bonded to the substrate, resulting in excellent slipperiness, dirt-wiping properties, and abrasion resistance. Furthermore, the hydrocarbon-terminated group-containing compound of the present invention exhibits rapid curing properties because it has a monovalent or divalent silacycloalkane-type reactive group, which improves the hydrolysis rate.

[0017] In this invention, "rapid curing" refers to the speed at which the surface properties of the coating of the surface treatment agent applied to the substrate are manifested (for example, the speed at which water repellency is manifested during film formation), and "having rapid curing properties" means that the surface properties of the coating of the surface treatment agent applied to the substrate are manifested in a short time. In the examples described later, the water contact angle of the substrate surface coating 30 minutes after application of the surface treatment agent was evaluated, and those with a good water contact angle (90° or more) were deemed to "have rapid curing properties".

[0018] In the hydrocarbon-terminal group-containing compound of the present invention, the monovalent hydrocarbon group having one or more carbon atoms at the end of the molecular chain has 10 or more carbon atoms, preferably 10 to 60 carbon atoms, more preferably 10 to 50 carbon atoms, even more preferably 10 to 40 carbon atoms, and particularly preferably 11 to 30 carbon atoms. The monovalent hydrocarbon group may contain at least one selected from oxygen, sulfur, nitrogen, and silicon atoms, and may be linear, cyclic, or a combination thereof. Linear is preferred. The monovalent hydrocarbon group may be unsubstituted or partially substituted. Furthermore, in the hydrocarbon-terminal group-containing compound of the present invention, it is preferable to have 1 to 3 monovalent hydrocarbon groups, and more preferably 2 or 3 from the viewpoint of water repellency.

[0019] Furthermore, if the hydrocarbon-terminal group-containing compound of the present invention has a linking group that bonds to the monovalent or divalent silacycloalkane-type reactive group, the linking group is preferably trivalent or higher, and more preferably trivalent or tetravalent.

[0020] In the hydrocarbon-terminated compound of the present invention, the monovalent or divalent silacycloalkane-type reactive group has at least one reactive silylene group in its cyclic structure, preferably one. The atoms forming the cyclic structure have at least two atoms selected from carbon atoms, oxygen atoms, nitrogen atoms, sulfur atoms, and silicon atoms. The number of ring members is not particularly limited as long as it does not impair the effects of the present invention, but is preferably 3 to 20, more preferably 4 to 10, even more preferably 4 to 8, and particularly preferably 4 to 6.

[0021] Further, from the viewpoint of abrasion resistance, the compound may have a monovalent group having a reactive silyl group in a side chain in the cyclic structure, and from the viewpoint of ease of production, the compound does not need to have a monovalent group having a reactive silyl group.

[0022] The monovalent or divalent silacycloalkane-type reactive group is preferably a group represented by the following general formulas (1) to (3). (wherein, U 1 is a nitrogen atom or a trivalent organic group, and U 2 is a carbon atom, a silicon atom, or a tetravalent organic group; V is a single bond or a divalent hydrocarbon group that may contain at least one selected from the group consisting of an oxygen atom, a nitrogen atom and a sulfur atom; Z is a carbon atom, a silicon atom, a nitrogen atom, or a trivalent or tetravalent organic group; W is a single bond, or an oxygen atom, a sulfur atom or an amino group that may have a divalent hydrocarbon group; A is a divalent reactive silylene group; T is a divalent hydrocarbon group that may have at least one selected from the group consisting of an oxygen atom, a nitrogen atom, a sulfur atom and a silicon atom interposed therein; each Y is independently a divalent hydrocarbon group that may contain at least one selected from the group consisting of an oxygen atom, a nitrogen atom, a sulfur atom and a silicon atom; each A' is independently a monovalent reactive silyl group; j is 0 or 1; and m is 1 or 2.)

[0023] In the above formula (1), U 1 is a nitrogen atom or a trivalent organic group, and examples of the trivalent organic group include a trivalent group represented by -SiR 3 =(R 3 is a hydroxyl group, an alkyl group having 1 to 3 carbon atoms, or an alkoxy group having 1 to 3 carbon atoms), a trivalent group represented by -CR 4 =(R 4 is a hydrogen atom, a hydroxyl group, or an alkyl group having 1 to 3 carbon atoms), a trivalent cyclic hydrocarbon group having 6 to 8 carbon atoms, a linear trivalent organopolysiloxane residue having 2 to 10 silicon atoms, particularly 2 to 8 silicon atoms, or a branched or cyclic trivalent organopolysiloxane residue having 3 to 10 silicon atoms, particularly 3 to 8 silicon atoms, and is preferably a trivalent group selected from the group consisting of a trivalent amide group, a trivalent carbamate group, a trivalent urea group, and a trivalent nitrogen-containing heterocycle-containing group (such as a trivalent cyanurate group, a trivalent isocyanurate group, and a trivalent triazine ring-containing group).

[0024] The organopolysiloxane residue is preferably one having 1 to 8 carbon atoms, more preferably 1 to 4 carbon atoms, and containing an alkyl group such as a methyl group, ethyl group, propyl group, or butyl group, or a phenyl group.

[0025] This kind of U 1 Examples include those listed below. In the structures below, there are no particular restrictions on the bonding positions, but it is preferable that the right-hand bonding point is bonded to V, and the lower or upper bonding point is bonded to W.

[0026] In the above equations (2) and (3), U 2 The group is a carbon atom, a silicon atom, or a tetravalent organic group. Preferably, the tetravalent organic group is a tetravalent group selected from a tetravalent hydrocarbon group having 6 to 8 carbon atoms, a linear tetravalent organopolysiloxane residue having 2 to 10 silicon atoms, particularly 2 to 8 silicon atoms, or a branched tetravalent organopolysiloxane residue having 3 to 10 silicon atoms, particularly 3 to 8 silicon atoms, and a tetravalent urea group.

[0027] 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 propylene group.

[0028] This kind of U 2 Examples include those listed below. In the structures below, there are no particular restrictions on the bonding positions, but it is preferable that the right-hand bonding point is bonded to V and the lower bonding point is bonded to W.

[0029] In the above formulas (1) to (3), V may be a single bond or at least one selected from an oxygen atom, a nitrogen atom, and a sulfur atom, preferably a divalent hydrocarbon group having 1 to 10 carbon atoms, and U 1 Base or U 2 It is a linking group that connects the group and the Z group. Examples of the divalent hydrocarbon group include alkylene groups having 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms, and more preferably 1 to 3 carbon atoms, which may contain at least one selected from oxygen, nitrogen, and sulfur atoms.

[0030] Examples of such V include, in addition to single bonds, the following. Note that in the structure below, the bond on the left is U. 1 or U 2 Therefore, it is preferable that the right-hand bond connects 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.)

[0031] In the above formulas (1) to (3), Z is a carbon atom, a silicon atom, a nitrogen atom, or a trivalent or tetravalent organic group, and as a trivalent or tetravalent organic 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 trivalent or tetravalent groups include trivalent groups represented by a hydrogen atom, a hydroxyl group, or an alkyl group having 1 to 3 carbon atoms, trivalent amide groups, trivalent carbamate groups, and trivalent or tetravalent urea groups.

[0032] Examples of such Z include those shown below. In the structure below, it is preferable that the left-hand connector connects to V, the right-hand connector connects to T, and the other connectors connect to Y.

[0033] In the above formulas (1) to (3), W is an oxygen atom, sulfur atom, or amino group which may have a single bond or a divalent hydrocarbon group. The amino group is represented by -NH-, and if it has a divalent hydrocarbon group, it is preferably a divalent hydrocarbon group having 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms, more preferably 1 to 3 carbon atoms, and especially an alkylene group. Furthermore, from the viewpoint of ease of manufacture, it is preferable that the atom bonded to A' is an atom other than a carbon atom.

[0034] Examples of such W groups include the following, in addition to single bonds. In the structure below, the bond on the left is U. 1 or U 2 Therefore, it is preferable that the right-hand connector connects to A. (In the formula, g is an integer from 1 to 10, preferably an integer from 1 to 6.)

[0035] In formulas (1) to (3) above, A is a divalent reactive silylene group, and examples of divalent groups include hydroxyl group-containing silylene groups and hydrolyzable silylene groups.

[0036] As for hydroxyl group-containing silylene groups and hydrolyzable silylene groups, see the following general formula (4) A group represented by the formula (wherein R is an alkyl group or phenyl group having 1 to 4 carbon atoms, X is independently a hydroxyl group or a hydrolyzable group, and n is 1 or 2, preferably 2) is preferred.

[0037] In formula (4) above, R is an alkyl group or phenyl group having 1 to 4 carbon atoms, such as a methyl group, ethyl group, propyl group, or butyl group, with methyl group being preferred. In formula (4) above, X is independently a hydroxyl group or a hydrolyzable group. Examples of such X include hydroxyl groups; alkoxy groups having 1 to 10 carbon atoms, such as methoxy, ethoxy, propoxy, isopropoxy, and butoxy groups; alkoxyalkoxy groups having 2 to 10 carbon atoms, such as methoxymethoxy and methoxyethoxy groups; acyloxy groups having 1 to 10 carbon atoms, such as acetoxy groups; alkenyloxy groups having 2 to 10 carbon atoms, such as isopropenoxy and cyclopentenyloxy groups; halogen groups having chlorine, bromo, and iodine groups; and dialkylamino groups having 2 to 10 carbon atoms, such as dimethylamino and diethylamino groups. Among these, methoxy, ethoxy, isopropenoxy, acetoxy, and chlorine groups are preferred. X may be the same or different.

[0038] Examples of such a group A include the following: (In the formula, Ac represents an acetyl group.)

