Hydrocarbon terminal group-containing oligomer, production method therefor, surface treatment agent, and article

Abstract

This hydrocarbon terminal group-containing oligomer for vapor deposition has a C1-C40 monovalent hydrocarbon group which may be linear, branched, or cyclic, or in a combined form thereof, has, as a hydrolyzable group, a monovalent hydrolyzable silyl group having a methoxy group or an ethoxy group, has, as a monomer component, only a hydrocarbon terminal group-containing silane compound having at least two methoxy groups or ethoxy groups in a molecule, and has an average degree nNMR of polymerization in terms of NMR of greater than 1 and at most 100. The hydrocarbon terminal group-containing oligomer can form a cured film having excellent water repellency and abrasion resistance.

Description

hydrocarbon-terminated oligomers, methods for producing the same, surface treatment agents, and articles.

[0001] The present invention relates to hydrocarbon-terminated oligomers, and more particularly to hydrocarbon-terminated oligomers for vapor deposition that form a coating with excellent water repellency and abrasion resistance, a method for producing the same, a surface treatment agent containing the hydrocarbon-terminated oligomer for vapor deposition, and an article having a cured coating formed by 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 grime. 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, conventional water- and oil-repellent layers have the problem that while they have high water- and oil-repellent properties and are excellent at wiping away dirt, they do not have sufficient abrasion resistance.

[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, fluorine-based compounds have the characteristic of being difficult to decompose in nature and tend to accumulate in the environment, which has led to a demand for the development of surface protective agents for non-fluorine-based materials.

[0007] Therefore, International Publication No. 2019 / 82583 (Patent Document 7) proposes a surface treatment agent that does not use fluorine groups. However, there is a growing demand for coatings formed by such surface treatment agents that can withstand harsher operating environments, and improved wear resistance is desired.

[0008] For coating substrates such as glass with surface treatment agents, vapor deposition is primarily used from a safety perspective. However, in vapor deposition, if the molecular weight or evaporation start temperature of the surface treatment agent is small, it may re-evaporate after being coated onto the substrate, causing vapor deposition failure. In such cases, the water-repellent and abrasion-resistant properties required of the surface treatment agent may not be achieved. As a method to improve the vapor deposition characteristics of surface treatment agents, it is conceivable to increase the molecular weight of the silane coupling agent, which is a surface treatment agent, by co-hydrolysis condensation polymerization or partial hydrolysis condensation.

[0009] Japanese Patent Publication No. 5950399 (Patent Document 8) reports that by applying a solution obtained by co-hydrolysis and condensation polymerization of an organic silane and a metal alkoxide in a solvent containing an organic solvent, water, and a catalyst to the surface of a substrate, the mobility of functional groups derived from the organic silane on the film surface can be controlled, thereby imparting excellent water repellency, slipperiness, droplet removal properties, and anti-fogging properties to the substrate surface. However, the coating method described in this document is a spin coating method, and abrasion resistance is not evaluated.

[0010] 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, International Publication No. 2019 / 82583, Japanese Patent No. 5950399

[0011] The present invention has been made in view of the above circumstances, and aims to provide a non-fluorine-based (i.e., one that does not contain fluorine atoms in the molecule) hydrocarbon-terminated oligomer with excellent vapor deposition coating properties that can form a cured film with excellent water repellency and abrasion resistance, a method for producing the same, a substantially non-fluorine-based surface treatment agent containing the condensate, and an article surface-treated with the surface treatment agent.

[0012] The present inventors, after diligent research to solve the above objective, have found a monomer component consisting only of hydrocarbon terminal group-containing silane compounds having a monovalent hydrocarbon group having 1 to 40 carbon atoms, which may be linear, branched, cyclic, or a combination thereof, and a monovalent hydrolyzable silyl group having a methoxy group or an ethoxy group as a hydrolyzable group, and having at least two of the methoxy group or ethoxy group in the molecule, with an NMR-calculated average degree of polymerization n NMR However, if the hydrocarbon-end group-containing oligomer for vapor deposition has a polymerization ratio greater than 1 and less than or equal to 100, it is a hydrolyzable condensate with an appropriate degree of polymerization. As a result, coating defects such as re-evaporation or non-evaporation do not occur during vapor deposition coating. Furthermore, because it becomes a condensate, intermolecular interactions are increased, and the hydrocarbon groups that are unevenly distributed on the coated surface tend to be densely oriented. Therefore, it has been found that a cured film with superior water repellency and abrasion resistance (especially resistance to eraser abrasion) can be formed compared to a hydrocarbon-end group-containing silane compound alone, leading to the present invention.

[0013] Accordingly, the present invention provides the following hydrocarbon terminal group-containing oligomers, methods for producing the same, surface treatment agents, and articles. [1] A hydrocarbon terminal group-containing silane compound having only a hydrocarbon terminal group having a monovalent hydrocarbon group having 1 to 40 carbon atoms, which may be linear, branched, cyclic, or a combination thereof, and a monovalent hydrolyzable silyl group having a methoxy group or an ethoxy group as a hydrolyzable group, and having at least two of the methoxy group or ethoxy group in the molecule, wherein the monomer component is the hydrocarbon terminal group-containing silane compound, with an average degree of polymerization n in NMR terms. NMR However, an oligomer containing hydrocarbon terminal groups for vapor deposition, which is greater than 1 and less than or equal to 100. [2] The monomer component is the following general formula (1) The hydrocarbon terminal group-containing oligomer for vapor deposition described in [1], which is a hydrocarbon terminal group-containing silane compound represented by the formula: (wherein R is a monovalent hydrocarbon group having 1 to 40 carbon atoms, which may be linear, branched, cyclic, or a combination thereof; Z is a divalent linking functional group independently comprising at least one selected from an oxygen atom, a nitrogen atom, a sulfur atom, and a silicon atom; Y is a divalent hydrocarbon group having 1 to 30 carbon atoms, which may be linear, branched, cyclic, or a combination thereof; W is a single bond, a carbon atom, a silicon atom, a nitrogen atom, or a 3 to 5 valent organic group; A is a monovalent hydrolyzable silyl group having a methoxy group or an ethoxy group; k1 is an integer from 0 to 3; k2 is an integer from 1 to 4; k3 is 0 or 1. However, there are at least two methoxy groups or ethoxy groups in one molecule.) [3] The hydrocarbon-terminated oligomer for vapor deposition according to [2], wherein Z is independently a divalent group selected from 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, divalent nitrogen-containing heterocyclic group, diorganosilylene group, and divalent organopolysiloxane residues having 2 to 10 silicon atoms in a linear chain or 3 to 10 silicon atoms in a branched or cyclic configuration. [4] The hydrocarbon-terminated oligomer for vapor deposition according to [2], wherein Y is independently a group of the following general formula (2) (In the formula, R 1 R is a monovalent hydrocarbon group having 1 to 10 carbon atoms, which may be linear, branched, cyclic, or a combination thereof. 2 is a divalent cyclic hydrocarbon group having 3 to 10 carbon atoms, which may independently have substituents. a is an integer from 0 to 30, b is an integer from 0 to 15, c is an integer from 0 to 10, and d is an integer from 0 to 6, and the sum of a, b, c, and d is an integer such that the sum of carbon atoms in formula (2) is 1 to 30. Each repeating unit shown in the parentheses a, b, c, and d may be randomly bonded.) A hydrocarbon terminal group-containing oligomer for vapor deposition as described in [2] or [3]. [5] In formula (1), W is a single bond, a carbon atom, a silicon atom, a nitrogen atom, a trivalent or tetravalent cyclic hydrocarbon group having 6 to 8 carbon atoms, -SiR10 = (R 10 represents 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 11 = (R 11 represents a trivalent group represented by a hydrogen atom, a hydroxyl group, or an alkyl group having 1 to 3 carbon atoms), a linear organopolysiloxane residue having 2 to 10 silicon atoms or a branched or cyclic trivalent to pentavalent organopolysiloxane residue having 3 to 10 silicon atoms, a trivalent amide group, a trivalent carbamate group, a trivalent or tetravalent urea group, and a trivalent or tetravalent nitrogen-containing heterocyclic group-containing group, which is a trivalent to pentavalent group selected from the group consisting of [2] to [4] of the hydrocarbon terminal group-containing oligomer for vapor deposition. [6] The evaporation start temperature at 5×10 -2 Pa or higher is 90 °C or higher, and the hydrocarbon terminal group-containing oligomer for vapor deposition according to any one of [1] to [5]. [7] A surface treatment agent containing the hydrocarbon terminal group-containing oligomer for vapor deposition according to any one of [1] to [6]. [8] An article having a cured film formed by the surface treatment agent according to [7]. [9] The hydrocarbon terminal group-containing silane compound represented by the above general formula (1), water, a catalyst, and an organic solvent as an optional component are mixed, and after allowing a partial hydrolysis-condensation reaction to proceed, the catalyst is deactivated, and the catalyst and reaction by-products generated after the reaction are distilled off, which is the method for producing a hydrocarbon terminal group-containing oligomer for vapor deposition according to [2].

[10] The amount of water used is more than 0 mol and 10 mol or less per 1 mol of the hydrolyzable silyl group in the hydrocarbon terminal group-containing silane compound, and the method for producing a hydrocarbon terminal group-containing oligomer for vapor deposition according to [9].

[11] The catalyst is an inorganic acid or an organic acid, or an inorganic base or an organic base, and the method for producing a hydrocarbon terminal group-containing oligomer for vapor deposition according to [9] or

[10] .

[12] The organic solvent is an alcohol, and the method for producing a hydrocarbon terminal group-containing oligomer for vapor deposition according to any one of [9] to

[11] .

[13] [1] The following general formula (3) (wherein, Z, Y, W, A, k2, k3 are the same as those in the above formula (1), E is a monovalent functional group capable of reacting with T described later and linking, and Y<00参照:https: / / www.patentguru.com / ja / 2019011177.html 2[1] is a divalent hydrocarbon group having 1 to 30 carbon atoms, which may be linear, branched, cyclic, or a combination thereof, and k4 is an integer from 0 to 2. ) A functional group-containing silane compound represented by ) is mixed with water, a catalyst, and optionally an organic solvent, and a partial hydrolysis condensation reaction is carried out, after which the catalyst is deactivated, and the catalyst and reaction by-products produced after the reaction are removed by distillation to obtain a functional group-containing oligomer. [2] The functional group-containing oligomer obtained in the above step is mixed with the following general formula (4a), (4b), or (4c) (In the formula, R, Z, and Y are the same as in formula (1) above, T is a monovalent functional group that can react with and link with E as described above, and Y 3A is a divalent hydrocarbon group having 1 to 28 carbon atoms, which may be linear, branched, cyclic, or a combination thereof, and R' is a monovalent hydrocarbon group having 1 to 38 carbon atoms, which may be linear, branched, cyclic, or a combination thereof. k5 is an integer from 0 to 2, the sum of k4 and k5 is an integer from 0 to 2, k6 is 0 or 1, the sum of k4 and k6 is 0 or 1.) A method for producing a hydrocarbon end group-containing oligomer for vapor deposition according to [2], comprising the step of reacting with a functional group-containing compound represented by ) to extend the chain length.

[14] A method for producing a hydrocarbon-terminal group-containing oligomer for vapor deposition according to

[13] , wherein E of formula (3) and T of formula (4a), (4b), or (4c) are a monovalent functional group that reacts and links with each other, and the pair (E, T) is any of (terminal olefin group, thiol group), (thiol group, terminal olefin group), (hydroxyl group, isocyanate group), (amino group, isocyanate group), (ester group, hydroxyl group), (hydroxyl group, ester group), (ester group, amino group), (amino group, ester group), (carboxyl group, hydroxyl group), (hydroxyl group, carboxyl group), (carboxyl group, amino group), (amino group, carboxyl group), and (leaving group, hydroxyl group).

[15] A method for producing a hydrocarbon-terminal group-containing oligomer for vapor deposition according to

[13] or

[14] , wherein the amount of water used is greater than 0 mol and 3 mol or less per 1 mol of hydrolyzable silyl group in the hydrocarbon-terminal group-containing silane compound.

[16] A method for producing a hydrocarbon-terminated oligomer for vapor deposition according to any one of

[13] to

[15] , wherein the catalyst is an inorganic acid or an organic acid, or an inorganic base or an organic base.

[17] A method for producing a hydrocarbon-terminated oligomer for vapor deposition according to any one of

[13] to

[16] , wherein the organic solvent is an alcohol.

[18] A hydrocarbon-terminated oligomer represented by the following average formula (5). (In the formula, R is a monovalent hydrocarbon group having 1 to 40 carbon atoms, which may be linear, branched, cyclic, or a combination thereof; Z is a divalent linking functional group containing at least one atom independently selected from oxygen, nitrogen, sulfur, and silicon atoms; Y is a divalent hydrocarbon group having 1 to 30 carbon atoms, which may be linear, branched, cyclic, or a combination thereof; k1 is an integer from 0 to 3; R X(wherein n is independently a methyl group, an ethyl group, or a hydrogen atom, and n is an average number greater than 1 and less than or equal to 100.)

[19] A hydrocarbon-terminated oligomer according to

[18] for vapor deposition.

[20] A surface treatment agent comprising the hydrocarbon-terminated oligomer according to

[18] or

[19] .

[21] An article having a cured film formed by the surface treatment agent according to

[20] .

[0014] The surface treatment agent containing hydrocarbon terminal group-containing oligomers of the present invention exhibits excellent vapor deposition coating properties, and articles surface-treated with this surface treatment agent have excellent water repellency and abrasion resistance.

[0015] [Hydroxide-Ended Group-Containing Oligomer] The hydrocarbon-ended group-containing oligomer for vapor deposition of the present invention is non-fluorinated (having no fluorine atoms in the molecule), may be linear, branched, cyclic, or a combination thereof, and has a monovalent hydrocarbon group having 1 to 40 carbon atoms, and a monovalent hydrolyzable silyl group having a methoxy group or an ethoxy group as a hydrolyzable group, and the monomer component consists only of hydrocarbon-ended group-containing silane compounds having at least two of the methoxy group or ethoxy group in the molecule, with an average degree of polymerization n in NMR terms. NMR However, it is characterized by being greater than 1 and less than or equal to 100. The surface treatment agent containing the hydrocarbon terminal group-containing oligomer of the present invention is suitable for vapor deposition coating.

[0016] In this invention, "monomer" refers to the smallest unit that constitutes an oligomer, and is a component used in preparing an oligomer.

[0017] Furthermore, in this invention, "oligomer" refers to a polymer with a relatively lower molecular weight than a polymer, in which multiple molecules of the same type are bonded together, but monomers may also be included as long as the average degree of polymerization is greater than 1.