[0039] In the above formulas (1) to (3), T may contain at least one selected from oxygen, nitrogen, sulfur, and silicon atoms, preferably a divalent hydrocarbon group having 1 to 10 carbon atoms, more preferably 2 to 6 carbon atoms, and even more preferably 2 to 4 carbon atoms, U 1 Base, U 2 It is a linking group that connects a group or a Z group to an A group. Examples of the divalent hydrocarbon group include alkylene groups having 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms, which may have at least one atom selected from oxygen, nitrogen, and sulfur atoms interposed between them, and divalent groups in which alkylene groups having 1 to 8 carbon atoms are bonded to each other via a diorganosilylene group.

[0040] Here, the group that bonds to the silicon atom of the diorganosilylene group is preferably an alkyl group such as a methyl group, ethyl group, propyl group, or butyl group, having 1 to 8 carbon atoms, preferably 1 to 4 carbon atoms, or a phenyl group.

[0041] Examples of such T groups include the following group. In the structure below, the bond on the left is U. 1 , U 2 (When j=0) or Z (when j=1), the right-hand bond is preferably bonded to A. (In the formula, a is an integer between 1 and 10, b, c, and d are each integers between 1 and 8, and the sum of b, c, and d is an integer less than or equal to 10.)

[0042] In the above formulas (1) to (3), Y may independently contain at least one selected from an oxygen atom, a nitrogen atom, a sulfur atom, and a silicon atom, preferably a divalent hydrocarbon group having 1 to 20 carbon atoms, more preferably 1 to 6 carbon atoms, and even more preferably 1 to 4 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 10 carbon atoms, preferably 1 to 6 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.

[0043] 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 group, methylethylene group), butylene groups (tetramethylene group, methylpropylene group), etc., having 2 to 6 carbon atoms, preferably 2 to 4 carbon atoms. In addition, the organopolysiloxane residue may contain a sylalkylene structure in which two silicon atoms are bonded by alkylene groups such as ethylene and propylene groups.

[0044] Examples of such Y include the following groups. In the structure below, it is preferable that the left bond is bonded to Z and the right bond is bonded to A'. (In the formula, a1 is an integer between 1 and 10, b1, c1, and d1 are each integers between 1 and 8, and the sum of b1, c1, and d1 is an integer less than or equal to 10. e is an integer between 1 and 9, and f is an integer between 2 and 4.)

[0045] In the above formulas (1) to (3), A' is independently a monovalent reactive silyl group, and examples include monovalent groups such as hydroxyl group-containing silyl groups (silanol groups) and hydrolyzable silyl groups. Among these, hydroxyl group-containing silyl groups (silanol groups) and hydrolyzable silyl groups are preferred.

[0046] The following general formula (7) is used for hydroxyl group-containing silyl groups and hydrolyzable silyl groups. A group represented by the formula (wherein R is independently an alkyl group having 1 to 4 carbon atoms or a phenyl group, X is independently a hydroxyl group or a hydrolyzable group, and n' is an integer from 1 to 3) is preferred.

[0047] In formula (7) above, R and X can be the same as those exemplified in formula (4) above. In formula (7) above, n' is an integer from 1 to 3, and is preferably 3 when X is a hydrolyzable group.

[0048] Examples of such A' groups include the following:

[0049] In the above formulas (1) to (3), j is 0 or 1, preferably 1 from the viewpoint of wear resistance and preferably 0 from the viewpoint of ease of manufacture. In the above formulas (1) to (3), m is 1 or 2, preferably 2 from the viewpoint of wear resistance and preferably 1 from the viewpoint of ease of manufacture.

[0050] In the above equations (1) to (3), the U in equation (1) forms a ring structure. 1 , V, Z, T, A, W and U in equations (2) and (3) 2 The total number of atoms in V, Z, T, A, and W (i.e., the number of ring members) is preferably 3 to 20, more preferably 4 to 10, even more preferably 4 to 8, and particularly preferably 4 to 6.

[0051] The following structures can be given as examples of the group represented by the above formulas (1) to (3). U 1 , U 2 By changing the combinations of V, Z, T, A, W, Y, A', j, and m, several hydrocarbon-terminal group-containing compounds can be obtained. The following structures are bonded to either monovalent hydrocarbon groups or polyvalent linking groups. (In the formula, a, a1, b, c, and g are the same as above, and the number of ring members is between 3 and 20.)

[0052] The hydrocarbon terminal group-containing compound of the present invention is preferably a compound represented by the following general formula (5) or (6). (In the formula, V, Z, W, A, T, Y, A', j, m are the same as above, R 1(The first part of the molecule is a monovalent unsubstituted or substituted hydrocarbon group having 10 to 60 carbon atoms, which may independently contain at least one atom selected from oxygen, sulfur, nitrogen, and silicon, and may be linear, cyclic, or a combination thereof; U and U' are carbon atoms, silicon atoms, nitrogen atoms, or trivalent or tetravalent organic groups, respectively; V' is a single bond or a divalent hydrocarbon group which may contain at least one atom selected from oxygen, nitrogen, and sulfur; k1 is 1 or 2, k2 is 0 or 1, k1 + k2 is 1 or 2, k3 is an integer from 1 to 3, k4 is 0 or 1, k3 + k4 is an integer from 1 to 3, and k5 is 0 or 1.)

[0053] In the above equations (5) and (6), R 1 This group may independently contain at least one selected from oxygen, sulfur, nitrogen, and silicon atoms, and may be linear, cyclic, or a combination thereof, and is an unsubstituted or substituted monovalent hydrocarbon group having 10 to 60 carbon atoms, preferably 10 to 50, more preferably 10 to 40, and even more preferably 11 to 30 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.

[0054] R 1 The base represented by the following formula is preferred. (In the formula, R AQ is independently a linear, cyclic, or combination thereof, unsubstituted or substituted monovalent hydrocarbon group having 10 to 60 carbon atoms, where Q is independently an oxygen atom, a sulfur atom, a diorganosilylene group, a sylalkylene structure or sylarylene structure, and a linear or branched or cyclic divalent organopolysiloxane residue having 2 to 10 silicon atoms, or 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, a divalent nitrogen-containing heterocyclic group (divalent oxazole group, divalent imidazole group, divalent tri Q' is a divalent group selected from the group consisting of an azole group, etc., 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, a trivalent nitrogen-containing heterocyclic group (trivalent cyanurate group, trivalent isocyanurate group, trivalent triazole group, etc.), 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, a linear or branched or cyclic tetravalent organopolysiloxane residue having 2 to 10 silicon atoms, etc., R B R is a divalent hydrocarbon group having 1 to 50 carbon atoms, which may be independently single-bonded, linear, or cyclic, and C (where p is a hydrogen atom, and p is an integer between 0 and 10. However, the total number of carbon atoms in each structure is 60 or less.)

[0055] In the above formula, R A These may be independently linear, cyclic, or a combination thereof, unsubstituted or substituted monovalent hydrocarbon groups having 10 to 60 carbon atoms, preferably 10 to 50, more preferably 10 to 40, and even more preferably 11 to 30 carbon atoms, preferably linear alkyl groups. Some of the hydrogen atoms in the linear alkyl group may be substituted with halogen atoms such as fluorine, bromine, or chlorine, or hydroxyl groups, and the molecular chain may also have unsaturated bonds such as alkenylene structures (double bonds) or alkynylene structures (triple bonds).A For example, the following can be cited: (In the formula, x is an integer between 9 and 59, preferably between 9 and 49, more preferably between 9 and 39, and even more preferably between 10 and 29 carbon atoms, and y is an integer of 1 or more such that the sum of the number of carbon atoms in each structure is 60 or less.)

[0056] In the above formula, Q is independently a divalent group selected from the group consisting of an oxygen atom, a sulfur atom, a diorganosilylene group, a sylalkylene structure or sylarylene structure, and 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).

[0057] 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 group, methylethylene group), butylene groups (tetramethylene group, methylpropylene group), etc., having 2 to 6 carbon atoms, preferably 2 to 4 carbon atoms. In addition, the organopolysiloxane residue may contain a sylalkylene structure in which two silicon atoms are bonded by alkylene groups such as ethylene and propylene groups.

[0058] Examples of such Q include those shown below. In the structure below, the left-hand coupling is R A or R B It is joined to the right side, and the joining hand is R B It is preferable that it be bonded with. (In the formula, f is an integer between 2 and 4, and e is an integer between 1 and 9.)

[0059] 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 trivalent amide group, or a trivalent nitrogen-containing heterocyclic group (such as a trivalent cyanurate group, a trivalent isocyanurate group, or a trivalent triazole group).

[0060] 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 propylene group.

[0061] Examples of such Q' include those shown below. In the structure below, the left-hand bond is R A or R B And the coupling on the right is R B And the other bonds are R C It is preferable that it be bonded with. (In the formula, f is an integer between 2 and 4.)

[0062] 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, a linear tetravalent organopolysiloxane residue having 2 to 10 silicon atoms, particularly 2 to 8 silicon atoms, or a branched or cyclic tetravalent organopolysiloxane residue having 3 to 10 silicon atoms, particularly 3 to 8 silicon atoms.

[0063] 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 propylene group.

[0064] Examples of such Q'' include those shown below. In the structure below, the left-hand bond is R A or R B And the coupling on the right is R B And the other bonds are R C It is preferable that it be bonded with.

[0065] In the above formula, R B These are divalent hydrocarbon groups having 1 to 50 carbon atoms, which may be independently single-bonded, linear, or cyclic, and the following are examples: (In the formula, z is an integer between 1 and 50, preferably between 1 and 20.)

[0066] In the above formula, R C It is a hydrogen atom.

[0067] 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 60 or less.

[0068] This kind of R 1 The following are preferred for use. (In the formula, x, y, and z are the same as above, except that the total number of carbon atoms in each structure is between 10 and 60.)

[0069] In the above formulas (5) and (6), U and U' are a carbon atom, a silicon atom, a nitrogen atom, or a trivalent or tetravalent organic group, respectively, and as a trivalent or tetravalent organic 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 Preferably, the group is a trivalent or tetravalent group selected from a trivalent group represented by a hydrogen atom, a hydroxyl group, or an alkyl group having 1 to 3 carbon atoms; a trivalent or tetravalent cyclic hydrocarbon group having 6 to 8 carbon atoms; a trivalent or tetravalent organopolysiloxane residue having 2 to 10 silicon atoms, particularly a linear chain with 2 to 8 silicon atoms, or a branched or cyclic trivalent or tetravalent organopolysiloxane residue having 3 to 10 silicon atoms, particularly a 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).

[0070] 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 propylene group.

[0071] Examples of such U and U' are shown below. In the structures below, there are no particular restrictions on the bond positions, however, in the case of U', it is preferable that the right-hand bond connects with V'.

[0072] In formula (6) above, V' may be a single bond or 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 U group. Examples of the divalent hydrocarbon group include alkylene groups 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, and alkylene groups having 1 to 14 carbon atoms including arylene groups having 6 to 8 carbon atoms (for example, alkylene-arylene groups having 7 to 20 carbon atoms).

[0073] Examples of such V' include, in addition to single bonds, those shown below. In the structure below, it is preferable that the left bond is bonded to U' and the right bond is bonded to U. (In the formula, q is an integer between 1 and 20, r, s, and t are each integers between 1 and 8, the sum of r and s is an integer between 2 and 20, and the sum of r, s, and t is an integer between 3 and 20.)

[0074] Furthermore, among the hydrocarbon terminal group-containing compounds represented by formula (5) or (6) above, it is preferable that the hydrocarbon terminal group-containing compound is represented by formula (8) or (9) below, and when such compound is used as a surface treatment agent, an improvement in chemical resistance can be expected. (In the formula, U, U', V', V, Z, W, A, T, Y, A', j, m, k5 are the same as above, R 1’ (These are independently linear, cyclic, or combinations thereof, monovalent hydrocarbon groups having 10 to 40 carbon atoms, where k6 is 1 or 2, and k7 is 2 or 3.)

[0075] In the above equations (8) and (9), R 1’ R is a monovalent hydrocarbon group having 10 to 40 carbon atoms, which may be independently linear, cyclic, or a combination thereof, and is preferably a monovalent hydrocarbon group having 11 to 30 carbon atoms. 1’ Having 10 or more carbon atoms prevents chemicals from penetrating the substrate-adhering portion, thus improving chemical resistance.

[0076] (In the formula, x' is an integer between 9 and 39, preferably between 10 and 29, and y' is an integer of 1 or more. However, the total number of carbon atoms in each structure is between 10 and 40.)

[0077] In equations (8) and (9) above, U, U', V', V, Z, W, A, T, Y, A', j, m, k5 are the same as U, U', V', V, Z, W, A, T, Y, A', j, m, k5 in equations (1) to (3), (5), and (6) above.

[0078] The following structures are examples of hydrocarbon terminal group-containing compounds represented by the above formula (5) or (6). 1 By changing the combinations of U, U', V, V', Z, W, A, T, Y, A', k1, k2, k1+k2, k3, k4, k3+k4, k5, j, and m, several different hydrocarbon end-group-containing compounds can be obtained.

[0079] (In the formula, x, y, z, q, r, s, a, a1, b, c, and g are each independently the same as above. R in formula (5) or (6) 1 The total number of carbon atoms in this group is between 10 and 60, and the number of ring members in the molecule is between 3 and 20.

[0080] Examples of methods for preparing hydrocarbon terminal group-containing compounds represented by the above formulas (5) and (6) include the following: [Preparation Method 1] A hydrocarbon terminal group-containing compound having an alkenyl group and an active hydrogen-containing group at its terminal is mixed with a compound having an SiH group and a hydrolyzable silyl group, and a base is added if necessary to react the active hydrogen-containing group in the hydrocarbon terminal group-containing compound having an alkenyl group and an active hydrogen-containing group at its terminal with the hydrolyzable silyl group in the compound having an SiH group and a hydrolyzable silyl group, thereby introducing the SiH group and hydrolyzable silyl group onto the active hydrogen-containing group in the hydrocarbon terminal group-containing compound having an alkenyl group and an active hydrogen-containing group at its terminal (Step 1). Next, a hydrocarbon terminal group-containing compound having an alkenyl group, an SiH group, and a hydrolyzable silyl group at its terminus is subjected to an intramolecular cyclization reaction by hydrosilylation addition of the alkenyl group and SiH group within the molecule in the presence of a hydrosilylation catalyst (Step 2), thereby producing a hydrocarbon terminal group-containing compound represented by formula (5) or (6) above (particularly a compound having a hydrolyzable silyl group at its terminus). If a compound having an SiH group and a hydrolyzable silyl group has a halogen group as the hydrolyzable group, the substituent (halogen atom) on the silyl group can be converted to another hydrolyzable group after the hydrosilylation reaction (Step 3).

[0081] Examples of hydrocarbon terminal group-containing compounds having an alkenyl group and an active hydrogen-containing group at their terminals include compounds represented by the following formulas (5-a) and (6-a). (In the formula, R 1 U, V, Z, U', V', k1, k2, k1+k2, k3, k4, k3+k4, k5, j, and m are the same as above. T 1 Y is a single bond, or a divalent hydrocarbon group which may contain at least one selected from oxygen, nitrogen, sulfur, and silicon atoms, 1 This is a divalent hydrocarbon group which may independently contain a single bond or at least one selected from an oxygen atom, a nitrogen atom, a sulfur atom, and a silicon atom, W 1 (This may be a hydroxyl group, thiol group, or amino group that has a divalent hydrocarbon group.)

[0082] In the above equations (5-a) and (6-a), T 1 The group is a single bond or may contain at least one atom selected from oxygen, nitrogen, sulfur, and silicon atoms, preferably a divalent hydrocarbon group having 1 to 8 carbon atoms. Examples of this divalent hydrocarbon group include an alkylene group having 1 to 8 carbon atoms, preferably 1 to 4 carbon atoms, which may contain at least one atom selected from oxygen, nitrogen, and sulfur atoms, and a divalent group in which an alkylene group having 1 to 8 carbon atoms is bonded to a diorganosilylene group.

[0083] Here, the group that bonds to the silicon atom of the diorganosilylene group is preferably an alkyl group such as a methyl group, ethyl group, propyl group, or butyl group, having 1 to 8 carbon atoms, preferably 1 to 4 carbon atoms, or a phenyl group.

[0084] This kind of T 1 Besides single bonds, other examples include those shown below. In the structure below, the bond on the left is bonded to Z, and the bond on the right is bonded to a carbon atom. (In the formula, a' is an integer between 1 and 8, b and c are integers between 1 and 8, c' and d' are integers between 0 and 6, and the sum of b, c, c', and d' is an integer less than or equal to 8.)

[0085] In the above equations (5-a) and (6-a), Y 1The group may independently contain a single bond or at least one selected from oxygen, nitrogen, sulfur, and silicon atoms, preferably a divalent hydrocarbon group having 1 to 18 carbon atoms, and the divalent hydrocarbon group may specifically contain at least one selected from oxygen, nitrogen, and sulfur atoms, preferably an alkylene group having 1 to 8 carbon atoms, preferably an alkylene group having 1 to 4 carbon atoms, or an arylene group having 6 to 8 carbon atoms (for example, a group having 7 to 8 carbon atoms). Examples include divalent groups in which an alkylene group having 16 atoms (alkylene / arylene groups), an alkylene group having 1 to 8 carbon atoms is bonded to a diorganosilylene group, a sylalkylene structure, a sylarylene structure, or a nitrogen-containing heterocyclic group, and divalent groups in which an alkylene group having 1 to 8 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.

[0086] 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 group, methylethylene group), butylene groups (tetramethylene group, methylpropylene group), etc., having 2 to 6 carbon atoms, preferably 2 to 4 carbon atoms. In addition, the organopolysiloxane residue may contain a sylalkylene structure in which two silicon atoms are bonded by alkylene groups such as ethylene and propylene groups.

[0087] This kind of Y 1 Besides single bonds, other examples include those shown below. In the structure below, the bond on the left is bonded to Z, and the bond on the right is bonded to a carbon atom. (In the formula, a' is an integer between 1 and 8, b and c are integers between 1 and 8, c' and d' are integers between 0 and 6, and the sum of b, c, c', and d' is an integer less than or equal to 8. e is an integer between 1 and 9, and f is an integer between 2 and 4.)

[0088] In the above equations (5-a) and (6-a), W 1 This group may have a divalent hydrocarbon group, or it may be a hydroxyl group, thiol group, or amino group. If it has a divalent hydrocarbon group, it is preferably a divalent hydrocarbon group having 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms, more preferably 1 to 3 carbon atoms, and especially preferably an alkylene group.

[0089] This kind of W 1 Examples of such groups include the following: (In the formula, g is the same as above.)

[0090] Examples of compounds represented by formulas (5-a) and (6-a) are shown below. (In the formula, x, y, z, a', a1', and c' are all independently the same as above.)

[0091] Examples of compounds having an SiH group and a hydrolyzable silyl group include trimethoxysilane, triethoxysilane, triacetoxysilane, and trichlorosilane.