[0018] The hydrocarbon-terminated oligomer of the present invention has an average degree of polymerization n (based on NMR). NMRHowever, it is sufficient if the average degree of polymerization is greater than or equal to 100, preferably 1.2 to 50, more preferably 1.2 to 30, and even more preferably 1.5 to 20. If the average degree of polymerization is within the above range, when used as a surface treatment agent, coating defects such as re-evaporation or non-evaporation will not occur in vapor deposition coating, and the intermolecular interactions will increase as a condensate is formed, making it easier for hydrocarbon groups unevenly distributed on the coated surface to be densely oriented, thus forming a cured film with excellent water repellency and eraser abrasion resistance.

[0019] NMR-based average degree of polymerization n of hydrocarbon-terminated oligomers NMR As a method for calculating n, when the hydrocarbon terminal group in the monomer component is a linear alkyl group and there are three methoxy groups for each hydrolyzable silyl group, it is calculated using the proton ratio of the remaining methoxy groups to the terminal methyl groups in the hydrocarbon terminal group in the hydrocarbon terminal group oligomer. When the NMR integral value of the methoxy group is set to 3, v is the NMR integral value of the methoxy group, and when the number of hydrolyzable silyl groups in the monomer component is L (L is an integer from 1 to 4, preferably 1), n NMR = 6L / (v-3L). This is based on the following idea: When a hydrocarbon terminal group-containing oligomer is an average n-mer (for example, represented by the average formula (5) described later), the ratio of the total number of protons of the terminal methyl groups in the hydrocarbon terminal group to the total number of protons of the remaining methoxy groups is equal to the ratio of the NMR integral values. Therefore, the ratio of the total number of protons of the terminal methyl groups to the total number of protons of the remaining methoxy groups = 3n:L(3n+6) = 3:v, and solving this for n yields the above formula.

[0020] Furthermore, the NMR-calculated average degree of polymerization n of hydrocarbon-terminated oligomers NMRAs a method for calculating n, when the hydrocarbon terminal group in the monomer component is a linear alkyl group and there are three ethoxy groups for each hydrolyzable silyl group, it is calculated using the proton ratio of the remaining ethoxy groups to the terminal methyl groups in the hydrocarbon terminal group in the hydrocarbon terminal group oligomer. When the NMR integral value of the terminal methyl group in the hydrocarbon terminal group is set to 3, the NMR integral value of the methylene group adjacent to the oxygen atom in the remaining ethoxy group is w, and when the number of hydrolyzable silyl groups in the monomer component is L (L is an integer from 1 to 4, preferably 1), n NMR = 4L / (w-2L). This is based on the fact that when the hydrocarbon terminal group-containing oligomer is an average n-mer (for example, one represented by the average formula (5) described later), the total number of protons of the terminal methyl groups in the hydrocarbon terminal group : the total number of protons of the methylene groups adjacent to the oxygen atom in the remaining ethoxy group = 3n:L(2n+4) = 3:w.

[0021] Furthermore, the NMR-calculated average degree of polymerization n of hydrocarbon-terminated oligomers NMR As a method for calculating n, when the hydrocarbon terminal group in the monomer component is a linear alkyl group and there are two methoxy groups for each hydrolyzable silyl group, it is calculated using the proton ratio of the remaining methoxy groups to the terminal methyl groups in the hydrocarbon terminal group in the hydrocarbon terminal group oligomer, and when the NMR integral value of the terminal methyl group in the hydrocarbon terminal group is set to 3, the NMR integral value of the remaining methoxy group is v', and when the number of hydrolyzable silyl groups in the monomer component is L (L is an integer from 1 to 4, preferably 1), n NMR This is based on the fact that when a hydrocarbon terminal group-containing oligomer is an average n-mer, the total number of protons of the terminal methyl groups : the total number of protons of the remaining methoxy groups (in this case, the number of protons of the methyl groups in the remaining methoxy groups that do not form oligomers at both ends is 6 for each hydrolyzable silyl group) = 3n : 6L = 3 : v'.

[0022] Furthermore, the NMR-calculated average degree of polymerization n of hydrocarbon-terminated oligomers NMRAs a method for calculating n, when the hydrocarbon terminal group in the monomer component is a linear alkyl group and there are two ethoxy groups for each hydrolyzable silyl group, it is calculated using the proton ratio of the remaining ethoxy groups to the terminal methyl groups in the hydrocarbon terminal group in the hydrocarbon terminal group oligomer. When the NMR integral value of the terminal methyl group in the hydrocarbon terminal group is set to 3, the NMR integral value of the methylene group adjacent to the oxygen atom in the remaining ethoxy group is w', and the number of hydrolyzable silyl groups in the monomer component is L (L is an integer from 1 to 4, preferably 1), then n NMR This is based on the fact that when a hydrocarbon terminal group-containing oligomer is an average n-mer, the total number of protons of the terminal methyl groups : the total number of protons of the remaining ethoxy groups (in this case, for each hydrolyzable silyl group, the number of protons of the methylene group adjacent to the oxygen atom in the remaining ethoxy group that does not form an oligomer at both ends is 4) = 3n : 4L = 3 : w'.

[0023] Furthermore, the NMR-calculated average degree of polymerization n of hydrocarbon-terminated oligomers NMR As a method for calculating n, when the hydrocarbon terminal group in the monomer component is a linear alkyl group and there is one methoxy group for each hydrolyzable silyl group, it is calculated using the proton ratio of the remaining methoxy group to the terminal methyl group in the hydrocarbon terminal group in the hydrocarbon terminal group oligomer. When the NMR integral value of the terminal methyl group in the hydrocarbon terminal group is set to 3, the NMR integral value of the remaining methoxy group is v'', and when the number of hydrolyzable silyl groups in the monomer component is L (L is an integer from 2 to 4, preferably 2 or 3), n NMR = 6 / (v''-3L+6). This is based on the fact that when a hydrocarbon terminal group-containing oligomer is an average n-mer, the total number of protons of the terminal methyl group : the total number of protons of the remaining methoxy group = 3n:6 + 3n(L-2) = 3:v''.

[0024] Furthermore, the NMR-calculated average degree of polymerization n of hydrocarbon-terminated oligomers NMRAs a method for calculating n, when the hydrocarbon terminal group in the monomer component is a linear alkyl group and there is one ethoxy group for each hydrolyzable silyl group, it is calculated using the proton ratio of the remaining methoxy group to the terminal methyl group in the hydrocarbon terminal group in the hydrocarbon terminal group oligomer. When the NMR integral value of the terminal methyl group in the hydrocarbon terminal group is set to 3, the NMR integral value of the methylene group adjacent to the oxygen atom in the remaining ethoxy group is w'', and when the number of hydrolyzable silyl groups in the monomer component is L (L is an integer from 2 to 4, preferably 2 or 3), n NMR = 4 / (w'' - 2L + 4). This is based on the fact that when a hydrocarbon terminal group-containing oligomer is an average n-mer, the total number of protons of the terminal methyl group : the total number of protons of the methylene group adjacent to the oxygen atom in the remaining ethoxy group = 3n : 4 + 2n(L - 2) = 3 : w''.

[0025] The hydrocarbon-terminated oligomer of the present invention is characterized in that it has a monovalent hydrocarbon group having 1 to 40 carbon atoms, which may be linear, branched, cyclic, or a combination thereof, and a monovalent hydrolyzable silyl group having a methoxy group or an ethoxy group as a hydrolyzable group, and the monomer component consists only of hydrocarbon-terminated silane compounds having at least two of the methoxy group or ethoxy group in the molecule.

[0026] Furthermore, the hydrocarbon-terminated oligomer of the present invention contains only the hydrocarbon-terminated silane compound described above as a monomer component, and does not contain metal alkoxides such as tetraethoxysilane or other tetraalkoxysilanes as monomer components. If metal alkoxides are included as monomer components, the resulting cured coating will have poor abrasion resistance.

[0027] [Hydrogen-Terminal Group-Containing Silane Compounds (Monomer Components)] Hydrocarbon-terminal group-containing silane compounds have a monovalent hydrocarbon group having 1 to 40 carbon atoms, which may be linear, branched, cyclic, or a combination thereof, and a monovalent hydrolyzable silyl group having a methoxy group or an ethoxy group as a hydrolyzable group, with at least two such methoxy or ethoxy groups in the molecule. The monovalent hydrocarbon group preferably has 3 to 40 carbon atoms, more preferably 8 to 30, even more preferably 10 to 30, and particularly preferably 10 to 25. If the number of carbon atoms exceeds 40, the hydrocarbon group becomes long, steric hindrance between molecular chains increases, and oligomer formation becomes difficult.

[0028] As the hydrocarbon-terminated silane compound, the hydrocarbon-terminated silane compound represented by the following general formula (1) is preferred. (In the formula, R is a monovalent hydrocarbon group having 1 to 40 carbon atoms, which may be linear, branched, cyclic, or a combination thereof; Z is a divalent linking functional group containing at least one atom independently selected from oxygen, nitrogen, sulfur, and silicon atoms; Y is a divalent hydrocarbon group having 1 to 30 carbon atoms, which may be linear, branched, cyclic, or a combination thereof; W is a single bond, carbon atom, silicon atom, nitrogen atom, or a 3 to 5 valent organic group; A is a monovalent hydrolyzable silyl group having a methoxy group or an ethoxy group; k1 is an integer from 0 to 3; k2 is an integer from 1 to 4; and k3 is 0 or 1. However, each molecule contains at least two methoxy groups or ethoxy groups.)

[0029] In formula (1) above, R may be linear, branched, cyclic, or a combination thereof, and is a monovalent hydrocarbon group having 1 to 40 carbon atoms, preferably 3 to 40, more preferably 8 to 30, even more preferably 10 to 30, and particularly preferably 10 to 25 carbon atoms. Furthermore, when k1 is 1 or more, from the viewpoint of solubility in solvents, it is preferable that k1 has 6 to 10 carbon atoms, and more preferably 8 to 10 carbon atoms. Examples of R include the following. (In the formula, x is an integer between 0 and 39, preferably between 2 and 39, more preferably between 7 and 29, and y and y' are integers greater than or equal to 0 such that the sum of the number of carbon atoms in each structure is 40 or less.)

[0030] For R, the value represented by the following formula (6) is more preferable. (In the formula, R 5 R is a methyl group, a cyclic alkyl group, or a phenyl group. 6 is a divalent cyclic hydrocarbon group having 3 to 10 carbon atoms, which may independently have substituents. y is an integer greater than or equal to 0, h is an integer from 0 to 6, preferably 0 or 1, and the sum of y and h is an integer such that the total number of carbon atoms in formula (6) is 40 or less. Each repeating unit shown in parentheses with y and h may be randomly bonded.

[0031] In the above formula (6), R 5 The group is a cyclic alkyl group such as a methyl group, cyclopentyl group, or cyclohexyl group, or a phenyl group, with a methyl group being preferred.

[0032] In the above formula (6), R 6 R is a divalent cyclic hydrocarbon group having 3 to 10 carbon atoms, which may independently have substituents. 6 Examples of divalent cyclic hydrocarbon groups represented by the formula are listed below.

[0033] In formula (1) above, Z, together with Y and W, is a linking group that connects the hydrocarbon chain at the end of the molecular chain (R in formula (1)) to the hydrolyzable silyl group (A in formula (1)). It is a divalent linking functional group containing at least one atom independently selected from oxygen, nitrogen, sulfur, and silicon. When a linking functional group is present in the molecule, intermolecular interactions and molecular chain mobility are improved, and improvements in water repellency and abrasion resistance can be expected in the cured film formed by a surface treatment agent containing a hydrocarbon end group-containing oligomer. The divalent linking functional group containing at least one selected from oxygen, nitrogen, sulfur, and silicon atoms is preferably 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, divalent nitrogen-containing heterocyclic group (such as a divalent oxazole group, divalent imidazole group, or divalent triazole group), diorganosilylene group, or a linear or branched or cyclic divalent organopolysiloxane residue with 2 to 10 silicon atoms. Particularly preferred are ether groups, thioether groups, carbamate groups, and urea groups.

[0034] Examples of such Z include those shown below. In the structure below, the left-hand connector connects to R or Y, and the right-hand connector connects to Y. (In the formula, R 7 (where e is an integer from 1 to 9.)

[0035] Here, R 7 These are independently a hydrogen atom, a methyl group, or a linear monovalent hydrocarbon group whose terminus is a cyclic alkyl group. Examples of such linear monovalent hydrocarbon groups whose terminus is a cyclic alkyl group include the following: (In the formula, R 8R is a divalent cyclic hydrocarbon group having 3 to 9 carbon atoms, which may independently have a methyl group or a cyclic alkyl group. 9 z is independently a methyl group, a cyclic alkyl group, or a phenyl group. z' is an integer greater than or equal to 0, and z' is an integer greater than or equal to 1 such that the sum of the number of carbon atoms in each structure is 20 or less.

[0036] In the above formula, R 8 R is a divalent cyclic hydrocarbon group having 3 to 9 carbon atoms, which may independently have a methyl group or a cyclic alkyl group. 8 Examples of divalent cyclic hydrocarbon groups represented by the formula are listed below.

[0037] Furthermore, in the above formula, R 9 The group is a cyclic alkyl group such as a methyl group, cyclopentyl group, or cyclohexyl group, or a phenyl group, with a methyl group being preferred.

[0038] In formula (1) above, Y is a linking group that, together with Z and W, connects the hydrocarbon chain at the end of the molecular chain (R in formula (1)) to the hydrolyzable silyl group (A in formula (1)). It may be independently linear, branched, cyclic, or a combination thereof, and is a divalent hydrocarbon group having 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms, more preferably 2 to 11 carbon atoms, and even more preferably 2 to 4 carbon atoms. Examples of Y include the group represented by the following general formula (2). (In the formula, R 1 R is a monovalent hydrocarbon group having 1 to 10 carbon atoms, which may be linear, branched, cyclic, or a combination thereof. 2 is a divalent cyclic hydrocarbon group having 3 to 10 carbon atoms, which may independently have substituents. a is an integer from 0 to 30, b is an integer from 0 to 15, c is an integer from 0 to 10, and d is an integer from 0 to 6, where the sum of a, b, c, and d is an integer such that the total number of carbon atoms in formula (2) is 1 to 30. Each repeating unit shown in parentheses with a, b, c, and d may be randomly combined.