[0092] In step 1 of preparation method 1, the amount of compound having an SiH group and a hydrolyzable silyl group used is preferably 1 to 20 mol, particularly 5 to 15 mol, per 1 mol of active hydrogen-containing group in the hydrocarbon terminal group-containing compound having an alkenyl group and an active hydrogen-containing group at the terminal.

[0093] In step 1 of preparation method 1, a base may be added when mixing a hydrocarbon terminal group-containing compound having an alkenyl group and an active hydrogen-containing group at its terminal end with a compound having an SiH group and a hydrolyzable silyl group. Examples of bases include triethylamine, ethyldiisopropylamine, imidazole, lutidine, DBU, DBN, pyridine, sodium bicarbonate, sodium carbonate, potassium carbonate, sodium methoxide, potassium methoxide, sodium ethoxide, potassium ethoxide, potassium tertifoxide, etc. When adding a base, the amount used is preferably 1 to 10 mol, particularly 1 to 5 mol, per 1 mol of active hydrogen-containing group in the hydrocarbon terminal group-containing compound having an alkenyl group and an active hydrogen-containing group at its terminal end. When adding a base, it is preferable to age the mixture at 0 to 100°C for 0.5 to 72 hours after adding the base.

[0094] In step 1 of preparation method 1, a solvent can be used when reacting a hydrocarbon terminal group-containing compound having an alkenyl group and an active hydrogen-containing group at its terminal with a compound having an SiH group and a hydrolyzable silyl group. Examples of solvents include aromatic hydrocarbons such as toluene and xylene, aliphatic or alicyclic hydrocarbons such as n-pentane, n-hexane, and cyclohexane, cyclic ether compounds such as tetrahydrofuran and dioxane, and ketones such as acetone and methyl ethyl ketone. 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 alkenyl group and an active hydrogen-containing group at its terminal.

[0095] In step 1 of preparation method 1, the reaction conditions for the hydrocarbon terminal group-containing compound having an alkenyl group and an active hydrogen-containing group at its terminal and the compound having an SiH group and a hydrolyzable silyl group are preferably a temperature of 0 to 120°C, particularly 20 to 100°C, for 0.5 to 72 hours, and especially 1 to 36 hours.

[0096] After step 1 is completed, it is preferable to remove the solvent and unreacted materials by distillation under reduced pressure.

[0097] In step 2 of preparation method 1, 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, an SiH group, and a hydrolyzable silyl group at its terminal end.

[0098] In step 2 of preparation method 1, a solvent can be used when carrying out the hydrosilylation addition reaction. Examples of solvents include aromatic hydrocarbons such as toluene and xylene, aliphatic or alicyclic hydrocarbons such as n-pentane, n-hexane, and cyclohexane, cyclic ether compounds such as tetrahydrofuran and dioxane, and ketones such as acetone and methyl ethyl ketone. 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 alkenyl group, an SiH group, and a hydrolyzable silyl group at its terminal end.

[0099] In step 2 of preparation method 1, the reaction conditions for reacting the alkenyl group and SiH group in the hydrocarbon terminal group-containing compound having an alkenyl group, an SiH group, and a hydrolyzable silyl group at its terminals are preferably a temperature of 0 to 120°C, particularly 20 to 100°C, for 0.5 to 72 hours, and especially 1 to 36 hours.

[0100] In step 2 of preparation method 1, after reacting the alkenyl group and SiH group in a hydrocarbon-terminated compound having an alkenyl group, an SiH group, and a hydrolyzable silyl group at its terminus, if an alkenyl group remains, the compound having an SiH group and a hydrolyzable silyl group is then mixed to carry out a hydrosilylation addition reaction between the remaining alkenyl group of the compound obtained in step 2 and the SiH group in the compound having an SiH group and a hydrolyzable silyl group.

[0101] Here, the amount of compound having SiH groups and hydrolyzable silyl groups to be further mixed is preferably 1 to 20 mol, and more preferably 1 to 5 mol, per 1 mol of residual alkenyl groups (theoretical amount: amount remaining after the above reaction) of the compound obtained in step 2.

[0102] The hydrosilylation addition reaction between the remaining alkenyl group of the compound obtained in step 2 and the SiH group in the compound having the SiH group and the hydrolyzable silyl group can be carried out under the same conditions as the hydrosilylation addition reaction in step 2.

[0103] In preparation method 1, if a compound having a SiH group and a hydrolyzable silyl group is used, such as trichlorosilane, in which the hydrolyzable group is a halogen group (a compound containing a SiH group and a halogenated silyl group), the substituent (halogen atom) on the silyl group can then be converted to another hydrolyzable group, such as an alkoxy group like a methoxy group or an acyloxy group like an acetoxy group (step 3). Examples of compounds that can be used to convert the substituent (halogen atom) on the silyl group to another hydrolyzable group include methanol, ethanol, isopropanol, ethylene glycol monomethyl ether, trimethyl orthoformate, acetic acid, and acetic anhydride. The amount used is preferably 2 to 27 mol, particularly 3 to 18 mol, per 1 mol of terminal alkenyl group of the hydrocarbon terminal group-containing compound having an alkenyl group and an active hydrogen-containing group at the terminal end used as a raw material.

[0104] In step 3 of preparation method 1, the reaction conditions for converting substituents (halogen atoms) on the silyl group to other hydrolyzable groups are preferably a temperature of 0 to 80°C, particularly 20 to 60°C, for 0.5 to 72 hours, and especially 1 to 36 hours.

[0105] Subsequently, it is preferable to remove the solvent and unreacted substances by distillation under reduced pressure.

[0106] Other methods for preparing hydrocarbon terminal group-containing compounds represented by formulas (5) and (6) above include the following: [Preparation Method 2] A hydrocarbon terminal group-containing compound having a leaving group at its terminal (for example, a halogen atom or a sulfonyl ester group) is mixed with a compound having an amino group and a hydrolyzable silyl group, and the leaving group in the hydrocarbon terminal group-containing compound having a leaving group at its terminal reacts with the amino group in the compound having the amino group and the hydrolyzable silyl group (Step 1). Subsequently, the reaction product is subjected to an intramolecular cyclization reaction in the presence of a basic or acidic compound, and in some cases under reduced pressure (Step 2), thereby producing hydrocarbon terminal group-containing compounds represented by formulas (5) and (6).

[0107] Examples of hydrocarbon terminal group-containing compounds having a leaving group at its terminal include compounds represented by the following formulas (5-b) and (6-b). (In the formula, R 1 U', V', Y, A', k3, k4, and k3+k4 are the same as above. X' is a halogen atom such as fluorine, chlorine, bromine, or iodine, or a sulfonyl ester group.

[0108] Examples of compounds represented by formulas (5-b) and (6-b) are shown below. (In the formula, x, y, z, q, r, and s are all independently the same as above.)

[0109] Examples of compounds having an amino group and a hydrolyzable silyl group include 3-(trimethoxysilyl)propylamine [also known as 3-aminopropyltrimethoxysilane], 3-(triethoxysilyl)propylamine, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, N-2-(aminoethyl)-3-aminopropyltriethoxysilane, and bis(3-trimethoxysilylpropyl)amine.

[0110] In step 1 of preparation method 2, the amount of compound having an amino group and a hydrolyzable silyl group used is preferably 1 to 6 mol, particularly 1.5 to 3 mol, per 1 mol of leaving group in the hydrocarbon terminal group-containing compound having a leaving group at its terminal end.

[0111] In step 1 of preparation method 2, the reaction conditions for reacting the leaving group in the hydrocarbon terminal group-containing compound having a leaving group at its terminal with the amino group in the compound having an amino group and a hydrolyzable silyl group are preferably a temperature of 25 to 180°C, particularly 50 to 150°C, for 0.5 to 72 hours, and especially 1 to 24 hours.

[0112] After step 1 is completed, it is preferable to remove the solvent and unreacted materials by distillation under reduced pressure.

[0113] In step 2 of preparation method 2, when the reaction product of a hydrocarbon-terminated compound having a leaving group at its terminus and a compound having an amino group and a hydrolyzable silyl group is subjected to an intramolecular cyclization reaction, a basic or acidic compound may be added. Examples of basic catalysts include triethylamine, ethyldiisopropylamine, imidazole, lutidine, DBU, DBN, pyridine, sodium bicarbonate, sodium carbonate, potassium carbonate, sodium methoxide, potassium methoxide, sodium ethoxide, potassium ethoxide, potassium tert-leaf toxide, etc. Examples of acidic catalysts include sulfonic acids such as sulfuric acid, ammonium sulfate, methanesulfonic acid, p-toluenesulfonic acid, dodecylbenzenesulfonic acid, and trifluoromethanesulfonic acid, carboxylic acids such as acetic acid, propionic acid, and trifluoroacetic acid, and their derivatives, as well as ionic nitrogen-containing compound derivatives or inorganic salts such as ammonium salts and pyridinium salts thereof. When adding a basic or acidic compound, the amount used is preferably 0.005 to 10 mol, and particularly 0.01 to 5 mol, per 1 mol of leaving group in the hydrocarbon terminal group-containing compound having a leaving group at its terminus.

[0114] In step 2 of preparation method 2, a solvent can be used when carrying out the reaction. Examples of solvents include aromatic hydrocarbons such as toluene and xylene, aliphatic or alicyclic hydrocarbons such as n-pentane, n-hexane, and cyclohexane, cyclic ether compounds such as tetrahydrofuran and dioxane, ketones such as acetone and methyl ethyl ketone, amides such as dimethylformamide and dimethylacetamide, and alcohols such as methanol, ethanol, and isopropanol. When using a solvent, the amount used is preferably 0.1 to 1,000 parts by mass, more preferably 0.5 to 300 parts by mass, per 100 parts by mass of the reaction product of the hydrocarbon terminal group-containing compound having a leaving group at its terminal and the compound having an amino group and a hydrolyzable silyl group.

[0115] In step 2 of preparation method 2, there are no particular restrictions on the reaction pressure, but it is preferable to carry out the synthesis under reduced pressure when removing a solvent such as alcohol by distillation. The pressure is preferably 10 kPa or less, and more preferably 5 kPa or less.

[0116] In step 2 of preparation method 2, the intramolecular cyclization reaction conditions for the reaction product of a hydrocarbon-terminated compound having a leaving group at its terminus and a compound having an amino group and a hydrolyzable silyl group are preferably a temperature of 20 to 160°C, particularly 25 to 140°C, for 0.5 to 72 hours, and especially 1 to 36 hours.

[0117] Subsequently, it is preferable to remove the remaining material by distillation under reduced pressure.

[0118] Other methods for preparing hydrocarbon terminal group-containing compounds represented by formulas (5) and (6) above include the following: [Preparation Method 3] A hydrocarbon terminal group-containing compound having an alkenyl group and an NH group at its terminus is mixed with a compound having an SiH group and a hydrolyzable silyl group, and a hydrosilylation addition reaction is carried out between the alkenyl group in the hydrocarbon terminal group-containing compound having an alkenyl group and an NH group at its terminus and the SiH group in the compound having an SiH group and a hydrolyzable silyl group in the presence of a hydrosilylation reaction catalyst (Step 1). Subsequently, the reaction product is subjected to an intramolecular cyclization reaction in the presence of a basic or acidic compound, and in some cases under reduced pressure (Step 2), thereby producing hydrocarbon terminal group-containing compounds represented by formulas (5) and (6).

[0119] Examples of hydrocarbon terminal group-containing compounds having an alkenyl group and an NH group at their terminals include compounds represented by the following formulas (5-c) and (6-c). (In the formula, R 1 V, Z, T 1 , Y 1 U', V', k3, k4, k3+k4, j, and m are the same as above.

[0120] Examples of compounds represented by formulas (5-c) and (6-c) are shown below.

[0121] Examples of compounds having an SiH group and a hydrolyzable silyl group include trimethoxysilane, triethoxysilane, triacetoxysilane, and trichlorosilane.

[0122] In step 1 of preparation method 3, the amount of compound having an SiH group and a hydrolyzable silyl group used is preferably 1 to 20 mol, particularly 2 to 15 mol, per 1 mol of alkenyl group in the hydrocarbon terminal group-containing compound having an alkenyl group and an NH group at the terminal.

[0123] In step 1 of preparation method 3, the hydrosilylation reaction catalyst can be the same as that exemplified in step 2 of preparation method 1. Preferably, it is a platinum-based compound such as a vinylsiloxane coordination compound. It is preferable that the platinum-based compound be dissolved in a solvent such as toluene, a lower alcohol, a higher alcohol, or a 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 and an NH group at its terminal ends.

[0124] In step 1 of preparation method 3, a solvent can be used when carrying out the hydrosilylation addition reaction. Examples of solvents are the same as those exemplified in step 2 of 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 alkenyl group and an NH group at its terminals.

[0125] In step 1 of preparation method 3, the hydrosilylation addition reaction conditions are preferably a temperature of 0 to 120°C, particularly 20 to 100°C, for 0.5 to 72 hours, and especially 1 to 36 hours.

[0126] After step 1 is completed, it is preferable to remove the solvent and unreacted materials by distillation under reduced pressure.

[0127] In step 2 of preparation method 3, when the reaction product of a hydrocarbon terminal group-containing compound having an alkenyl group and an NH group at its terminus and a compound having an SiH group and a hydrolyzable silyl group is subjected to an intramolecular cyclization reaction, a basic or acidic compound may be added. Examples of basic or acidic compounds are the same as those exemplified in step 2 of preparation method 2. When adding a basic or acidic compound, the amount used is preferably 0.005 to 10 mol, particularly 0.01 to 5 mol, per 1 mol of NH group in the hydrocarbon terminal group-containing compound having an alkenyl group and an NH group at its terminus.

[0128] In step 2 of preparation method 3, a solvent can be used when carrying out the reaction. Examples of solvents are the same as those exemplified in step 2 of preparation method 2. When using a solvent, the amount used is preferably 0.1 to 1,000 parts by mass, more preferably 1 to 300 parts by mass, per 100 parts by mass of the reaction product of the hydrocarbon terminal group-containing compound having an alkenyl group and an NH group at its terminals and the compound having an SiH group and a hydrolyzable silyl group.

[0129] In step 2 of preparation method 3, there are no particular restrictions on the reaction pressure, but it is preferable to carry out the synthesis under reduced pressure when distilling off a solvent such as alcohol. The pressure is preferably 10 kPa or less, and more preferably 5 kPa or less.

[0130] In step 2 of preparation method 3, the intramolecular cyclization reaction conditions for the reaction product of a hydrocarbon terminal group-containing compound having an alkenyl group and an NH group at its terminals and a compound having an SiH group and a hydrolyzable silyl group are preferably a temperature of 20 to 160°C, particularly 25 to 140°C, for 0.5 to 72 hours, and especially 1 to 36 hours.

[0131] Subsequently, it is preferable to remove the remaining material by distillation under reduced pressure.

[0132] [Surface Treatment Agent] The present invention further provides a non-PFAS surface treatment agent that contains the above-mentioned non-PFAS hydrocarbon terminal group-containing compound as a main component. The surface treatment agent may contain the above-mentioned hydrocarbon terminal group-containing compound, preferably a hydrocarbon terminal group-containing compound represented by formulas (5) and (6), 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 formulas (5) and (6). Furthermore, it is preferable to use a surface treatment agent in which the reactive group of the hydrocarbon terminal group-containing compound is a hydrolyzable silylene group, and in this case, the surface treatment agent may also contain a partially (hydrolyzed) condensate obtained by partially hydrolyzing the hydrolyzable silylene group by a known method.

[0133] 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).

[0134] The surface treatment agent may contain a suitable solvent. Such a solvent is preferably a non-PFAS solvent, 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.

[0135] 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.

[0136] 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 conditions vary depending on the curing method, but for example, in the case of direct coating (brush application, dipping, spraying, etc.), it is preferable to use 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 use a temperature 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 results in faster curing after coating.

[0137] 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.

[0138] The substrate to be 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. SiO2-treated glass and film are particularly preferred.

[0139] The surface treatment agent of the present invention can form a hardened film with high levels of water repellency, slipperiness, dirt-wiping properties, and abrasion resistance.

[0140] [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 above articles, and is therefore particularly useful as a water-repellent layer for touch panel displays, anti-reflective films, eyeglass lenses, and the like.

[0141] Furthermore, the surface treatment agent of the present invention is also useful as an anti-fouling coating for sanitary products such as bathtubs and washbasins, an anti-fouling coating for windows or tempered glass of automobiles, trains, and aircraft, headlamp covers, etc., a water-repellent coating for exterior wall building materials, a stain-preventing coating for kitchen building materials, an anti-fouling and anti-sticker / graffiti coating for telephone booths, a coating to prevent dirt from adhering to works of art, etc., and a stain-preventing coating for compact discs, DVDs, etc.

[0142] Furthermore, the hydrocarbon-end group-containing compounds of the present invention can be suitably used as release agents or paint additives for molds, resin modifiers, flow modifiers or dispersibility modifiers for inorganic fillers, and lubricity enhancers for tapes, films, and the like.

[0143] 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 It is a value calculated by dividing by the molecular weight of the polymer identified by ¹H-NMR analysis. Furthermore, the film thickness is a value measured by a spectroscopic ellipsometry measurement method using a spectroscopic ellipsometer. Room temperature is 25°C.

[0144] [Synthesis Example 1] In a reaction vessel, the following formula (1A) 1.00 g (1.82×10 -3 mol) of the compound represented by, 1.00 g of toluene, and 2.47 g (1.82×10 -2 mol) of trichlorosilane were mixed and aged at 50°C for 24 hours. Thereafter, the solvent and unreacted materials were distilled off under reduced pressure, 1.16 g (1.79×10 -3 mol) of the obtained recovered product, 1.00 g of toluene, and 6.96×10 -3 g of a toluene solution of chloroplatinic acid / vinylsiloxane complex (containing 2.15×10 -8 mol as elemental Pt) were mixed and aged at 80°C for 24 hours. Subsequently, 2.33×10 -2 g of methanol (7.29×10 -4 mol), 0.696 g (6.56×10 -3 mol) of trimethyl orthoformate were mixed and aged at room temperature for 24 hours. Thereafter, the solvent and unreacted materials were distilled off under reduced pressure to obtain 1.10 g of a product.

[0145] The obtained compound was 1 confirmed by ¹H-NMR to have a structure represented by the following formula (1B).

[0146] [Synthesis Example 2] In a reaction vessel, the following formula (2A) 1.00 g (2.63×10 -3 mol) of the compound represented by, 1.00 g of toluene, and 0.798 g (7.89×10 -3 mol) of triethylamine were mixed and aged at room temperature for 4 hours. Subsequently, 3.56 g (2.63×10 -2 mol) of trichlorosilane was added, mixed, and aged at 50°C for 24 hours. Thereafter, the solvent and unreacted materials were distilled off under reduced pressure, followed by filtration, 1.25 g (2.61×10 -3mol), 1.00 g of toluene, and 1.00×10 of a toluene solution of chloroplatinic acid / vinylsiloxane complex -2 g (containing 3.10×10 -8 mol of elemental Pt) were mixed and aged at 80°C for 24 hours. Subsequently, 3.37×10 -2 g (1.05×10 -3 mol) of methanol and 1.00 g (9.42×10 -3 mol) of trimethyl orthoformate were mixed and aged at room temperature for 24 hours. Thereafter, the solvent and unreacted materials were distilled off under reduced pressure to obtain 1.20 g of a product.