[0039] In the above equation (2), R 1R is a monovalent hydrocarbon group having 1 to 10 carbon atoms, which may be linear, branched, cyclic, or a combination thereof. Specifically, examples include alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, neopentyl, hexyl, cyclohexyl, octyl, nonyl, and decyl groups; aryl groups such as phenyl, tolyl, xylyl, and naphthyl groups; aralkyl groups such as benzyl, phenylethyl, and phenylpropyl groups; and combinations thereof. 1 The following formula is preferred. (In the formula, g is an integer between 0 and 4.)

[0040] In the above equation (2), R 2 This is a divalent cyclic hydrocarbon group having 3 to 10 carbon atoms, which may independently have substituents, and preferably one of those exemplified below.

[0041] In formula (2) above, a is an integer from 0 to 30, preferably from 0 to 20; b is an integer from 0 to 15, preferably from 0 to 5; c is an integer from 0 to 10, preferably from 0 to 5; and d is an integer from 0 to 6, preferably 0 or 1. The sum of a, b, c, and d is an integer such that the total number of carbon atoms in formula (2) is 1 to 30, preferably from 1 to 10. Furthermore, the repeating units shown in parentheses with a, b, c, and d may be combined randomly.

[0042] Examples of Y include those shown below. In the structure below, the left-hand connector connects to Z or W, and the right-hand connector connects to Z, W, or A. (In the formula, a1 is an integer between 1 and 30, a2 is an integer greater than or equal to 1, b1 is an integer between 1 and 15, c1 is an integer between 1 and 10, and g is an integer between 0 and 4, provided that the total number of carbon atoms in each structure is 30 or less.)

[0043] In formula (1) above, W is a single bond, a carbon atom, a silicon atom, a nitrogen atom, or a 3- to 5-valent organic group, and the 3- to 5-valent organic group is a 6- to 8 carbon atom trivalent or tetravalent cyclic hydrocarbon group, -SiR 10 = (R 10 (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 11 = (R 11 Examples of trivalent groups include trivalent groups represented by a hydrogen atom, a hydroxyl group, or an alkyl group having 1 to 3 carbon atoms; linear trivalent to pentavalent organopolysiloxane residues having 2 to 10 silicon atoms, particularly 2 to 8 silicon atoms, or branched or cyclic trivalent to 3 to 10 silicon atoms, particularly 3 to 8 silicon atoms; trivalent amide groups; trivalent carbamate groups; trivalent or tetravalent urea groups; and trivalent or tetravalent nitrogen-containing heterocyclic groups (such as trivalent cyanurate groups, trivalent isocyanurate groups, and trivalent or tetravalent triazine ring-containing groups).

[0044] The organopolysiloxane residue may have an alkyl group such as a methyl group, ethyl group, propyl group, or butyl group, or a phenyl group, having 1 to 8 carbon atoms, more preferably 1 to 4 carbon atoms. The organopolysiloxane residue may also contain a sylalkylene structure in which two silicon atoms are linked by an alkylene group such as an ethylene group or a propylene group.

[0045] Examples of such W include, in addition to single bonds, those shown below. In the structure below, the leftmost bond connects to Y in the brackets enclosed by R or k1, and the other bond connects to Y in the brackets enclosed by k3. (In the formula, f is an integer between 2 and 4.)

[0046] In formula (1) above, A is a monovalent hydrolyzable silyl group having a methoxy group or an ethoxy group, and a group represented by the following general formula is preferred. (In the formula, R 0k2 is independently an alkyl group having 1 to 4 carbon atoms or a phenyl group, X is independently a methoxy group or an ethoxy group, and m is an integer from 1 to 3, preferably 3. However, when m is 1, k2 is an integer from 2 to 4.

[0047] Examples of such A include the following:

[0048] In formula (1) above, k1 is a number indicating the number of repetitions of -Z-Y-, and is an integer from 0 to 3. When k1 is 0, the intermolecular interactions due to van der Waals forces between R (especially alkyl groups) are strengthened, and the R (especially alkyl groups) tend to be densely oriented. When k1 is 1 or greater, even if the molecular chain length is long and steric hindrance increases, the molecular mobility is improved by the linking functional group Z, so the molecular chains become densely oriented. When k1 is 4 or greater, the molecules become more prone to bending, and it becomes difficult for the molecules to be densely oriented. Furthermore, from the viewpoint of molecular orientation and molecular mobility, it is preferable that k1 is 0 or 1, and when k1 is 0 or 1, it is preferable that R in formula (1) above is represented by the following formula (6). (In the formula, R 5 , R 6 (The sum of y, h, and y and h is the same as above.)

[0049] In formula (1) above, k2 is an integer from 1 to 4, and is preferably 1 from the viewpoint of the ease with which the hydrolysis condensation reaction proceeds when forming an oligomer. k3 is 0 or 1, is 0 when W is a single bond, and is 1 when W is not a single bond. The hydrocarbon terminal group-containing silane compound represented by formula (1) has at least two methoxy groups or ethoxy groups, preferably 2 to 12, more preferably 3 to 9, in one molecule.

[0050] The following structures are examples of hydrocarbon terminal group-containing silane compounds represented by the above formula (1). By changing the combination of R, Z, Y, W, A, k1, and k3 in the above formula (1), several different hydrocarbon terminal group-containing compounds can be obtained.

[0051]

[0052]

[0053]

[0054]

[0055]

[0056]

[0057]

[0058]

[0059] (In the formula, x, y, a1, a2, b1, c1, and g are each independently the same as above. The total number of carbon atoms in the part corresponding to R in formula (1) is 40 or less, and the total number of carbon atoms in the part corresponding to Y is between 1 and 30.)

[0060] [Synthesis Method for Hydrocarbon End-Group Containing Silane Compounds] Examples of methods for synthesizing hydrocarbon end-group containing silane compounds represented by general formula (1) include the following: [Synthesis Method 1-1] A hydrocarbon end-group containing compound having an alkenyl group at the end and a compound having an SiH group and a hydrolyzable silyl group are mixed and subjected to a hydrosilylation addition reaction in the presence of a hydrosilylation catalyst to produce a hydrocarbon end-group containing silane compound represented by formula (1). 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 is then converted to a methoxy group or an ethoxy group.

[0061] Examples of hydrocarbon terminal group-containing compounds having an alkenyl group at the terminal include compounds represented by the following formulas (1A-1) or (1A-2). (In the formula, R, Z, Y, W, k1, k2 are the same as above. R' is a monovalent hydrocarbon group having 1 to 38 carbon atoms, which may be linear, branched, cyclic, or a combination thereof, and Y 1 (This is a monovalent hydrocarbon group having 2 to 30, preferably 2 to 20, alkenyl groups, which may be linear, branched, cyclic, or a combination thereof.)

[0062] In the above formula (1A-1), R' is a monovalent hydrocarbon group having 1 to 38 carbon atoms, which may be linear, branched, cyclic, or a combination thereof. Examples include the following: (In the formula, x' is an integer between 0 and 37.)

[0063] In the above formula (1A-2), Y 1 This is a monovalent hydrocarbon group having an alkenyl group with 2 to 30 carbon atoms, preferably 2 to 20 carbon atoms, which may be linear, branched, cyclic, or a combination thereof, and examples include those having the terminals shown below. (In the formula, R 12 Each Y may independently be a hydrogen atom, or may be linear, branched, cyclic, or a combination thereof. 1 (A monovalent hydrocarbon group whose total number of carbon atoms in its structure is 30 or less.)

[0064] Y 1 The following are preferred. (In the formula, g is the same as above, a' is an independent integer of 0 or more, and the total number of carbon atoms in each of the above structures is 30 or less.)

[0065] Examples of compounds represented by formula (1A-1) are listed below. (In the formula, x' is the same as above.)

[0066] Examples of compounds represented by formula (1A-2) are listed below. (In the formula, x, a1, and a' are all independently the same as above.)

[0067] Examples of compounds having an SiH group and a hydrolyzable silyl group in synthesis method 1-1 include trimethoxysilane, triethoxysilane, and trichlorosilane.

[0068] In synthesis method 1-1, the amount of compound having an SiH group and a hydrolyzable silyl group used is preferably 1 to 10 mol, particularly 3 to 10 mol, per 1 mol of alkenyl group in the hydrocarbon terminal group-containing compound having an alkenyl group at the terminal end.

[0069] In synthesis method 1-1, 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 in terms of transition metal (mass) relative to the mass of the hydrocarbon-terminal group-containing compound having an alkenyl group at the terminal, and more preferably 0.01 to 100 ppm.

[0070] In synthesis method 1-1, co-catalysts to activate the hydrosilylation reaction and co-catalysts to prevent the conversion of alkenyl groups can be used. Examples of co-catalysts to activate the hydrosilylation reaction include acetic acid, formic acid, and propionic acid. Examples of co-catalysts to prevent the conversion of alkenyl groups include formamide, acetamide, and acetonitrile. When these co-catalysts are incorporated, the amount used is preferably 10 to 1,000,000 ppm by mass, and more preferably 100 to 10,000 ppm, relative to the mass of the hydrocarbon terminal group-containing compound having an alkenyl group at the terminal end.

[0071] In synthesis method 1-1, 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, and ketones such as acetone and methyl ethyl ketone. When using a solvent, the amount used is preferably 0 to 1,000 parts by mass, and more preferably 50 to 200 parts by mass, per 100 parts by mass of the hydrocarbon terminal group-containing compound having an alkenyl group at the terminal end.

[0072] In synthesis method 1-1, the reaction conditions for the hydrocarbon terminal group-containing compound having an alkenyl group at its terminus and the compound having an SiH group and a hydrolyzable silyl group are preferably a temperature of 20 to 120°C, particularly 60 to 100°C, for 0.5 to 72 hours, and especially 1 to 48 hours.

[0073] In synthesis method 1-1, 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 an SiH group and a silyl halogen group), the substituent (halogen atom) on the silyl group is then converted to a methoxy group or an ethoxy group. Examples of compounds that can be used to convert the substituent (halogen atom) on the silyl group to a methoxy group or an ethoxy group include methanol and ethanol. The amount used is preferably 3 to 9 mol, particularly 3 to 5 mol, per 1 mol of halogen atoms in the reaction product of the hydrocarbon terminal group-containing compound having an alkenyl group at the terminal and the SiH group and silyl halogen group-containing compound.

[0074] In synthesis method 1-1, the reaction conditions for converting substituents (halogen atoms) on the silyl group to methoxy or ethoxy 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.

[0075] Other methods for synthesizing hydrocarbon-terminal group-containing silane compounds represented by general formula (1) include the following: [Synthesis Method 1-2] A hydrocarbon-terminal group-containing compound having an SiH group at the terminal end can be mixed with a compound having an alkenyl group and a hydrolyzable silyl group, and a hydrosilylation addition reaction can be carried out in the presence of a hydrosilylation catalyst to produce a hydrocarbon-terminal group-containing silane compound represented by formula (1).

[0076] Here, examples of hydrocarbon terminal group-containing compounds having an SiH group at the terminal include compounds represented by the following formula (1B). (In the formula, R, Z, Y, k1, k2 are the same as above. W 1These are linear organopolysiloxane residues with 1 to 10 silicon atoms, or branched or cyclic organopolysiloxane residues with 3 to 10 silicon atoms, and are 3 to 5 valent.

[0077] In the above formula (1B), W 1 These are linear organopolysiloxane residues with 1 to 10 silicon atoms, or branched or cyclic organopolysiloxane residues with 3 to 10 silicon atoms, particularly branched or cyclic organopolysiloxane residues with 3 to 8 silicon atoms, provided that the hydrogen atoms enclosed in k2 are bonded to silicon atoms. 1 Examples are shown below. In the structure below, the bond on the left bonds with Y, and the other bonds bond with hydrogen atoms.

[0078] Examples of compounds represented by formula (1B) are listed below. (In the formula, x and a1 are independently the same as above.)

[0079] Examples of compounds having an alkenyl group and a hydrolyzable silyl group include vinyltrimethoxysilane, allyltrimethoxysilane, and octenyltrimethoxysilane.

[0080] In synthesis methods 1-2, the amount of compound having an alkenyl group and a hydrolyzable silyl group used is preferably 1 to 5 mol, particularly 1 to 3 mol, per 1 mol of SiH group in the hydrocarbon-terminated compound having an SiH group at its terminus.

[0081] In synthesis method 1-2, the hydrosilylation reaction catalyst can be the same as that exemplified in the hydrosilylation reaction catalyst of synthesis method 1-1. Preferably, it is a platinum-based compound such as a vinylsiloxane coordination compound. The platinum-based compound is preferably used dissolved in a solvent such as toluene, a lower alcohol, a higher alcohol, or a silicone-based solvent. The amount of hydrosilylation reaction catalyst used is preferably 0.001 to 1,000 ppm in terms of transition metal (mass) relative to the mass of the hydrocarbon-terminated compound having an SiH group at the terminal, and more preferably 0.01 to 100 ppm.

[0082] In synthesis method 1-2, co-catalysts to activate the hydrosilylation reaction and co-catalysts to prevent the conversion of alkenyl groups can be used. Examples of co-catalysts to activate the hydrosilylation reaction include acetic acid, formic acid, and propionic acid. Examples of co-catalysts to prevent the conversion of alkenyl groups include formamide, acetamide, and acetonitrile. The amount of these co-catalysts used is preferably 10 to 1,000,000 ppm by mass, and more preferably 100 to 10,000 ppm, relative to the mass of the hydrocarbon-terminated compound having an SiH group at the terminal end.

[0083] In synthesis method 1-2, a solvent can be used when carrying out the reaction. Examples of solvents are the same as those exemplified in the solvent for synthesis method 1-1 above. When a solvent is used, the amount used is preferably 0 to 1,000 parts by mass, and more preferably 50 to 200 parts by mass, per 100 parts by mass of the hydrocarbon terminal group-containing compound having an SiH group at the terminal end.

[0084] In synthesis method 1-2, the reaction conditions are preferably a temperature of 20 to 120°C, particularly 60 to 100°C, for 0.5 to 72 hours, and especially 1 to 36 hours.

[0085] Other methods for preparing hydrocarbon-terminated silane compounds represented by general formula (1) include the following: [Synthesis Method 1-3] A hydrocarbon-terminated silane compound represented by formula (1) (particularly a compound having a hydrolyzable silyl group at the end via a urethane bond) can be produced by mixing a hydrocarbon-terminated silane compound having a hydroxyl group at the end with a compound having an isocyanate group and a hydrolyzable silyl group and reacting them in the presence of a catalyst.

[0086] Here, examples of hydrocarbon terminal group-containing compounds having a hydroxyl group at the terminal include compounds represented by the following formula (1C). (In the formula, R, Z, and Y are the same as above. p is an integer between 0 and 2.)

[0087] Examples of compounds represented by formula (1C) are listed below. (In the equation, x, y, and a1 are independently the same as above.)

[0088] Examples of compounds having an isocyanate group and a hydrolyzable silyl group include 3-isocyanatopropyltrimethoxysilane and 3-isocyanatopropyltriethoxysilane.

[0089] In synthesis methods 1-3, the amount of compound having an isocyanate group and a hydrolyzable silyl group used is preferably 1 to 3 mol, particularly 1 to 1.5 mol, per 1 mol of hydroxyl group in the hydrocarbon terminal group-containing compound having a hydroxyl group at the terminal end.

[0090] In synthesis methods 1-3, examples of catalysts include titanium compounds such as tetrakis(2-ethylhexyl) orthotitanate, tetra-n-butyl titanate, and tetra-n-propyl titanate; zirconium compounds such as tetra-n-butyl zirconate and tetra-n-propyl zirconate; tin compounds such as dibutyltin dimethoxide and dibutyltin dilaurate; bismuth compounds such as bismastris(2-ethylhexanoate); and amine catalysts such as diazabicycloundecene. The amount of catalyst used is 0.01 to 100 parts by mass, particularly preferably 0.1 to 20 parts by mass, per 100 parts by mass of the hydrocarbon-terminated compound having a hydroxyl group at its terminus.

[0091] In synthesis methods 1-3, a solvent can be used when carrying out the reaction. Examples of solvents are the same as those exemplified in the solvent for synthesis method 1-1 above. The amount of solvent used is preferably 0 to 1,000 parts by mass, particularly 50 to 200 parts by mass, per 100 parts by mass of the hydrocarbon terminal group-containing compound having a hydroxyl group at the terminal end.

[0092] In synthesis methods 1-3, the reaction conditions are preferably a temperature of 20 to 100°C, particularly 30 to 60°C, for 0.5 to 72 hours, and especially 1 to 36 hours.

[0093] Other methods for synthesizing hydrocarbon-terminal group-containing silane compounds represented by general formula (1) include the following: [Synthesis Method 1-4] A hydrocarbon-terminal group-containing compound represented by formula (1) can be produced by mixing a hydrocarbon-terminal group-containing compound having an alkenyl group at the terminal end with a compound having a thiol group and a hydrolyzable silyl group, or a hydrocarbon-terminal group-containing compound having a thiol group at the terminal end with an alkenyl group and a hydrolyzable silyl group, and reacting them in the presence of a polymerization initiator.

[0094] Examples of hydrocarbon terminal group-containing compounds having an alkenyl group at the terminal include compounds represented by the following formulas (1E-1) or (1E-2). (In the formula, R', R, Z, Y, Y 1 (p is the same as above.)

[0095] Examples of compounds represented by formula (1E-1) are listed below. (In the formula, x' is the same as above.)

[0096] Examples of compounds represented by formula (1E-2) are listed below. (In the formula, x, a1, and a' are independently the same as above.)

[0097] Furthermore, examples of compounds having a thiol group and a hydrolyzable silyl group include compounds represented by the following formula (1F). (In the formula, Z, Y, and A are the same as above. q is an integer between 0 and 2, and the sum of p and q is between 0 and 2.)

[0098] Examples of compounds represented by formula (1F) are listed below. (In the formula, a1 is the same as above.)

[0099] Furthermore, examples of hydrocarbon terminal group-containing compounds having a thiol group at the terminal include compounds represented by the following formula (1G). (In the formula, R, Z, Y, and p are the same as above.)

[0100] Examples of compounds represented by formula (1G) are listed below. (In the formula, x is the same as above.)

[0101] Furthermore, in synthesis methods 1-4, examples of compounds having an alkenyl group and a hydrolyzable silyl group include compounds represented by the following formula (1H). (In the formula, Y 1 (Z, Y, A, q, and p+q are the same as above.)

[0102] Examples of compounds represented by formula (1H) are listed below. (In the formula, a' is the same as above.)

[0103] In synthesis methods 1-4, the amount of compound having a thiol group and a hydrolyzable silyl group used is preferably 1 to 5 mol, particularly 1 to 3 mol, per mol of alkenyl group in the hydrocarbon terminal group-containing compound having an alkenyl group at the terminal end.

[0104] In synthesis methods 1-4, examples of polymerization initiators include azo compounds such as 2,2'-azobisisobutyronitrile and 2,2'-azobis(isobutyrate)dimethyl, diacyl peroxides such as benzoyl peroxide and lauroyl peroxide, dialkyl peroxides such as dicumyl peroxide and di-tert-butyl peroxide, peroxycarbonates such as diisopropyl peroxydicarbonate and bis(4-tert-butylcyclohexyl) peroxydicarbonate, and alkyl peresters such as t-butyl peroxyoctoate and tert-butyl peroxybenzoate. The amount of polymerization initiator used is preferably 0.01 to 3 mol, particularly 0.1 to 1.5 mol, per 1 mol of alkenyl group in the hydrocarbon terminal group-containing compound having an alkenyl group at the terminal or thiol group in the hydrocarbon terminal group-containing compound having a thiol group at the terminal.

[0105] In addition, a solvent can be used when carrying out the reaction in synthesis method 1-4. Examples of solvents are the same as those exemplified in the solvent for synthesis method 1-1 above. When using a solvent, the amount used is preferably 0 to 1,000 parts by mass, particularly 50 to 800 parts by mass, per 100 parts by mass of the hydrocarbon terminal group-containing compound having an alkenyl group at the terminal or the hydrocarbon terminal group-containing compound having a thiol group at the terminal.

[0106] In synthesis methods 1-4, the reaction conditions are preferably a temperature of 20 to 100°C, particularly 40 to 80°C, for 0.5 to 72 hours, and especially 1 to 36 hours.

[0107] As for the hydrocarbon terminal group-containing silane compound represented by formula (1) above, from the viewpoint of the orientation of the hydrocarbon terminal group of the hydrocarbon terminal group-containing oligomer of the present invention, it is preferable that W is a single bond (i.e., k2=1, k3=0).

[0108] As a hydrocarbon terminal group-containing silane compound represented by formula (1) above, a hydrocarbon terminal group-containing oligomer in which W is a single bond (i.e., k2=1, k3=0) is the monomer component can be represented by the following average formula (5). (In the formula, R, Z, Y, and k1 are the same as in formula (1) above, R X (where n is independently a methyl group, an ethyl group, or a hydrogen atom, n is an average number greater than 1 and less than or equal to 100, preferably 1.2 to 50, more preferably 1.2 to 30, and even more preferably 1.5 to 20.)

[0109] In the above formula (5), R X These are independently a methyl group, an ethyl group, or a hydrogen atom, and Si-OR X This functional group has adhesive reactivity to the surface of various substrates made of materials such as paper, cloth, metals and their oxides, glass, plastics (resins), ceramics, and quartz, which are the target of surface treatment.

[0110] The following structures are examples of the hydrocarbon terminal group-containing oligomer represented by formula (5) above. R, Z, Y, k1, R X By changing the combination of n, several hydrocarbon terminal group-containing oligomers can be obtained. In the structure below, n is a number greater than 1 and less than or equal to 100, n1 and n2 are numbers greater than 0, and the sum of n1 and n2 is a number greater than 1 and less than or equal to 100. (In the formula, x, y, a1, n, n1, n2, and n1+n2 are the same as above.)

[0111] One method for preparing the hydrocarbon-terminated oligomer of the present invention is as follows: [Method 1 for preparing hydrocarbon-terminated oligomer] A hydrocarbon-terminated silane compound is mixed with water, an (acid or base) catalyst, and an organic solvent if necessary. The mixture is heated and stirred if necessary to allow a partial hydrolysis condensation reaction to proceed. The (acid or base) catalyst is then inactivated, and the reaction by-products generated after the reaction are removed by distillation. Finally, the oligomer containing the target hydrocarbon-terminated oligomer is obtained by filtration.

[0112] The hydrocarbon terminal group-containing silane compound described above is preferably a hydrocarbon terminal group-containing silane compound represented by the following general formula (1) described above. (In the formula, R, Z, Y, W, A, k1, k2, and k3 are the same as above.)

[0113] In method 1 for preparing hydrocarbon-terminated oligomers, the amount of water used in the reaction is preferably more than 0 mol and 10 mol or less, more preferably 0.001 to 3 mol, and even more preferably 0.01 to 2 mol, per 1 mol of hydrolyzable silyl groups in the hydrocarbon-terminated silane compound. If the amount of water used exceeds 10 mol, the degree of polymerization of the oligomer becomes too high, and vapor deposition coating may not be possible.

[0114] In method 1 for preparing hydrocarbon-terminated oligomers, the catalyst used in the reaction is preferably an acid, particularly an inorganic acid such as hydrochloric acid, nitric acid, or sulfuric acid, or an organic acid such as trifluoroacetic acid, or a base, particularly an inorganic base such as sodium hydroxide or potassium hydroxide, or an organic base such as diazabicycloundecene. The amount of catalyst used is preferably greater than 0 to 0.1 mol, and more preferably 0.0001 to 0.05 mol, per mol of hydrolyzable silyl groups in the hydrocarbon-terminated silane compound.

[0115] In method 1 for preparing hydrocarbon-terminated oligomers, organic solvents can also be used in the reaction. These solvents are alcohols such as methanol, ethanol, propanol, and butanol, with methanol and ethanol being particularly preferred. The amount of organic solvent used is preferably 0 to 1,000 parts by mass, and more preferably 0 to 10 parts by mass, per 100 parts by mass of the hydrocarbon-terminated silane compound.

[0116] In method 1 for preparing hydrocarbon-terminated oligomers, the conditions for the partial hydrolysis condensation reaction are preferably a temperature of 20 to 120°C, particularly 20 to 60°C, for 0.5 to 24 hours, and especially 3 to 16 hours.

[0117] In method 1 for preparing hydrocarbon-terminated oligomers, the method for inactivating the acid catalyst is not particularly limited as long as it can deactivate the acid catalyst, but it is preferable that the method is easy to remove after deactivation. Examples include Kyoward 500 and propylene oxide. In the case of Kyoward 500, 0.00001 to 0.5 parts by mass is preferred, and more preferably 0.01 to 0.1 parts by mass, per 100 parts by mass of the hydrocarbon-terminated silane compound. In the case of propylene oxide, 1 to 10 mol is preferred, and more preferably 1.5 to 5 mol, per 1 mol of acid used in the reaction system.

[0118] In method 1 for preparing hydrocarbon-terminated oligomers, the method for inactivating the base catalyst is not particularly limited as long as it can inactivate the base catalyst, but it is preferable that the method is easy to remove after inactivation. For example, Kyoward 700 can be used. In the case of Kyoward 700, the amount is preferably 0.00001 to 0.5 parts by mass, and more preferably 0.01 to 0.1 parts by mass, per 100 parts by mass of the hydrocarbon-terminated silane compound.

[0119] In method 1 for preparing hydrocarbon-terminated oligomers, if the inactivator used to deactivate the catalyst is a solid, the remaining inactivator is filtered out. For example, if Kyoward 500 or Kyoward 700 is used as the catalyst inactivator, the reaction solution is filtered using a PTFE membrane filter with a pore size of 0.2 μm and a pressure filter to remove the inactivator. If the inactivator used to deactivate the catalyst is a liquid, it is removed simultaneously with the distillation of the reaction byproducts as described below.

[0120] In method 1 for preparing hydrocarbon-terminated oligomers, if reaction by-products and solvents are used, the solvent is removed by distillation using a strip. The pressure during stripping is 1 × 10⁻⁶. -2 ~1 x 105 The pressure (Pa), temperature (20-150°C), and duration (1-5 hours) are preferred, but the temperature, pressure, and duration may also be varied. Particularly preferred is 1 x 10⁻⁶ 5 After stripping, the temperature was 100-120°C and the time was 1-2 hours, then 1 x 10 5 A preferred method involves stripping the material at Pa, a temperature of 120-150°C, and a duration of 3-5 hours.

[0121] Another method for preparing the hydrocarbon-terminated oligomer of the present invention is as follows: [Method 2 for preparing hydrocarbon-terminated oligomer] A functional group-containing oligomer obtained in [Step 1] is reacted with a compound having another functional group that can be linked to the functional group of the functional group-containing oligomer and a hydrocarbon-terminated group at both ends, thereby extending the chain length in [Step 2].

[0122] [Step 1] In the method 2 for preparing hydrocarbon terminal group-containing oligomers, Step 1 is a step in which a functional group-containing silane compound is mixed with water, a catalyst, and an organic solvent if necessary, and a partial hydrolysis condensation reaction is carried out, after which the catalyst is deactivated, and the catalyst and reaction by-products produced after the reaction are removed by distillation to obtain a functional group-containing oligomer.

[0123] Here, the functional group-containing silane compound is represented by the following general formula (3). (In the formula, Z, Y, W, A, k2, k3 are the same as above, E is a monovalent functional group that can react with and link with T as described later, Y 2 k4 is a divalent hydrocarbon group having 1 to 30 carbon atoms, which may be linear, branched, cyclic, or a combination thereof, and k4 is an integer from 0 to 2.

[0124] In formula (3) above, E is a monovalent functional group that can react with and link with T, which will be described later. Examples include terminal olefin groups (e.g., alkenyl groups), thiol groups, isocyanate groups, hydroxyl groups, amino groups, ester groups, carboxyl groups, halogen groups, and other leaving groups. Terminal olefin groups and thiol groups are particularly preferred.

[0125] Examples of such E include the following: (In the formula, g, R 7 (This is the same as above.)

[0126] In the above equation (3), Y 2 E may be linear, branched, cyclic, or a combination thereof, and is a divalent hydrocarbon group having 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms, more preferably 2 to 11 carbon atoms, and even more preferably 2 to 4 carbon atoms. However, if E is a terminal olefin group, Y 2 The total number of carbon atoms in E, including the number of carbon atoms in the terminal olefin group, is 30 or less.

[0127] Y 2 Examples similar to those exemplified in Y above can be given, but the following are more preferable. (In the formula, a'a2, b1, c1, and g are the same as above, provided that the total number of carbon atoms in each structure is 30 or less.)

[0128] The following structure is an example of the structure of a functional group-containing silane compound represented by the above formula (3). E and Y in the above formula (3) 2 By changing the combination of Z, Y, W, A, k3, and k4, several hydrocarbon-terminal group-containing compounds can be obtained.

[0129] (In the formula, a1 and a' are the same as above.)

[0130] In the second method for preparing hydrocarbon-terminated oligomers, the amount of water used in the partial hydrolysis condensation reaction of the functional group-terminated silane compound represented by formula (3) is preferably more than 0 mol and 3 mol or less, and more preferably 0.1 to 1.5 mol, per mol of hydrolyzable silyl groups in the hydrocarbon-terminated silane compound. If the amount of water used exceeds 3 mol, the degree of polymerization of the oligomer becomes too high, and vapor deposition coating may not be possible.