[0147] The obtained compound was 1 confirmed by 1H-NMR to have a structure represented by the following formula (2B).

[0148] [Synthesis Example 3] In a reaction vessel, the following formula (3A) 1.00 g (1.35×10 -3 mol) of the compound represented by, 1.00 g of toluene, and 1.82 g (1.35×10 -2 mol) of trichlorosilane were mixed and aged at 50°C for 24 hours. Thereafter, the solvent and unreacted materials were distilled off under reduced pressure, and 1.13 g (1.35×10 -3 mol) of the obtained recovered product, 1.00 g of toluene, and 5.14×10 -3 g (containing 1.59×10 -8 mol of elemental Pt) of a toluene solution of chloroplatinic acid / vinylsiloxane complex were mixed and aged at 80°C for 24 hours. Subsequently, 0.729 g (5.39×10 -3 mol) of trichlorosilane was added and mixed, followed by aging at 50°C for 24 hours. Thereafter, 0.345 g (1.08×10 -2 mol) of methanol was added and mixed, followed by aging at 40°C for 24 hours. Thereafter, the solvent and unreacted materials were distilled off under reduced pressure to obtain 1.21 g of a product.

[0149] The obtained compound was 1 confirmed by 1H-NMR to have a structure represented by the following formula (3B).

[0150] [Synthesis Example 4] In a reaction vessel, the following formula (4A) 1.00 g (2.19 × 10) of the compound represented by -3 mol), 3-aminopropyltrimethoxysilane 0.786 g (4.38 x 10) -3 The mixture (mol) was aged at 120°C for 4 hours. After that, the solvent and unreacted material were removed by vacuum distillation, and the resulting recovered product was 1.29 g (2.15 × 10⁻⁶). -3 1.27 × 10 mol) 28 mass% methanol solution of sodium methoxide -2 g (6.57 x 10 -5 The mixture (mol) was aged at 120°C and 3.0 kPa for 8 hours. The residue was then removed by reduced pressure distillation to obtain 1.25 g of the product.

[0151] The resulting compound was 1 ¹H-NMR confirmed that the structure is represented by the following formula (4B).

[0152] [Synthesis Example 5] In the reaction vessel, the following formula (5A) 1.00 g (1.21 × 10) of the compound represented by -3 mol), toluene 1.00 g, trichlorosilane 1.63 g (1.21 x 10) -2 The mixture (mol) was aged at 50°C for 24 hours. After that, the solvent and unreacted material were removed by vacuum distillation, and 1.10 g (1.18 × 10) of the recovered product was obtained. -3 mol), 1.00 g of toluene, and 4.60 × 10¹⁶ toluene solution of chloroplatinate / vinylsiloxane complex -3 g (as Pt alone: ​​1.42 × 10) -8 (containing mol) was mixed and aged at 80°C for 24 hours. Subsequently, methanol 2.32 × 10 -2 g (7.23 x 10 -4 mol), trimethyl orthoformate 0.691 g (6.51 x 10 -3 The mixture (mol) was allowed to mature at room temperature for 24 hours. After that, the solvent and unreacted materials were removed by distillation under reduced pressure to obtain 1.10 g of the product.

[0153] The resulting compound was 1 ¹H-NMR confirmed that the structure is represented by the following formula (5B).

[0154] [Synthesis Example 6] In the reaction vessel, the following formula (6A) 1.00 g (1.51 × 10) of the compound represented by -3 mol), toluene 1.00 g, trichlorosilane 2.05 g (1.51 x 10 -2 The mixture (mol) was aged at 50°C for 24 hours. After that, the solvent and unreacted material were removed by vacuum distillation, and the resulting recovered product was 1.14 g (1.50 × 10⁻⁶). -3 mol), 1.00 g of toluene, and 5.78 × 10¹⁶ toluene solution of chloroplatinate / vinylsiloxane complex -3 g (as Pt alone, 1.79 × 10) -8 (containing mol) was mixed and aged at 80°C for 24 hours. Subsequently, 0.618 g of acetic anhydride (6.05 x 10) was added. -3 The mixture (mol) was aged at 40°C for 12 hours. After that, the solvent and unreacted materials were removed by vacuum distillation to obtain 1.13 g of product.

[0155] The resulting compound was 1 ¹H-NMR confirmed that the structure is represented by the following formula (6B). (In the formula, Ac represents an acetyl group.)

[0156] [Synthesis Example 7] In the reaction vessel, the following formula (7A) 1.00 g (2.71 × 10) of the compound represented by -3 mol), toluene 1.00 g, trichlorosilane 3.67 g (2.71 x 10 -2 The mixture (mol) was aged at 50°C for 24 hours. After that, the solvent and unreacted material were removed by vacuum distillation and filtration, and the resulting recovered product was 1.24 g (2.65 × 10⁻⁶). -3 mol), 1.00 g of toluene, and 1.04 × 10¹⁶ toluene solution of chloroplatinate / vinylsiloxane complex -2 g (as Pt alone, 3.20 × 10) -8 A mixture containing mol was added and aged at 80°C for 24 hours. Subsequently, methanol 3.48 × 10 -2 g (1.09 × 10 -3 mol), trimethyl orthoformate 1.04 g (9.76 x 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 1.20 g of the product.

[0157] The resulting compound was 1 ¹H-NMR confirmed that the structure is represented by the following formula (7B).

[0158] [Synthesis Example 8] In the reaction vessel, the following formula (8A) 1.00 g (1.30 × 10) of the compound represented by -3 mol), 3-aminopropyltrimethoxysilane 0.467 g (2.60 x 10 -3 The mixture (mol) was heated and aged at 120°C for 4 hours. After that, the solvent and unreacted material were removed by vacuum distillation, and the resulting recovered product was 1.17 g (1.28 × 10⁻¹⁰). -3 1.50 × 10 mol) 28% by mass methanol solution of sodium methoxide -2 g (7.80 x 10 -5 The mixture (mol) was aged at 120°C and 3.0 kPa for 8 hours. The residue was then removed by reduced pressure distillation to obtain 1.11 g of product.

[0159] The resulting compound was 1 ¹H-NMR confirmed that the structure is represented by the following formula (8B).

[0160] [Synthesis Example 9] In the reaction vessel, the following formula (9A) 1.00 g (2.17 × 10) of the compound represented by -3 mol), toluene 1.00 g, trichlorosilane 2.94 g (2.17 x 10 -2 The mixture (mol) was aged at 50°C for 24 hours. After that, the solvent and unreacted material were removed by vacuum distillation, and 1.21 g (2.17 × 10) of the recovered product was obtained. -3 mol), 1.00 g of toluene, and 8.29 × 10¹⁶ toluene solution of chloroplatinate / vinylsiloxane complex -3 g (Pt alone: ​​2.56 × 10) -8 (containing mol) was mixed and aged at 80°C for 24 hours. Subsequently, 2.35 g of trichlorosilane (1.74 x 10) was added. -2 The mixture (mol) was aged at 50°C for 24 hours. Afterwards, methanol 6.26 × 10 -2 g (1.96 × 10 -3mol), trimethyl orthoformate 1.87 g (1.76 x 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 1.39 g of the product.

[0161] The resulting compound was 1 ¹H-NMR confirmed that the structure is represented by the following formula (9B).

[0162] [Synthesis Example 10] In the reaction vessel, the following formula (10A) 1.00 g (1.19 × 10) of the compound represented by -3 mol), toluene 1.00 g, trichlorosilane 1.62 g (1.19 x 10) -2 The mixture (mol) was aged at 50°C for 24 hours. After that, the solvent and unreacted material were removed by vacuum distillation, and 1.08 g (1.15 × 10) of the recovered product was obtained. -3 mol), 1.00 g of toluene, and 4.56 × 10¹⁶ toluene solution of chloroplatinate / vinylsiloxane complex -3 g (as Pt alone: ​​1.41 × 10) -8 (containing mol) was mixed and aged at 80°C for 24 hours. Subsequently, methanol 1.53 × 10 -2 g (4.78 x 10 -4 mol), trimethyl orthoformate 0.456 g (4.30 x 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 1.06 g of the product.

[0163] The resulting compound was 1 ¹H-NMR confirmed that the structure is represented by the following formula (10B).

[0164] [Synthesis Example 11] In the reaction vessel, the following formula (11A) 1.00 g (2.13 × 10) of the compound represented by [formula] -3 mol), toluene 1.00 g, trichlorosilane 2.89 g (2.13 x 10 -2 The mixture (mol) was aged at 50°C for 24 hours. After that, the solvent and unreacted material were removed by vacuum distillation and filtration, and 1.20 g (2.12 × 10) of the recovered product was obtained. -3mol), 1.00 g of toluene, and 8.15 × 10¹⁵ solution of chloroplatinate / vinylsiloxane complex in toluene. -3 g (Pt alone is 2.52 × 10) -8 (containing mol) was mixed and aged at 80°C for 24 hours. Subsequently, methanol 2.74 × 10 -2 g (8.54 x 10 -4 mol), trimethyl orthoformate 0.815 g (7.69 x 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 1.13 g of the product.

[0165] The resulting compound was 1 ¹H-NMR confirmed that the structure is represented by the following formula (11B).