[0131] In method 2 for preparing hydrocarbon-terminated oligomers, the catalyst used in the partial hydrolysis condensation reaction of the functional group-terminated silane compound represented by formula (3) above is preferably an acid, particularly an inorganic acid such as hydrochloric acid, nitric acid, or sulfuric acid, or an organic acid such as trifluoroacetic acid, or a base, particularly an inorganic base such as sodium hydroxide or potassium hydroxide, or an organic base such as diazabicycloundecene. The amount of catalyst used is preferably more than 0 to 0.1 mol, and more preferably 0.001 to 0.05 mol, per 1 mol of hydrolyzable silyl groups in the hydrocarbon-terminated silane compound.

[0132] In method 2 for preparing hydrocarbon-terminated oligomers, an organic solvent may be used in the partial hydrolysis condensation reaction of the functional group-containing silane compound represented by formula (3) above. These solvents are alcohols such as methanol, ethanol, propanol, and butanol, with methanol and ethanol being particularly desirable. The amount of organic solvent used is preferably 0 to 1,000 parts by mass, and more preferably 0 to 10 parts by mass, per 100 parts by mass of the hydrocarbon-terminated silane compound.

[0133] In the second method for preparing hydrocarbon terminal group-containing oligomers, the conditions for the partial hydrolysis condensation reaction of the functional group-containing silane compound represented by formula (3) are preferably a temperature of 20 to 120°C, particularly 20 to 60°C, for 0.5 to 24 hours, and especially 3 to 16 hours.

[0134] In method 2 for preparing hydrocarbon-terminated oligomers, the method for inactivating the acid catalyst in the partial hydrolysis condensation reaction of the functional group-containing silane compound represented by formula (3) above is not particularly limited as long as it can inactivate the acid catalyst, but it is preferable that the inactivation is easily removed. Examples include Kyoward 500 and propylene oxide. In the case of Kyoward 500, 0.00001 to 0.5 parts by mass is preferred, and more preferably 0.01 to 0.1 parts by mass, per 100 parts by mass of the hydrocarbon-terminated silane compound. In the case of propylene oxide, 1 to 10 mol is preferred, and more preferably 1.5 to 5 mol, per 1 mol of acid used in the reaction system.

[0135] In method 2 for preparing hydrocarbon terminal group-containing oligomers, the method for inactivating the base catalyst used in the partial hydrolysis condensation reaction of the functional group-containing silane compound represented by formula (3) above is not particularly limited as long as it can inactivate the base catalyst, but it is preferable that the inactivation is easily removed. For example, Kyoward 700 can be mentioned. In the case of Kyoward 700, it is preferably 0.00001 to 0.5 parts by mass, and more preferably 0.01 to 0.1 parts by mass, per 100 parts by mass of the hydrocarbon terminal group-containing silane compound.

[0136] In method 2 for preparing hydrocarbon terminal group-containing oligomers, if the inactivator used to deactivate the catalyst in the partial hydrolysis condensation reaction of the functional group-containing silane compound represented by formula (3) is a solid, the remaining inactivator is filtered out. For example, if Kyoward 500 or Kyoward 700 is used as the catalyst deactivator, the reaction solution is filtered using a PTFE membrane filter with a pore size of 0.2 μm and a pressure filter to remove the inactivator. If the inactivator used to deactivate the catalyst is a liquid, it is removed simultaneously with the distillation of the reaction byproducts as described below.

[0137] In method 2 for preparing hydrocarbon-terminated oligomers, if the reaction byproduct and solvent produced in the partial hydrolysis condensation reaction of the functional group-containing silane compound represented by formula (3) above are used, the solvent is removed by distillation using stripping. The pressure used for stripping is 1 × 10⁻⁶ -2 ~1 x 10 5 The pressure (Pa), temperature (20-150°C), and duration (1-5 hours) are preferred, but the temperature, pressure, and duration may also be varied. Particularly preferred is 1 x 10⁻⁶ 5 After stripping, the temperature was 100-120°C and the time was 1-2 hours, then 1 x 10 5 A preferred method involves stripping the material at Pa, a temperature of 120-150°C, and a duration of 3-5 hours.

[0138] Examples of functional group-containing oligomers obtained by the partial hydrolysis condensation reaction of a functional group-containing silane compound represented by formula (3) above include the compound represented by formula (7) below. (In the formula, E, Y 2 Z, Y, RX (k4 and n are the same as above.)

[0139] [Step 2] In the method for preparing hydrocarbon-terminated oligomers, step 2 is a step in which the functional group-containing oligomer obtained in step 1 is reacted with another functional group that can be linked to the functional group of the oligomer, and a compound having a hydrocarbon-terminated group at both ends, thereby extending the chain length and obtaining the target hydrocarbon-terminated oligomer.

[0140] Here, examples of compounds having another functional group that can be linked to the functional group of a functional group-containing oligomer, and a hydrocarbon terminal group at both ends, include functional group-containing compounds represented by the following general formulas (4a), (4b), or (4c). (In the formula, R, Z, Y, and R' are the same as above, T is a monovalent functional group that can react with and link with E as described above, and Y 3 k5 is a divalent hydrocarbon group having 1 to 28 carbon atoms, which may be linear, branched, cyclic, or a combination thereof; k5 is an integer from 0 to 2, the sum of k4 and k5 is an integer from 0 to 2; k6 is 0 or 1, and the sum of k4 and k6 is 0 or 1.

[0141] In the above formulas (4a), (4b), and (4c), T is a monovalent functional group that can react with and link with E as described above. Examples include thiol groups, terminal olefin groups (e.g., alkenyl groups), isocyanate groups, hydroxyl groups, amino groups, ester groups, carboxyl groups, halogen groups, and other leaving groups. Terminal olefin groups and thiol groups are particularly preferred. When T is a terminal olefin group, the result is represented by formula (4b) or (4c), and when T is not a terminal olefin group, the result is represented by formula (4a).

[0142] Examples of such T include the following: (In the formula, g, R 7 (This is the same as above.)

[0143] Furthermore, the monovalent functional group E and the monovalent functional group T react with each other and link together, and it is preferable that the pair (E, T) is one of the following: (terminal olefin group, thiol group), (thiol group, terminal olefin group), (hydroxyl group, isocyanate group), (amino group, isocyanate group), (ester group, hydroxyl group), (hydroxyl group, ester group), (ester group, amino group), (amino group, ester group), (carboxyl group, hydroxyl group), (hydroxyl group, carboxyl group), (carboxyl group, amino group), (amino group, carboxyl group), (leaving group, hydroxyl group).

[0144] In the above equation (4b), Y 3 This is a divalent hydrocarbon group having 1 to 28 carbon atoms, preferably 1 to 18 carbon atoms, more preferably 2 to 9 carbon atoms, which may be linear, branched, cyclic, or a combination thereof. However, Y 3 The number of carbon atoms in (4c) is 30 or less, including the number of carbon atoms in the terminal olefin group of T. Also, the number of carbon atoms in R' in formula (4c) is 40 or less, including the number of carbon atoms in the terminal olefin group of T.

[0145] Y 3 Examples similar to those exemplified in Y above can be given, but the following are more preferable. (In the formula, a2, a', b1, c1, and g are the same as above, provided that the total number of carbon atoms in each structure is 30 or less.)

[0146] The following structure is an example of a functional group-containing compound (a compound having a functional group and a hydrocarbon terminal group at both ends) represented by the above formulas (4a), (4b), and (4c). R, Z, Y, T, Y 3 By changing the combination of R', k5, and k6, several functional group-containing compounds can be obtained.

[0147] (In the formula, x', x, y, R 7, a1, a2, a', and g are the same as described above. y" is an integer of 0 or more and is an integer such that the total number of carbon atoms in the R' structure is 38 or less.)

[0148] In Step 2 of the method for preparing a hydrocarbon terminal group-containing oligomer 2, as a method for reacting a functional group-containing oligomer obtained by subjecting the functional group-containing silane compound represented by the above formula (3) to a partial hydrolysis and condensation reaction with a functional group-containing compound represented by the above formula (4a), (4b), or (4c) to extend the chain length, for example, the following methods can be mentioned. [Synthesis Method 2-1] A functional group-containing oligomer obtained by subjecting a functional group-containing silane compound represented by the above formula (3) in which E is a thiol group to a partial hydrolysis and condensation reaction, and a functional group-containing compound in which T in the above formula (4b) or (4c) is a terminal alkenyl group, or a functional group-containing oligomer obtained by subjecting a functional group-containing silane compound represented by the above formula (3) in which E is a terminal alkenyl group to a partial hydrolysis and condensation reaction, and a functional group-containing compound in which T in the above formula (4a) is a thiol group are mixed and reacted in the presence of a polymerization initiator to produce a hydrocarbon terminal group-containing oligomer.

[0149] Here, examples of the functional group-containing oligomer obtained by subjecting a functional group-containing silane compound represented by the above formula (3) in which E is a thiol group to a partial hydrolysis and condensation reaction can be as follows. (In the formula, Y 2 , Z, Y, R X , k4, and n are the same as described above.)

[0150] Further, examples of the functional group-containing compound in which T in the above formula (4b) or (4c) is a terminal alkenyl group can be as follows. (In the formula, x', x, and a' are the same as described above.)

[0151] Here, examples of the functional group-containing oligomer obtained by subjecting a functional group-containing silane compound represented by the above formula (3) in which E is a terminal alkenyl group to a partial hydrolysis and condensation reaction can be as follows. (In the formula, Y 2 , Z, Y, R X , k4, and n are the same as described above.)

[0152] The following are specific examples of oligomers represented by the above formula. (In the formula, n and a' are the same as above.)

[0153] Furthermore, examples of functional group-containing compounds in which T in formula (4a) is a thiol group are shown below. (In the formula, x is the same as above.)

[0154] In synthesis method 2-1, the amount of the functional group-containing compound in formula (4b) or (4c) in which T is a terminal alkenyl group is preferably 1 to 5 mol, particularly 1 to 3 mol, per mol of functional group-containing oligomer obtained by a partial hydrolysis condensation reaction of a functional group-containing silane compound represented by formula (3) in which E is a thiol group. Furthermore, the amount of the functional group-containing compound in formula (4a) in which T is a thiol group is preferably 1 to 5 mol, particularly 1 to 3 mol, per mol of functional group-containing oligomer obtained by a partial hydrolysis condensation reaction of a functional group-containing silane compound represented by formula (3) in which E is a terminal alkenyl group.

[0155] In synthesis method 2-1, examples of polymerization initiators include azo compounds such as 2,2'-azobisisobutyronitrile and 2,2'-azobis(isobutyrate)dimethyl, diacyl peroxides such as benzoyl peroxide and lauroyl peroxide, dialkyl peroxides such as dicumyl peroxide and di-tert-butyl peroxide, peroxycarbonates such as diisopropyl peroxydicarbonate and bis(4-tert-butylcyclohexyl) peroxydicarbonate, and alkyl peresters such as t-butyl peroxyoctoate and tert-butyl peroxybenzoate, among other peroxide compounds. The amount of polymerization initiator used is preferably 0.01 to 3 mol, particularly 0.1 to 1.5 mol, per mol of thiol groups in a functional group-containing oligomer obtained by partial hydrolysis condensation of a functional group-containing silane compound represented by the above formula (3) in which E is a thiol group, or per mol of terminal alkenyl groups in a functional group-containing oligomer obtained by partial hydrolysis condensation of a functional group-containing silane compound represented by the above formula (3) in which E is a terminal alkenyl group.

[0156] In addition, a solvent can be used when carrying out the reaction in synthesis method 2-1. Examples of solvents are the same as the solvent used in synthesis method 1-1 described above. When using a solvent, the amount to be used is preferably 0 to 3,000 parts by mass, particularly 50 to 2,000 parts by mass, per 100 parts by mass of the functional group-containing oligomer obtained by a partial hydrolysis condensation reaction of a functional group-containing silane compound represented by formula (3) above, in which E is a thiol group, or a functional group-containing oligomer obtained by a partial hydrolysis condensation reaction of a functional group-containing silane compound represented by formula (3) above, in which E is a terminal alkenyl group.

[0157] In synthesis method 2-1, the reaction conditions are preferably a temperature of 20 to 100°C, particularly 40 to 80°C, for 0.5 to 72 hours, and especially 1 to 36 hours.

[0158] In step 2 of method 2 for preparing hydrocarbon end group-containing oligomers, the following method can be used to extend the chain length by reacting a functional group-containing oligomer obtained by partially hydrolyzing and condensing a functional group-containing silane compound represented by formula (3) with a functional group-containing compound represented by formula (4a), (4b), or (4c). [Synthesis method 2-2] A hydrocarbon end group-containing oligomer can be produced by mixing a functional group-containing oligomer obtained by partially hydrolyzing and condensing a functional group-containing silane compound represented by formula (3) in which E is a hydroxyl group or an amino group with a functional group-containing compound in which T in formula (4a) is an isocyanate group, and reacting the mixture in the presence of a catalyst if necessary.

[0159] Here, examples of functional group-containing oligomers obtained by a partial hydrolysis condensation reaction of a functional group-containing silane compound represented by the above formula (3), in which E is a hydroxyl group or an amino group, are shown below. (In the formula, Y 2 Z, Y, R X (k4 and n are the same as above.)

[0160] Furthermore, examples of functional group-containing compounds in which T in formula (4a) is an isocyanate group are shown below. (In the formula, x is the same as above.)

[0161] In synthesis method 2-2, the amount of the functional group-containing compound in formula (4a) in which T is an isocyanate group is preferably 0.8 to 1.2 mol, and particularly 0.95 to 1.05 mol, per mol of the functional group-containing oligomer obtained by a partial hydrolysis condensation reaction of a functional group-containing silane compound represented by formula (3) in which E is a hydroxyl group or an amino group.

[0162] In synthesis method 2-2, a catalyst can be used in the above reaction, especially when E is a hydroxyl group. Examples of catalysts include titanium compounds such as tetrakis(2-ethylhexyl) orthotitanate, tetra-n-butyl titanate, and tetra-n-propyl titanate; zirconium compounds such as tetra-n-butyl zirconate and tetra-n-propyl zirconate; tin compounds such as dibutyltin dimethoxide and dibutyltin dilaurate; bismuth compounds such as bismastris(2-ethylhexanoate); and amine catalysts such as diazabicycloundecene. When using a catalyst, the amount used is preferably 0.01 to 100 parts by mass, particularly 0.1 to 20 parts by mass, per 100 parts by mass of the functional group-containing compound in which T is an isocyanate group.

[0163] In synthesis method 2-2, the reaction conditions are preferably a temperature of 20 to 100°C, particularly 23 to 60°C, for 0.5 to 72 hours, and especially 1 to 36 hours.

[0164] In addition, a solvent can be used when carrying out the reaction in synthesis method 2-2. Examples of solvents are the same as the solvent used in synthesis method 1-1 described above. When using a solvent, the amount to use is preferably 0 to 3,000 parts by mass, particularly 10 to 2,000 parts by mass, per 100 parts by mass of the functional group-containing oligomer obtained by a partial hydrolysis condensation reaction of a functional group-containing silane compound represented by formula (3) above, in which E is a hydroxyl group or an amino group.

[0165] In Step 2 of Preparation Method 2 of the hydrocarbon terminal group-containing oligomer, as a method for reacting the functional group-containing oligomer obtained by subjecting the functional group-containing silane compound represented by the above formula (3) to a partial hydrolysis and condensation reaction with the functional group-containing compound represented by the above formula (4a), (4b) or (4c) to extend the chain length, the following methods can be mentioned. [Synthesis Method 2-3] By mixing the functional group-containing oligomer obtained by subjecting the functional group-containing silane compound represented by the above formula (3) in which E is a hydroxyl group to a partial hydrolysis and condensation reaction with the functional group-containing compound in which T in the above formula (4a) is an ester group, or the functional group-containing oligomer obtained by subjecting the functional group-containing silane compound represented by the above formula (3) in which E is an ester group to a partial hydrolysis and condensation reaction with the functional group-containing compound in which T in the above formula (4a) is a hydroxyl group, and reacting them in the presence of a catalyst, a hydrocarbon terminal group-containing oligomer can be produced.

[0166] Here, examples of the functional group-containing oligomer obtained by subjecting the functional group-containing silane compound represented by the above formula (3) in which E is a hydroxyl group to a partial hydrolysis and condensation reaction are as follows. (In the formula, Y 2 , Z, Y, R X , k4, n are the same as above.)

[0167] Examples of the functional group-containing compound in which T in the above formula (4a) is an ester group are as follows. (In the formula, x is the same as above. R 2-3 is an alkyl group having 1 to 5 carbon atoms.)

[0168] Examples of the functional group-containing oligomer obtained by subjecting the functional group-containing silane compound represented by the above formula (3) in which E is an ester group to a partial hydrolysis and condensation reaction are as follows. (In the formula, Y 2 , Z, Y, R X , R 2-3 , k4, n are the same as above.)

[0169] Examples of the functional group-containing compound in which T in the above formula (4a) is a hydroxyl group are as follows. (In the formula, x is the same as above.)

[0170] In synthesis method 2-3, the amount of the functional group-containing compound in formula (4a) where T is an ester group is preferably 0.8 to 1.2 mol, particularly 0.95 to 1.05 mol, per mol of functional group-containing oligomer obtained by a partial hydrolysis condensation reaction of a functional group-containing silane compound represented by formula (3) where E is a hydroxyl group.

[0171] In synthesis method 2-3, a catalyst is used in the above reaction. Examples of catalysts include inorganic acids such as hydrochloric acid and sulfuric acid, and organic acids such as trifluoroacetic acid and p-toluenesulfonic acid. The amount of catalyst used is preferably 0.0001 to 100 parts by mass, particularly 0.001 to 0.1 parts by mass, per 100 parts by mass of a functional group-containing oligomer obtained by a partial hydrolysis condensation reaction of a functional group-containing silane compound represented by formula (3) above, in which E is a hydroxyl group, or a functional group-containing oligomer obtained by a partial hydrolysis condensation reaction of a functional group-containing silane compound represented by formula (3) above, in which E is an ester group.

[0172] In synthesis method 2-3, the method for inactivating the acid catalyst is not particularly limited as long as it can deactivate the acid catalyst, but it is preferable that the deactivator can be easily removed after deactivation. For example, Kyoward 500 can be mentioned. In the case of Kyoward 500, the amount is preferably 0.00001 to 0.01 parts by mass, more preferably 0.01 to 0.05 parts by mass, per 100 parts by mass of a functional group-containing oligomer obtained by a partial hydrolysis condensation reaction functional group-containing oligomer obtained by a functional group-containing oligomer obtained by a partial hydrolysis condensation reaction of a functional group-containing oligomer obtained by a functional group-containing oligomer obtained by a functional group-containing oligomer obtained by a functional group-containing oligomer obtained by a functional group-containing oligomer obtained by a functional group-containing oligomer obtained by a functional group-containing oligomer obtained by a functional group-containing oligomer obtained by a functional group-containing oligomer obtained by a functional group-containing oligomer obtained by a

[0173] In synthesis method 2-3, the reaction conditions are preferably a temperature of 20 to 200°C, particularly 65 to 120°C, for 1 to 72 hours, and especially 4 to 24 hours.

[0174] In synthesis method 2-3, a solvent can be used when carrying out the reaction. Examples of solvents are the same as those used in synthesis method 1-1 described above. When using a solvent, the amount to be used is preferably 0 to 3,000 parts by mass, particularly 10 to 2,000 parts by mass, per 100 parts by mass of a functional group-containing oligomer obtained by a partial hydrolysis condensation reaction of a functional group-containing silane compound represented by formula (3) above, where E is a hydroxyl group, or a functional group-containing oligomer obtained by a partial hydrolysis condensation reaction of a functional group-containing silane compound represented by formula (3) above, where E is an ester group.

[0175] In step 2 of method 2 for preparing hydrocarbon end group-containing oligomers, the following methods can be used to extend the chain length by reacting a functional group-containing oligomer obtained by partially hydrolyzing and condensing a functional group-containing silane compound represented by formula (3) with a functional group-containing compound represented by formula (4a), (4b), or (4c). [Synthesis method 2-4] A hydrocarbon end group-containing oligomer can be produced by mixing a functional group-containing oligomer obtained by partially hydrolyzing and condensing a functional group-containing silane compound represented by formula (3) in which E is a hydroxyl group with a functional group-containing compound in which T in formula (4a) is a carboxyl group, or by reacting a functional group-containing oligomer obtained by partially hydrolyzing and condensing a functional group-containing silane compound represented by formula (3) in which E is a carboxyl group with a functional group-containing compound in which T in formula (4a) is a hydroxyl group, in the presence of a catalyst.

[0176] Here, examples of functional group-containing oligomers obtained by a partial hydrolysis condensation reaction of a functional group-containing silane compound represented by the above formula (3), in which E is a hydroxyl group, are shown below. (In the formula, Y 2 Z, Y, R X (k4 and n are the same as above.)

[0177] Furthermore, examples of functional group-containing compounds in which T in formula (4a) is a carboxyl group are shown below. (In the formula, x is the same as above.)

[0178] Furthermore, examples of functional group-containing oligomers obtained by a partial hydrolysis condensation reaction of a functional group-containing silane compound represented by the above formula (3), in which E is a carboxyl group, are shown below. (In the formula, Y 2 Z, Y, R X (k4 and n are the same as above.)

[0179] Furthermore, examples of functional group-containing compounds in which T in formula (4a) is a hydroxyl group are shown below. (In the formula, x is the same as above.)

[0180] In synthesis method 2-4, the amount of the functional group-containing compound in formula (4a) where T is a carboxyl group is preferably 0.8 to 1.2 mol, particularly 0.95 to 1.05 mol, per mol of functional group-containing oligomer obtained by a partial hydrolysis condensation reaction of a functional group-containing silane compound represented by formula (3) where E is a hydroxyl group. Alternatively, the amount of the functional group-containing compound in formula (4a) where T is a hydroxyl group is preferably 0.8 to 1.5 mol, particularly 0.95 to 1.1 mol, per mol of functional group-containing oligomer obtained by a partial hydrolysis condensation reaction of a functional group-containing silane compound represented by formula (3) where E is a carboxyl group.

[0181] In synthesis method 2-4, a catalyst is used in the above reaction. Examples of catalysts include inorganic acids such as hydrochloric acid and sulfuric acid, and organic acids such as trifluoroacetic acid and p-toluenesulfonic acid. The amount of catalyst used is preferably 0.0001 to 100 parts by mass, particularly 0.001 to 0.1 parts by mass, per 100 parts by mass of a functional group-containing oligomer obtained by a partial hydrolysis condensation reaction of a functional group-containing silane compound represented by formula (3) above, in which E is a hydroxyl group, or a functional group-containing oligomer obtained by a partial hydrolysis condensation reaction of a functional group-containing silane compound represented by formula (3) above, in which E is a carboxyl group.

[0182] In synthesis method 2-4, the acid catalyst can be deactivated by the method described in synthesis method 2-3.

[0183] In synthesis method 2-4, the reaction conditions are preferably a temperature of 20 to 200°C, particularly 65 to 120°C, for 1 to 72 hours, and especially 4 to 24 hours.

[0184] In addition, in synthesis method 2-4, when carrying out the reaction, it is preferable to use a Dean-Stark apparatus to remove the water produced as a by-product during the reaction from the reaction system and to shift the equilibrium towards the product system.

[0185] In synthesis method 2-4, 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, and alcohols such as methanol and ethanol. When using a Dean-Stark apparatus, benzene and toluene are preferred. When using a solvent, the amount to be used is preferably 10 to 10,000 parts by mass, particularly 1,000 to 5,000 parts by mass, per 100 parts by mass of a functional group-containing oligomer obtained by a partial hydrolysis condensation reaction of a functional group-containing silane compound represented by formula (3) above, where E is a hydroxyl group, or a functional group-containing oligomer obtained by a partial hydrolysis condensation reaction of a functional group-containing silane compound represented by formula (3) above, where E is a carboxyl group.

[0186] In step 2 of method 2 for preparing hydrocarbon end group-containing oligomers, the following methods can be used to extend the chain length by reacting a functional group-containing oligomer obtained by partially hydrolyzing and condensing a functional group-containing silane compound represented by formula (3) with a functional group-containing compound represented by formula (4a), (4b), or (4c). [Synthesis method 2-5] A hydrocarbon end group-containing oligomer can be produced by mixing a functional group-containing oligomer obtained by partially hydrolyzing and condensing a functional group-containing silane compound represented by formula (3) in which E is a hydroxyl group with a functional group-containing compound in which T in formula (4a) is a leaving group, or by mixing a functional group-containing oligomer obtained by partially hydrolyzing and condensing a functional group-containing silane compound represented by formula (3) in which E is a leaving group with a functional group-containing compound in which T in formula (4a) is a hydroxyl group, and reacting the mixture in the presence of a base.

[0187] Here, examples of functional group-containing oligomers obtained by a partial hydrolysis condensation reaction of a functional group-containing silane compound represented by the above formula (3), in which E is a hydroxyl group, are shown below. (In the formula, Y 2 Z, Y, R X (k4 and n are the same as above.)

[0188] Furthermore, examples of functional group-containing compounds in which T in formula (4a) is a leaving group are shown below. (In the formula, x is the same as above.)

[0189] Furthermore, examples of functional group-containing oligomers obtained by a partial hydrolysis condensation reaction of a functional group-containing silane compound represented by the above formula (3), in which E is a leaving group, are shown below. (In the formula, Y 2 Z, Y, R X (k4 and n are the same as above.)

[0190] Furthermore, examples of functional group-containing compounds in which T in formula (4a) is a hydroxyl group are shown below. (In the formula, x is the same as above.)

[0191] In synthesis method 2-5, the amount of the functional group-containing compound in formula (4a) in which T is a leaving group is preferably 0.8 to 1.2 mol, particularly 0.95 to 1.05 mol, per mol of functional group-containing oligomer obtained by a partial hydrolysis condensation reaction of a functional group-containing silane compound represented by formula (3) in which E is a hydroxyl group.

[0192] In synthesis method 2-5, the base used in the above reaction is not particularly limited, but examples include lithium hydroxide, sodium hydride, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, cesium carbonate, potassium tert-butoxide, etc. The amount of base used is preferably 1 to 3 mol, particularly 1 to 1.5 mol, per 1 mol of hydroxyl groups in the functional group-containing oligomer obtained by partial hydrolysis condensation of a functional group-containing silane compound represented by formula (3) above, in which E is a hydroxyl group, or per 1 mol of hydroxyl groups in the functional group-containing compound in formula (4a) above, in which T is a hydroxyl group.

[0193] In synthesis method 2-5, the reaction conditions are preferably a temperature of 20 to 100°C, particularly 30 to 60°C, for 0.5 to 72 hours, and especially 1 to 24 hours.

[0194] In synthesis method 2-5, 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, and cyclic ether compounds such as tetrahydrofuran and dioxane. When using a solvent, the amount used is preferably 0 to 2,000 parts by mass, particularly 50 to 1,500 parts by mass, per 100 parts by mass of the hydrocarbon terminal group-containing compound having a hydroxyl group at the terminal end.

[0195] In synthesis method 2-5, salts and residual bases generated after the reaction are removed by filtration. The filtration method is not particularly limited, but for example, the reaction solution is filtered using a PTFE membrane filter with a pore size of 0.2 μm and a pressure filter.

[0196] A hydrocarbon end group-containing oligomer represented by formula (1) can be produced by any of the above synthesis methods 2-1 to 2-5.

[0197] The hydrocarbon terminal group-containing oligomer of the present invention is 5 × 10 -2 The evaporation start temperature at Pa is preferably 90°C or higher, and preferably 110°C or higher. Here, the evaporation start temperature is determined by performing a thermomass measurement of the hydrocarbon end group-containing oligomer under vacuum (1 × 10⁻⁶). -3 Pa ~ 5 x 10 -2 The sample boat was heated to 50°C at Pa), and then the temperature was increased by 50°C per minute until it reached 500°C. The degree of mass loss of the compound was examined, and the temperature at which the mass loss was 5% or more was taken as the temperature at which the mass loss occurred. If the evaporation start temperature is below 90°C, re-evaporation is likely to occur, and adhesion to the substrate may be insufficient. The evaporation start temperature of the hydrocarbon terminal group-containing oligomer of the present invention is determined by using only hydrocarbon terminal group-containing silane compounds as monomer components, which have a monovalent hydrocarbon group having 1 to 40 carbon atoms, which may be linear, branched, cyclic, or a combination thereof, and a monovalent hydrolyzable silyl group having a methoxy group or an ethoxy group as a hydrolyzable group, and which have at least two such methoxy groups or ethoxy groups in the molecule, and the average degree of polymerization n in NMR terms. NMR By setting the value to be greater than 1 and less than or equal to 100, the temperature can be set to 90°C or higher.