[0166] [Synthesis Example 12] In the reaction vessel, the following formula (12A) 1.00 g (2.65 × 10) of the compound represented by -3 mol), toluene 1.00 g, trimethoxysilane 1.29 g (1.06 x 10) -2 mol), and 1.01 × 10¹⁶ toluene solution of chloroplatinate / vinylsiloxane complex -2 g (3.13 × 10 as Pt alone) -8 The mixture (containing mol) was aged at 80°C for 24 hours. After that, the solvent and unreacted material were removed by vacuum distillation, and 1.61 g of the recovered product (2.58 × 10⁻⁶) was obtained. -3 3.07 × 10 mol) 28 mass% methanol solution of sodium methoxide -2 g (1.59 x 10 -4 The mixture (mol) was aged at 120°C and 3.0 kPa for 8 hours. The residue was then removed by reduced pressure distillation to obtain 1.48 g of product.

[0167] The resulting compound was 1 ¹H-NMR confirmed that the structure is represented by the following formula (12B).

[0168] [Synthesis Example 13] In the reaction vessel, the following formula (13A) 1.00 g (2.74 × 10) of the compound represented by -3mol), 3-aminopropyltrimethoxysilane 0.981 g (5.47 x 10) -3 The mixture (mol) was aged at 120°C for 4 hours. After that, the solvent and unreacted material were removed by vacuum distillation, and the resulting recovered product was 1.37 g (2.71 × 10⁻¹⁰). -3 3.17 × 10 mol) 28 mass% methanol solution of sodium methoxide -2 g (1.64 × 10 -4 The mixture (mol) was aged at 120°C and 3.0 kPa for 8 hours. The residue was then removed by reduced pressure distillation to obtain 1.23 g of product.

[0169] The resulting compound was 1 ¹H-NMR confirmed that the structure is represented by the following formula (13B).

[0170] [Synthesis Example 14] In the reaction vessel, the following formula (14A) 1.00 g (3.24 × 10) of the compound represented by -3 mol), toluene 1.00 g, trichlorosilane 4.39 g (3.24 x 10 -2 The mixture (mol) was aged at 50°C for 24 hours. After that, the solvent and unreacted material were removed by vacuum distillation and filtration, and the resulting recovered product was 1.32 g (3.23 × 10⁻⁶). -3 mol), 1.00 g of toluene, and 1.24 × 10¹⁴ toluene solution of chloroplatinate / vinylsiloxane complex -2 g (3.83 × 10 as Pt alone) -8 (containing mol) was mixed and aged at 80°C for 24 hours. Subsequently, methanol 4.15 × 10 -2 g (1.30 x 10 -3 mol), trimethyl orthoformate 1.24 g (1.17 x 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 1.24 g of the product.

[0171] The resulting compound was 1 ¹H-NMR confirmed that the structure is represented by the following formula (14B).

[0172] [Synthesis Example 15] In the reaction vessel, the following formula (15A) 1.00 g (1.32 × 10) of the compound represented by -3 mol), 3-aminopropyltrimethoxysilane 0.473 g (2.64 x 10 -3 The mixture (mol) was aged at 120°C for 4 hours. After that, the solvent and unreacted material were removed by vacuum distillation, and the resulting recovered product was 1.18 g (1.31 × 10⁻⁶). -3 1.53 × 10 mol) 28% by mass methanol solution of sodium methoxide -2 g (7.92 x 10 -5 The mixture (mol) was aged at 120°C and 3.0 kPa for 8 hours. The residue was then removed by reduced pressure distillation to obtain 1.04 g of product.

[0173] The resulting compound was 1 ¹H-NMR confirmed that the structure is represented by the following formula (15B).

[0174] [Synthesis Example 16] In the reaction vessel, the following formula (16A) 1.00 g (1.76 × 10) of the compound represented by -3 mol), 3-aminopropyltrimethoxysilane 0.630 g (3.51 x 10 -3 The mixture (mol) was aged at 120°C for 4 hours. After that, the solvent and unreacted material were removed by vacuum distillation, and the resulting recovered product was 1.23 g (1.72 × 10⁻¹⁰). -3 2.03 × 10 mol) 28 mass% methanol solution of sodium methoxide -2 g (1.04 × 10 -4 The mixture (mol) was aged at 120°C and 3.0 kPa for 8 hours. The residue was then removed by reduced pressure distillation to obtain 1.15 g of product.

[0175] The resulting compound was 1 ¹H-NMR confirmed that the structure is represented by the following formula (16B).

[0176] [Example 1] The compound obtained in Synthesis Example 1 was dissolved in toluene to a concentration of 20% by mass to prepare a surface treatment agent.

[0177] [Example 2] The compound obtained in Synthesis Example 2 was dissolved in isooctane to a concentration of 20% by mass to prepare a surface treatment agent.

[0178] [Example 3] The compound obtained in Synthesis Example 4 was dissolved in dibutyl ether to a concentration of 20% by mass to prepare a surface treatment agent.

[0179] [Example 4] The compound obtained in Synthesis Example 6 was dissolved in dibutyl ether to a concentration of 20% by mass to prepare a surface treatment agent.

[0180] [Example 5] The compound obtained in Synthesis Example 8 was dissolved in toluene to a concentration of 10% by mass to prepare a surface treatment agent.

[0181] [Example 6] The compound obtained in Synthesis Example 9 was dissolved in isononane to a concentration of 20% by mass to prepare a surface treatment agent.

[0182] [Example 7] The compound obtained in Synthesis Example 11 was dissolved in toluene to a concentration of 90% by mass to prepare a surface treatment agent.

[0183] [Example 8] The compound obtained in Synthesis Example 12 was dissolved in isooctane to a concentration of 10% by mass to prepare a surface treatment agent.

[0184] [Example 9] The compound obtained in Synthesis Example 13 was dissolved in propylene glycol monomethyl ether acetate to a concentration of 30% by mass to prepare a surface treatment agent.

[0185] [Example 10] The compound obtained in Synthesis Example 15 was dissolved in dibutyl ether to a concentration of 50% by mass to prepare a surface treatment agent.

[0186] [Example 11] The compound obtained in Synthesis Example 16 was dissolved in a hexane / isooctane mixed solution (mass ratio 50 / 50) to a concentration of 20% by mass to prepare a surface treatment agent.

[0187] [Example 12] The compound obtained in Synthesis Example 1 was used as a surface treatment agent without dilution.

[0188] [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.

[0189] [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.

[0190] [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.

[0191] [Comparative Example 4] The following formula (D') A surface treatment agent was prepared by dissolving the compound represented by [formula] in toluene to a concentration of 20% by mass.

[0192] Formation of a cured film for rapid curing evaluation Glass (Corning Gorilla Glass (Model No.: Gorilla III, Size: 100 mm x 50 mm x 0.7 mm)) whose outermost surface was coated with SiO2 to a thickness of 10 nm under the following conditions was subjected to vacuum deposition (equipment: ULVAC KIKO, Model No.: VTR-350M) of each surface treatment agent prepared in the above examples and comparative examples (processing conditions: pressure: 2.0 x 10 -2 A rapidly curing film for evaluation of fast curing properties was formed by curing for 30 minutes in an atmosphere of Pa, heating temperature: 700°C, 25°C, and relative humidity of 50%. [SiO2 layer deposition conditions] Deposition apparatus: OTFC-1300 (Optolan Co., Ltd.) Deposition material: SiO2 Deposition chamber pressure: 0.015 Pa Deposition rate: 0.8 nm / s Deposition film thickness: 10 nm

[0193] The rapid curing properties of the glass with the above-mentioned cured coating were evaluated using the method described below.

[0194] Evaluation of Rapid Curing Properties The contact angle (hydrophobicity) of the cured 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 are shown in Table 1. In this invention, a good (hydrophobic) water contact angle is defined as 90° or higher, and those with a result of 90° or higher are considered to have rapid curing properties (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

[0195] Formation of various hardened coatings for evaluation Glass (Corning Gorilla Glass (Model No.: Gorilla III, Size: 100 mm x 50 mm x 0.7 mm)) whose outermost surface was coated with SiO2 to a thickness of 10 nm under the following conditions was subjected to vacuum deposition (equipment: ULVAC KIKO, Model No.: VTR-350M) of each surface treatment agent prepared in the above examples and comparative examples (processing conditions: pressure: 2.0 x 10 -2 Cured films with thicknesses of 3-5 nm for various evaluation purposes were formed by curing in an atmosphere of 150°C (heating temperature: 700°C) for 30 minutes. [SiO2 layer deposition conditions] Deposition apparatus: OTFC-1300 (Optolan Co., Ltd.) Deposition material: SiO2 Deposition chamber pressure: 0.015 Pa Deposition rate: 0.8 nm / s Deposition film thickness: 10 nm

[0196] The glass coated with the above-described hardened film was evaluated for water repellency, slipperiness, dirt-wiping ability, and abrasion resistance using the method shown below.

[0197] 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 are shown in Table 1. In this invention, a good (water-repellent) water contact angle was defined as 90° or higher (the same applies hereafter). [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

[0198] 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)

[0199] 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 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 Properties Evaluation Criteria] A: 4 rubbings or less B: 5 rubbings or more C: Ink cannot be wiped off

[0200] Abrasion Resistance Evaluation The glass with the hardened coating prepared as described above was rubbed every 500 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 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 (number of times the water contact angle fell below 80°) are shown in Table 1. [Steel Wool Abrasion Resistance Test Conditions] Steel wool: Bonster #0000 Contact area: 1 cm 2 Distance traveled (one way): 40 mm; Speed: 4,800 mm / min; Load: 500 gf / cm 2

[0201] Examples 1 to 12 showed improved hydrolysis rates and faster adhesion to the substrate, resulting in a quicker development of the water contact angle. Furthermore, water repellency was achieved, along with good slipperiness, dirt-wiping properties, and abrasion resistance. Comparative Examples 1 to 4 showed longer hydrolysis times and a slower development of the water contact angle. As described above, the surface treatment agents in the examples demonstrated that, in vapor deposition coating, a cured film of a non-fluorinated hydrocarbon-terminated compound with rapid curing properties and excellent water repellency, slipperiness, dirt-wiping properties, and abrasion resistance could be obtained.