[0198] [Surface Treatment Agent] The present invention further provides a surface treatment agent containing the hydrocarbon end group-containing oligomer described above. The surface treatment agent is preferably non-fluorinated (made of a material that does not contain fluorine atoms). The surface treatment agent only needs to contain the hydrocarbon end group-containing oligomer described above, and may also contain unreacted raw materials, reaction intermediates, hydrocarbon end group-containing silane compounds which are monomer components that did not polymerize completely, etc. Furthermore, the present invention provides an NMR-calculated average degree of polymerization nNMR As long as the conditions within the range are met, it may also contain a partially hydrolyzed condensate obtained by further partially hydrolyzing and condensing the hydrolyzable silyl group of the hydrocarbon terminal group-containing oligomer described above.

[0199] Furthermore, from the viewpoint of improving wear resistance, it is preferable that the surface treatment agent of the present invention does not contain metal alkoxides such as tetraalkoxysilanes such as tetraethoxysilane and / or their partially hydrolyzed condensates.

[0200] 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), or organic bases (e.g., amines, trialkylamines, nitrogen-containing cyclic compounds). Among these, acetic acid, tetra-n-butyl titanate, and dibutyltin dilaurate are particularly desirable. When using a hydrolysis condensation catalyst, the amount 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 hydrocarbon-end-group-containing oligomer.

[0201] The surface treatment agent may contain a suitable solvent. Such solvents are preferably non-fluorinated solvents, and examples include hydrocarbon solvents (petroleum benzine, toluene, xylene, hexane, cyclohexane, methylcyclohexane, ethylcyclohexane, heptane, octane (n-octane, isooctane, etc.), nonane (n-nonane, isononane, etc.)), ketone solvents (acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, etc.), ether solvents (tetrahydrofuran (THF), dipropyl ether, dibutyl ether, methylcyclopentyl ether, methyl t-butyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, propylene glycol dimethyl ether, etc.), alcohol solvents (propylene glycol monomethyl ether, butanol, isopropanol, etc.), and ester solvents (ethyl acetate, propyl acetate, butyl acetate, pentyl acetate, propylene glycol monomethyl ether acetate). Among these, toluene, hexane, heptane, isooctane, isononane, cyclopentanone, dipropyl ether, dibutyl ether, methylcyclopentyl ether, methyl t-butyl ether, ethylene glycol dimethyl ether, propyl acetate, butyl acetate, and propylene glycol monomethyl ether acetate are preferred in terms of solubility, wettability, etc.

[0202] The above solvents may be mixed in two or more forms, and it is preferable to uniformly dissolve the hydrocarbon end group-containing oligomer. The optimal concentration of hydrocarbon end group-containing oligomer to be dissolved in the solvent varies depending on the processing method, and any amount that is easy to weigh is acceptable. However, when 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 hydrocarbon end group-containing oligomer. When vapor deposition is performed, it is preferable to use 1 to 100 parts by mass, particularly 3 to 50 parts by mass, per 100 parts by mass of the total of the solvent and hydrocarbon end group-containing oligomer. In either coating case, 100 parts by mass refers to the case where no solvent is used and the coating is performed directly.

[0203] 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. Vapor deposition is particularly preferred. 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 heat at 25 to 200°C, particularly 25 to 150°C, for 30 minutes to 36 hours, and especially 1 to 24 hours. When applied by vapor deposition, it is desirable to heat at a range of 20 to 200°C for 1 to 24 hours. Curing may also be performed under humid conditions.

[0204] 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.

[0205] 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.

[0206] The surface treatment agent of the present invention can form a hardened film with high levels of water repellency and abrasion resistance.

[0207] [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.

[0208] 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.

[0209] The present invention will be described in more detail below with reference to synthesis examples, examples, and comparative examples, but the present invention is not limited to the following examples. In the following examples, the mol amount of the compound is, with respect to the measured mass of the target compound, 1 The value was calculated by dividing by the molecular weight of the compound identified by 1H-NMR analysis. Furthermore, the film thickness was measured using spectroscopic ellipsometry with a spectroscopic ellipsometer. The room temperature was 25°C.

[0210] [Synthesis Example 1] In the reaction vessel, the following formula (A) 5.00 g (1.90 x 10) of the compound represented by -2 mol), 0.12 M hydrochloric acid 3.42 × 10 -1 g (hydrochloric acid 4.10 × 10 -5 mol, equivalent to 1.90 x 10⁻¹⁰ moles of water -2 The mixture (mol) was aged at 60°C for 16 hours. Then, Kyoward 500 was added in 5.00 x 10 -3 Add g and stir at 25°C for 1 hour. The reaction solution was then heated to atmospheric pressure (1 × 10⁻⁶). 5 The mixture was aged at 100°C under atmospheric pressure (Pa, the same applies hereafter) for 1 hour, and the by-product water was removed. Subsequently, it was aged at 120°C under atmospheric pressure for 3 hours, and filtered to obtain 4.1 g of hydrocarbon-terminal group-containing oligomer.

[0211] [Synthesis Example 2] The 0.12 M hydrochloric acid from Synthesis Example 1 is mixed with 6.85 × 10⁻¹⁶ M hydrochloric acid. -1 g (hydrochloric acid 4.10 × 10 -5 mol, equivalent to 3.80 moles of water × 10⁻⁶ -2 Except for the change to mol, partial hydrolysis condensation was carried out in the same manner as in Synthesis Example 1 to obtain 3.8 g of hydrocarbon-terminated oligomer.

[0212] [Synthesis Example 3] 0.12 M hydrochloric acid from Synthesis Example 1 is mixed with 3.46 × 10⁻¹⁶ 2.2 M sodium hydroxide aqueous solution. -1 g (sodium hydroxide 6.98 × 10 -4 mol, equivalent to 1.77 x 10⁻⁶ moles of water -2 The change was made to mol, and Kyoword 500 was changed to Kyoword 700 (5.00 x 10 -3 Except for the change to g), partial hydrolysis condensation was carried out in the same manner as in Synthesis Example 1 to obtain 3.9 g of hydrocarbon terminal group-containing oligomer.

[0213] [Synthesis Example 4] In the reaction vessel, the following formula (B) 5.00 g of the compound represented by (1.33 × 10) -2 mol), 2.4 M hydrochloric acid 2.40 × 10 -1 g (hydrochloric acid 5.76 × 10 -4 mol, equivalent to 1.33 moles of water × 10⁻⁶ -2 The mixture (mol) was aged at 60°C for 16 hours. Then, Kyoward 500 was added in 5.00 x 10 -3 The mixture was added and stirred at 25°C for 1 hour. The reaction solution was aged at 100°C under atmospheric pressure for 1 hour to remove the by-product water. Subsequently, it was aged at 120°C under atmospheric pressure for 3 hours and filtered to obtain 4.2 g of hydrocarbon-terminated oligomer.

[0214] [Synthesis Example 5] The 2.4 M hydrochloric acid from Synthesis Example 4 is mixed with 1.20 × 10⁻¹⁰ 4.8 M hydrochloric acid. -1 g (hydrochloric acid 5.76 × 10 -4 mol, equivalent to 6.66 moles of water × 10 -3 Except for the change to mol, partial hydrolysis condensation was carried out in the same manner as in Synthesis Example 4 to obtain 4.1 g of hydrocarbon terminal group-containing oligomer.

[0215] [Synthesis Example 6] In the reaction vessel, the following formula (C) 2.00 g (4.64 × 10) of the compound represented by -2 mol), 2.4 M hydrochloric acid 8.36 × 10 -2 g (hydrochloric acid 2.01 × 10 -4 mol, equivalent to 4.64 moles of water × 10⁻⁶ -2The mixture (mol) was aged at 60°C for 3 hours. Afterwards, activated carbon and Kyoward 500 were added in 2.00 x 10 -3 The mixture was added and stirred at 60°C for 1 hour. The reaction solution was aged at 100°C under atmospheric pressure for 1 hour to remove the by-product water. Subsequently, it was aged at 120°C under atmospheric pressure for 3 hours and filtered to obtain 1.3 g of hydrocarbon-terminated oligomer.

[0216] [Synthesis Example 7] The 2.4 M hydrochloric acid from Synthesis Example 6 is mixed with 4.8 M hydrochloric acid (4.18 × 10⁻¹⁰). -2 g (hydrochloric acid 2.01 × 10 -4 mol, equivalent to 2.32 moles of water × 10⁻⁶ -4 Except for the change to mol, partial hydrolysis condensation was carried out in the same manner as in Synthesis Example 6 to obtain 1.4 g of hydrocarbon terminal group-containing oligomer.

[0217] [Synthesis Example 8] In a reaction vessel, add 10.00 g of 1-decanethiol (5.74 x 10 -2 mol), toluene 25.00g, vinyltrimethoxysilane 10.20g (6.88 x 10 -2 mol), and 1.32 g (5.74 x 10) of 2,2'-azobis(isobutyrate)dimethyl -3 The mixture (mol) was aged at 75°C for 1 hour. Then, the solvent and unreacted materials were removed by reduced pressure distillation to obtain 18.13 g of product.

[0218] The resulting compound was 1 ¹H-NMR confirmed that the structure is represented by the following formula (D).

[0219] In the reaction vessel, the following formula (D) obtained above 5.00 g (1.55 x 10) of the compound represented by -2 mol), 0.12 M hydrochloric acid 2.79 × 10 -1 g (hydrochloric acid 3.35 × 10 -5 mol, equivalent to 1.55 moles of water × 10⁻⁶ -2 The mixture (mol) was aged at 60°C for 3 hours. Afterwards, activated carbon and Kyoward 500 were added in 5.00 x 10 -3The mixture was added and stirred at 60°C for 1 hour. The reaction solution was aged at 100°C under atmospheric pressure for 1 hour to remove the by-product water. Subsequently, it was aged at 120°C under atmospheric pressure for 3 hours and filtered to obtain 4.1 g of hydrocarbon-terminated oligomer.

[0220] [Synthesis Example 9] 1.40 × 10⁻¹⁶ of the 0.12 M hydrochloric acid from Synthesis Example 8 -1 g (hydrochloric acid 1.68 × 10 -5 mol, equivalent to 7.77 moles of water × 10⁻⁶ -3 Except for the change to mol, partial hydrolysis condensation was carried out in the same manner as in Synthesis Example 8 to obtain 4.2 g of hydrocarbon-terminated oligomer.

[0221] [Synthesis Example 10] In a reaction vessel, add 5.00 g of vinyltrimethoxysilane (3.37 x 10 -2 mol), 2.4 M hydrochloric acid 6.07 × 10 -1 g (hydrochloric acid 1.46 × 10 -3 mol, equivalent to 3.37 moles of water × 10⁻⁶ -2 The mixture (mol) was aged at 25°C for 3 hours. Then, Kyoward 500 was added at 5.00 x 10 -3 The mixture was added and stirred at 25°C for 1 hour. The reaction solution was aged at 100°C under atmospheric pressure for 1 hour to collect the by-products. Subsequently, it was aged at 120°C under atmospheric pressure for 3 hours, and Kyoward 500 was removed by filtration to obtain 2.9 g of functional group-end-containing oligomer.

[0222] In the reaction vessel, add 5.00 × 10⁻¹⁶ of the functional group-end-containing oligomer synthesized above. -1 g (5.14 × 10⁻¹⁰ NMR internal standard calculation) -3 mol), toluene 10.00g, 1-decanethiol 8.96 x 10 -1 g (5.14 x 10 -3 mol), and 2,2'-Azobis(isobutyrate)dimethyl 1.18 × 10 -1 g (5.14 x 10 -4 The mixture (mol) was aged at 75°C for 1 hour. Then, the solvent and unreacted products were removed by vacuum distillation to obtain 1.3 g of hydrocarbon-terminated oligomer.

[0223] [Synthesis Example 11] The 2.4 M hydrochloric acid from Synthesis Example 10 is mixed with 3.04 × 10⁻¹⁰ 0.12 M hydrochloric acid. -1 g (hydrochloric acid 3.65 × 10-5 mol, equivalent to 1.69 x 10⁻¹⁰ moles of water -2 Except for the change to mol, partial hydrolysis condensation was carried out in the same manner as in Synthesis Example 10 to obtain 3.9 g of a functional group-end-containing oligomer.

[0224] In the reaction vessel, add 5.00 × 10⁻¹⁶ of the functional group-end-containing oligomer synthesized above. -1 g (3.96 × 10⁻¹⁰ NMR internal standard calculation) -3 mol), toluene 10.00g, 1-decanethiol 6.90 x 10 -1 g (3.96 x 10 -3 mol), and 2,2'-Azobis(isobutyrate)dimethyl 9.12 × 10 -2 g (3.96 x 10 -4 The mixture (mol) was aged at 75°C for 1 hour. Then, the solvent and unreacted products were removed by vacuum distillation to obtain 1.1 g of hydrocarbon-terminated oligomer.

[0225] [Synthesis Example 12] In the reaction vessel, the following formula (E) 10.00 g (3.63 × 10) of the compound represented by -2 Mix mol) and 50.00 g of tetrahydrofuran and stir at 0°C. Then add 90.7 mL (1.81 × 10) of allyl magnesium chloride (2.0 M tetrahydrofuran solution). -1 A mol (unit of volume) was added dropwise, and the mixture was aged at 25°C for 24 hours. 50.00 g of 2 M hydrochloric acid was added to the resulting solution, and the aqueous layer was extracted three times with toluene. The combined organic layers were washed with pure water and saturated brine, and dried over magnesium sulfate. Subsequently, the mixture was treated with activated carbon, and the solvent and unreacted materials were removed by vacuum distillation to obtain 7.65 g of product.

[0226] The resulting compound was 1 ¹H-NMR confirmed that the structure is represented by the following formula (F).

[0227] In the reaction vessel, the following formula (F) obtained above 7.00 g (2.39 × 10) of the compound represented by -2 mol), toluene 7.00g, triethoxysilane 39.26g (2.39 x 10) -1mol), 2.60 × 10¹³ toluene solution of chloroplatinic acid / vinylsiloxane complex -3 g (8.05 × 10 as Pt alone) -9 (containing mol), and formamide 3.30 × 10 -3 g (7.33 × 10 -5 The mixture (mol) was aged at 80°C for 48 hours. After that, the solvent and unreacted materials were removed by vacuum distillation to obtain 15.12 g of the product.

[0228] The resulting compound was 1 ¹H-NMR confirmed that the structure is represented by the following formula (G).