[0202]

[0203] [Example 13] The compound obtained in Synthesis Example 1 was dissolved in dibutyl ether to a concentration of 0.1% by mass to prepare a surface treatment agent.

[0204] [Example 14] The compound obtained in Synthesis Example 3 was dissolved in toluene to a concentration of 0.1% by mass to prepare a surface treatment agent.

[0205] [Example 15] The compound obtained in Synthesis Example 5 was dissolved in dibutyl ether to a concentration of 0.1% by mass to prepare a surface treatment agent.

[0206] [Example 16] The compound obtained in Synthesis Example 7 was dissolved in toluene to a concentration of 0.1% by mass to prepare a surface treatment agent.

[0207] [Example 17] The compound obtained in Synthesis Example 10 was dissolved in a hexane / isooctane mixed solution (mass ratio 50 / 50) to a concentration of 0.1% by mass to prepare a surface treatment agent.

[0208] [Example 18] The compound obtained in Synthesis Example 12 was dissolved in toluene to a concentration of 0.1% by mass to prepare a surface treatment agent.

[0209] [Example 19] The compound obtained in Synthesis Example 14 was dissolved in toluene to a concentration of 0.1% by mass to prepare a surface treatment agent.

[0210] [Example 20] The compound obtained in Synthesis Example 15 was dissolved in toluene to a concentration of 0.1% by mass to prepare a surface treatment agent.

[0211] [Example 21] The compound obtained in Synthesis Example 16 was dissolved in toluene to a concentration of 0.1% by mass to prepare a surface treatment agent.

[0212] [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 0.1% by mass.

[0213] [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 0.1% by mass.

[0214] [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 0.1% by mass.

[0215] [Comparative Example 8] A surface treatment agent was prepared by dissolving the compound represented by the above formula (D') in dibutyl ether to a concentration of 0.1% by mass.

[0216] For the rapid curing evaluation, a hardened film was formed on a glass sheet (Corning Gorilla Glass, part number: Gorilla III, size: 100 mm x 50 mm x 0.7 mm) under the following conditions. Each surface treatment agent prepared in the above examples and comparative examples was spray-coated and cured for 30 minutes at 25°C and 50% relative humidity in an atmosphere of 80°C and 80% relative humidity to form a hardened film for rapid curing evaluation with a thickness of 3 to 5 nm. [Spray coating conditions] Atmosphere: 25°C / 50% Nozzle distance: 50 mm Air pressure: 150 kPa Speed: 300 mm / min Pitch: 5 mm

[0217] The rapid curing properties of the glass with the above-mentioned cured coating were evaluated using the method described below.

[0218] Evaluation of Rapid Curing Properties The contact angle (hydrophobicity) of the cured 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 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

[0219] Various evaluation-grade hardened coatings were formed on glass (Corning Gorilla Glass (product code: Gorilla III, size: 100 mm x 50 mm x 0.7 mm)) under the following conditions: each surface treatment agent prepared in the above examples and comparative examples was spray-coated and cured for 30 minutes in a 150°C atmosphere to form various evaluation-grade hardened coatings with a thickness of 3 to 5 nm. [Spray coating conditions] Atmosphere: 25°C / 50% Nozzle distance: 50 mm Air pressure: 150 kPa Speed: 300 mm / min Pitch: 5 mm

[0220] The glass coated with the above-described hardened film was evaluated for water repellency, slipperiness, dirt-wiping ability, and abrasion resistance using the method shown below.

[0221] 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 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

[0222] 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)

[0223] 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 rubs required to remove the ink was evaluated according to the following criteria. The results are shown in Table 2. [Stain Removal Properties Evaluation Criteria] A: 4 rubs or less B: 5 rubs or more C: Ink cannot be wiped off

[0224] Abrasion Resistance Evaluation The glass with the hardened coating prepared as described above was rubbed every 500 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 the water contact angle fell below 80° was recorded to evaluate abrasion resistance. The test environment conditions were 25°C and 40% relative humidity. The results (number of times the water contact angle fell below 80°) are shown in Table 2. [Steel Wool Abrasion Resistance Test Conditions] Steel wool: Bonster #0000 Contact area: 1 cm 2 Distance traveled (one way): 40 mm; Speed: 4,800 mm / min; Load: 500 gf / cm 2

[0225] Examples 13 to 21 showed improved hydrolysis rates and faster adhesion to the substrate, resulting in a quicker development of the water contact angle. Furthermore, water repellency was achieved, along with good slipperiness, dirt-wiping properties, and abrasion resistance. Comparative Examples 5 to 8 showed longer hydrolysis times and slower development of the water contact angle. As described above, the surface treatment agents in these examples demonstrated that even with spray coating, a cured film of a non-fluorinated hydrocarbon-terminated compound containing compounds could be obtained that exhibited rapid curing properties and high levels of water repellency, slipperiness, dirt-wiping properties, and abrasion resistance.

[0226]

Claims

1. A hydrocarbon end group-containing compound having a monovalent unsubstituted or substituted hydrocarbon group having 10 or more carbon atoms, which may contain at least one selected from oxygen, sulfur, nitrogen, and silicon atoms at the end of the molecular chain, and which may be linear, cyclic, or a combination thereof, and a monovalent or divalent silacycloalkane-type reactive group.

2. The hydrocarbon terminal group-containing compound according to claim 1, wherein the monovalent hydrocarbon group and the monovalent or divalent silacycloalkane-type reactive group are bonded directly or via a polyvalent linking group.

3. The hydrocarbon terminal group-containing compound according to claim 1, wherein the monovalent hydrocarbon group has 10 or more carbon atoms and 60 or fewer carbon atoms.

4. The hydrocarbon terminal group-containing compound according to claim 1, wherein the monovalent hydrocarbon group is linear.

5. The hydrocarbon terminal group-containing compound according to claim 1, wherein the ring member number of the monovalent or divalent silacycloalkane-type reactive group is 3 to 20.

6. The above monovalent or divalent silacicloalkane-type reactive group is one of the following general formulas (1) to (3) (In the formula, U 1 is a nitrogen atom or a trivalent organic group, U 2 A 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 an oxygen atom, a nitrogen atom, and a sulfur atom; Z is a carbon atom, a silicon atom, a nitrogen atom, or a trivalent or tetravalent organic group; W is a single bond, or an oxygen atom, a sulfur atom, or an amino group which may have a divalent hydrocarbon group; A is a divalent reactive silylene group; T is a divalent hydrocarbon group which may interpose at least one selected from an oxygen atom, a nitrogen atom, a sulfur atom, and a silicon atom; 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; A' is independently a monovalent reactive silyl group; j is 0 or 1; m is 1 or 2.

7. The hydrocarbon terminal group-containing compound according to claim 6, wherein the total number of atoms forming a cyclic structure in formulas (1) to (3) above is 3 to 20.

8. A in the above equations (1) to (3) is the following general equation (4) A hydrocarbon terminal group-containing compound according to claim 6, wherein the group is represented by (wherein R is an alkyl group or phenyl group having 1 to 4 carbon atoms, X is independently a hydroxyl group or a hydrolyzable group, and n is 1 or 2).

9. The following general formula (5) or (6) (In the formula, R 1 is an unsubstituted or substituted monovalent hydrocarbon group having 10 to 60 carbon atoms, which may independently contain at least one selected from oxygen, sulfur, nitrogen, and silicon atoms, and may be linear, cyclic, or a combination thereof; U and U' are each a carbon atom, silicon atom, nitrogen atom, or a trivalent or tetravalent organic group; V and V' are single bonds or divalent hydrocarbon groups which may contain at least one selected from oxygen, nitrogen, and sulfur atoms; Z is a carbon atom, silicon atom, nitrogen atom, or a trivalent or tetravalent organic group; and W is an acid which may have a single bond or a divalent hydrocarbon group. The hydrocarbon terminal group-containing compound according to claim 1, wherein A is a divalent reactive silylene group, T is 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, 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 monovalent reactive silyl group which is k1 is 1 or 2, k2 is 0 or 1, k1 + k2 is 1 or 2, k3 is an integer from 1 to 3, k4 is 0 or 1, k3 + k4 is an integer from 1 to 3, k5 is 0 or 1, j is 0 or 1, and m is 1 or 2.

10. In formula (5) or (6) above, R 1 However, the following formula (In the formula, R A Q is an unsubstituted or substituted monovalent hydrocarbon group having 10 to 60 carbon atoms, which may be linear, cyclic, or a combination thereof, and Q is an oxygen atom, a sulfur atom, a diorganosilylene group, a sylalkylene structure or sylarylene structure, and a linear or branched or cyclic divalent organopolysiloxane residue having 2 to 10 silicon atoms, or 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, 2 Q' is a divalent group selected from the group consisting of valence nitrogen-containing heterocyclic groups, 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 or branched or cyclic trivalent organopolysiloxane residue having 2 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, a linear or branched or cyclic tetravalent organopolysiloxane residue having 2 to 10 silicon atoms, and R B R is a divalent hydrocarbon group having 1 to 50 carbon atoms, which may be independently single-bonded, linear, or cyclic, and C The hydrocarbon terminal group-containing compound according to claim 9, wherein is a hydrogen atom, and p is an integer from 0 to 10, provided that the total number of carbon atoms in each structure is 60 or less.

11. A surface treatment agent comprising a hydrocarbon terminal group-containing compound 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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