[0229] In the reaction vessel, the following formula (G) obtained above 5.00 g of the compound represented by (6.37 × 10) -3 mol), 0.12 M hydrochloric acid 3.44 × 10 -1 g (hydrochloric acid 4.13 × 10 -5 mol, equivalent to 1.91 moles of water × 10⁻⁶ -2 The mixture (mol) was aged at 60°C for 16 hours. Then, Kyoward 500 was added in 5.00 x 10 -3 The mixture was added and stirred at 25°C for 1 hour. The reaction solution was aged at 100°C under atmospheric pressure for 1 hour to remove the by-product water. Subsequently, it was aged at 120°C under atmospheric pressure for 3 hours and filtered to obtain 3.8 g of hydrocarbon-terminated oligomer.

[0230] [Synthesis Example 13] The 0.12 M hydrochloric acid from Synthesis Example 12 was mixed with 1.72 × 10⁻¹⁰ 0.12 M hydrochloric acid. -2 g (hydrochloric acid 2.06 × 10 -6 mol, equivalent to 9.54 moles of water × 10⁻⁶ -4 Except for the change to mol, partial hydrolysis condensation was carried out in the same manner as in Synthesis Example 12 to obtain 3.9 g of hydrocarbon terminal group-containing oligomer.

[0231] [Comparative Compound 1] Compound represented by the following formula (A)

[0232] [Comparative Compound 2] Compound represented by the following formula (B)

[0233] [Comparative Compound 3] Compound represented by the following formula (C)

[0234] [Comparative Compound 4] Compound represented by the following formula (D)

[0235] [Comparative Compound 5] Compound represented by the following formula (G)

[0236] [Examples 1-13, Comparative Examples 1-5] Evaluate vapor deposition coating properties. Thermomass measurements were performed to investigate the degree of mass loss of hydrocarbon-terminated oligomers and comparative compounds. Under vacuum (1 × 10⁻⁶) -3 Pa ~ 5 x 10 -2 The sample boat was heated to 50°C at Pa) and then the temperature was increased by 50°C per minute until it reached 500°C, and the degree of mass loss of the compound was examined. The evaporation onset temperature was defined as the temperature at which the mass loss was 5% or more as determined by thermomass measurement. The results (evaporation onset temperature) are shown in Tables 1 to 5. Comparative compound 4 was left blank because it began to lose mass before the temperature was increased while being heated to 50°C. The hydrocarbon-terminated oligomers of synthesis examples 1 to 13 had higher molecular weights due to partial hydrolysis condensation, resulting in higher evaporation onset temperatures than the monomer components of comparative compounds 2, 3, and 5.

[0237] The average degree of polymerization of hydrocarbon-terminated oligomers obtained in the synthesis examples was measured using the following method based on NMR. The results are shown in Tables 1 to 5. Average degree of polymerization of hydrocarbon-terminated oligomers based on NMR n NMR This was done using an NMR analyzer (manufacturer: JEOL Ltd., instrument name: JNM-ECS400), 1 The terminal groups of the target oligomer were analyzed using 1H-NMR to determine the values. Specifically, in Examples 1 to 11 and Comparative Examples 1 to 4, the terminal hydrolyzable group is a methoxy group, and the number of hydrolyzable silyl groups in the monomer component is 1. Therefore, when the NMR integral value of the terminal methyl group in the hydrocarbon terminal group of the hydrocarbon terminal group-containing oligomer is set to 3, the NMR integral value v of the remaining methoxy group was determined, and n NMR= Derived from 6 / (v-3). In Examples 12, 13, and Comparative Example 5, the terminal hydrolyzable group is a methoxy group, and the number of hydrolyzable silyl groups L in the monomer component is 3. Therefore, when the NMR integral value of the terminal methyl group in the hydrocarbon terminal group is set to 3, the NMR integral value w of the methylene group adjacent to the oxygen atom in the remaining ethoxy group is determined, and n NMR This was derived from = 12 / (w-6).

[0238] Preparation of Surface Treatment Agents and Formation of Cured Films Surface treatment agents were prepared by dissolving hydrocarbon-end group-containing oligomers and comparative compounds of the synthesis examples shown in Tables 1 to 5 below in toluene so that the oligomers and compounds each made up 10% by mass. Each surface treatment agent was vapor-deposited onto glass (Gorilla, manufactured by Corning) that had been coated with SiO2 to a thickness of 10 nm on its outermost surface, and cured for 1 hour at 80°C and 80% relative humidity, and then for 12 hours at 25°C and 50% relative humidity to form a cured film with a thickness of 3 to 5 nm.

[0239] The water repellency and abrasion resistance of the glass with a hardened coating were evaluated using the method described below.

[0240] 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.) (droplet: 2 μl, temperature: 25°C, relative humidity: 40%). The degree of water repellency improvement was calculated as follows. A contact angle (water repellency) of 85° or higher was considered good. The results (water contact angle) are shown in Tables 1 to 5.

[0241] 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 recorded to evaluate abrasion resistance. The test environment conditions were 25°C and 40% relative humidity. A good result was defined as 2,000 or more times the contact angle fell below 80°. The results (number of times the water contact angle fell below 80°) are shown in Tables 1 to 5. [Eraser Abrasion Resistance Test Conditions] Eraser: MINOAN Contact area: 1 cm 2Travel distance (one way): 40 mm Travel speed: 3,200 mm / min Load: 1 kgf / 6 mmφ

[0242] The hydrocarbon-end group-containing oligomers of Synthesis Examples 1 to 13, described in Tables 1 to 5 below, have a larger molecular weight compared to the monomer components of Comparative Compounds 1 to 5, which are comparative examples. As a result, their evaporation initiation temperature is higher, and they are less prone to re-evaporation. Furthermore, the hydrocarbon-end group-containing oligomers of Synthesis Examples 1 to 13, described in Tables 1 to 5 below, have closer hydrocarbon chain distances, which makes it easier for the hydrocarbon chains to be densely oriented. Consequently, the hydrocarbon-end group-containing oligomers of Synthesis Examples 1 to 13 exhibited superior water repellency and eraser abrasion resistance compared to the monomer components of Comparative Compounds 1 to 5, which are comparative examples. In summary, the surface treatment agents used in the examples of the hydrocarbon-end group-containing oligomers of the present invention were able to obtain a cured film that achieved a high level of both water repellency and abrasion resistance in vapor deposition coating.

[0243]

[0244]

[0245]

[0246]

[0247]

Claims

1. A monomer component consisting only of hydrocarbon-terminal group-containing silane compounds having a monovalent hydrocarbon group having 1 to 40 carbon atoms, which may be linear, branched, cyclic, or a combination thereof, and a monovalent hydrolyzable silyl group having a methoxy or ethoxy group as a hydrolyzable group, and having at least two such methoxy or ethoxy groups in the molecule, with an NMR-calculated average degree of polymerization n NMR However, the hydrocarbon end group-containing oligomer for vapor deposition is greater than 1 and less than or equal to 100.

2. The monomeric component is the following general formula (1) The hydrocarbon terminal group-containing oligomer for vapor deposition according to claim 1, which is a hydrocarbon terminal group-containing silane compound represented by the formula: (wherein R is a monovalent hydrocarbon group having 1 to 40 carbon atoms, which may be linear, branched, cyclic, or a combination thereof; Z is a divalent linking functional group independently comprising at least one selected from an oxygen atom, a nitrogen atom, a sulfur atom, and a silicon atom; Y is a divalent hydrocarbon group having 1 to 30 carbon atoms, which may be linear, branched, cyclic, or a combination thereof; W is a single bond, a carbon atom, a silicon atom, a nitrogen atom, or a 3 to 5 valent organic group; A is a monovalent hydrolyzable silyl group having a methoxy group or an ethoxy group; k1 is an integer from 0 to 3; k2 is an integer from 1 to 4; k3 is 0 or 1. However, each molecule has at least two methoxy groups or ethoxy groups.) 3. The hydrocarbon-terminated oligomer for vapor deposition according to claim 2, wherein Z is independently a divalent group selected from ether groups, carbonyl (ketone) groups, ester groups, carbonate groups, thioether groups, sulfinyl groups, sulfonyl groups, thioester groups, thiocarbonate groups, thiocarbamate groups, amino groups, amide groups, carbamate groups, urea groups, divalent nitrogen-containing heterocyclic groups, diorganosilylene groups, and divalent organopolysiloxane residues having 2 to 10 silicon atoms in a linear chain or 3 to 10 silicon atoms in a branched or cyclic configuration.

4. In equation (1), Y independently satisfies the following general equation (2) (In the formula, R 1 R is a monovalent hydrocarbon group having 1 to 10 carbon atoms, which may be linear, branched, cyclic, or a combination thereof. 2 is a divalent cyclic hydrocarbon group having 3 to 10 carbon atoms, which may independently have substituents. a is an integer from 0 to 30, b is an integer from 0 to 15, c is an integer from 0 to 10, and d is an integer from 0 to 6, and the sum of a, b, c, and d is an integer such that the sum of the carbon atoms in formula (2) is from 1 to 30. Each repeating unit shown in the parentheses with a, b, c, and d may be randomly bonded.) The hydrocarbon terminal group-containing oligomer for vapor deposition according to claim 2, which is a group represented by ).

5. In formula (1), W is a single bond, a carbon atom, a silicon atom, a nitrogen atom, a trivalent or tetravalent cyclic hydrocarbon group having 6 to 8 carbon atoms, -SiR 10 = (R 10 (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 11 = (R 11 The hydrocarbon terminal group-containing oligomer for vapor deposition according to claim 2, wherein the group is a trivalent group represented by a hydrogen atom, a hydroxyl group, or an alkyl group having 1 to 3 carbon atoms; a linear or branched or cyclic trivalent to pentavalent organopolysiloxane residue having 2 to 10 silicon atoms; a trivalent amide group; a trivalent carbamate group; a trivalent or tetravalent urea group; and a trivalent or tetravalent nitrogen-containing heterocyclic group.

6. 5 x 10 -2 The hydrocarbon-end group-containing oligomer for vapor deposition according to claim 1, wherein the evaporation initiation temperature under Pa is 90°C or higher.

7. A surface treatment agent comprising a hydrocarbon-terminated oligomer for vapor deposition according to any one of claims 1 to 6.

8. An article having a cured coating formed by the surface treatment agent described in claim 7.

9. A method for producing a hydrocarbon-terminated oligomer for vapor deposition according to claim 2, comprising mixing a hydrocarbon-terminated silane compound represented by the above general formula (1) with water, a catalyst, and an organic solvent as an optional component, carrying out a partial hydrolysis condensation reaction, then deactivating the catalyst, and distilling off the catalyst and reaction by-products generated after the reaction.

10. The method for producing a hydrocarbon-terminated oligomer for vapor deposition according to claim 9, wherein the amount of water used is greater than 0 mol and less than or equal to 10 mol per mol of hydrolyzable silyl groups in the hydrocarbon-terminated silane compound.

11. The method for producing a hydrocarbon-terminated oligomer for vapor deposition according to claim 9, wherein the catalyst is an inorganic acid or an organic acid, or an inorganic base or an organic base.

12. The method for producing a hydrocarbon-terminated oligomer for vapor deposition according to claim 9, wherein the organic solvent is an alcohol.

13. [1] The following general formula (3) (In the formula, Z, Y, W, A, k2, and k3 are the same as those in the above formula (1), E is a monovalent functional group that can react with and link to T described later, and Y 2 is a divalent hydrocarbon group having 1 to 30 carbon atoms, which may be linear, branched, cyclic, or a combination thereof, and k4 is an integer of 0 to 2.) A functional group-containing silane compound represented by the formula is mixed with water, a catalyst, and optionally an organic solvent, and after allowing a partial hydrolysis and condensation reaction to proceed, the catalyst is deactivated, and the catalyst and reaction by-products generated after the reaction are distilled off to obtain a functional group-containing oligomer. [2] The functional group-containing oligomer obtained in the above step and the following general formula (4a), (4b), or (4c) (In the formula, R, Z, Y are the same as those in the above formula (1), T is a monovalent functional group that can react with and link to E described above, and Y 3 is a divalent hydrocarbon group having 1 to 28 carbon atoms, which may be linear, branched, cyclic, or a combination thereof, and R' is a monovalent hydrocarbon group having 1 to 38 carbon atoms, which may be linear, branched, cyclic, or a combination thereof. k5 is an integer of 0 to 2, the sum of k4 and k5 is an integer of 0 to 2, k6 is 0 or 1, and the sum of k4 and k6 is 0 or 1.) The method for producing a hydrocarbon terminal group-containing oligomer for vapor deposition according to claim 2, which includes a step of reacting with a functional group-containing compound represented by the formula to extend the chain length.

14. A method for producing a hydrocarbon terminal group-containing oligomer for vapor deposition according to claim 13, wherein E of formula (3) and T of formula (4a), (4b), or (4c) are a monovalent functional group that reacts and links with each other, and the pair (E, T) is any of (terminal olefin group, thiol group), (thiol group, terminal olefin group), (hydroxyl group, isocyanate group), (amino group, isocyanate group), (ester group, hydroxyl group), (hydroxyl group, ester group), (ester group, amino group), (amino group, ester group), (carboxyl group, hydroxyl group), (hydroxyl group, carboxyl group), (carboxyl group, amino group), (amino group, carboxyl group), and (leaving group, hydroxyl group).

15. The method for producing a hydrocarbon-terminated oligomer for vapor deposition according to claim 13, wherein the amount of water used is greater than 0 mol and less than or equal to 3 mol per mol of hydrolyzable silyl groups in the hydrocarbon-terminated silane compound.

16. The method for producing a hydrocarbon-terminated oligomer for vapor deposition according to claim 13, wherein the catalyst is an inorganic acid or an organic acid, or an inorganic base or an organic base.

17. The method for producing a hydrocarbon-terminated oligomer for vapor deposition according to claim 13, wherein the organic solvent is an alcohol.

18. A hydrocarbon-terminal group-containing oligomer represented by the following average formula (5). (In the formula, R is a monovalent hydrocarbon group having 1 to 40 carbon atoms, which may be linear, branched, cyclic, or a combination thereof; Z is a divalent linking functional group containing at least one atom independently selected from oxygen, nitrogen, sulfur, and silicon atoms; Y is a divalent hydrocarbon group having 1 to 30 carbon atoms, which may be linear, branched, cyclic, or a combination thereof; k1 is an integer from 0 to 3; R X (where n is independently a methyl group, an ethyl group, or a hydrogen atom, and n is a number greater than 1 and less than or equal to 100 on average.) 19. The hydrocarbon-terminated oligomer according to claim 18, which is for vapor deposition.

20. A surface treatment agent comprising the hydrocarbon-terminated oligomer according to claim 18 or 19.

21. An article having a cured coating formed by the surface treatment agent described in claim 20.

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