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

Abstract

A hydrocarbon-terminal-group-containing compound represented by formula (1) has improved intermolecular interactions and improved mobility of molecular chains when used as a surface treatment agent for a non-fluorine material, and a surface treatment agent containing the compound can form a cured coating film having excellent water repellency, slipperiness, ease of dirt removal, abrasion resistance, in particular, steel wool abrasion resistance, and alkali resistance. (In the formula, R represents a monovalent hydrocarbon group having 1-60 carbon atoms; Z represents a divalent linking functional group containing at least one selected from O, N, S, and Si; Y represents a divalent hydrocarbon group having 1-30 carbon atoms; W represents C, Si, N, or a trivalent to pentavalent organic group; A represents a monovalent reactive group; k1 represents 1-3; and k2 represents 2-4.)

Description

Hydrocarbon-terminated compounds, surface treatment agents, and articles

[0001] The present invention relates to hydrocarbon-terminated compound materials, and more particularly to non-fluorinated hydrocarbon-terminated compound materials that form a film with excellent water repellency, slipperiness, dirt-wiping properties, abrasion resistance, and alkali resistance; a surface treatment agent containing the compound; and an article surface-treated with the surface treatment agent.

[0002] In recent years, the use of touch panels in displays such as smartphones and in-car displays has accelerated. However, because touch panels have exposed screens, they are frequently in direct contact with fingers and cheeks, making them prone to dirt and 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 treatment 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 improvements in abrasion resistance and alkali resistance are desired.

[0008] 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

[0009] 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 have fluorine atoms in its molecule) hydrocarbon-terminated compound that can form a cured film with excellent water repellency, slipperiness, dirt-wiping properties, abrasion resistance, and alkali resistance, a non-fluorine-based surface treatment agent containing the compound, and an article surface-treated with the surface treatment agent.

[0010] As a result of diligent research to solve the above-mentioned objectives, the present inventors have found that when a hydrocarbon terminal group-containing compound represented by general formula (1), described later, which has a monovalent hydrocarbon group having 1 to 60 carbon atoms and 2 to 4 reactive groups at the end of its molecular chain, and has 1 to 3 linking functional groups in the linking group (molecular chain) between the monovalent hydrocarbon group and the 2 to 4 reactive groups, is used as a surface treatment agent for the above-mentioned nonfluorine-based material, intermolecular interactions and molecular chain mobility are improved, and a surface treatment agent containing this compound can form a hardened film with excellent water repellency, slipperiness, dirt-wiping properties, abrasion resistance, especially resistance to steel wool abrasion and alkali resistance, thus leading to the present invention.

[0011] Accordingly, the present invention provides the following hydrocarbon terminal group-containing compounds, surface treatment agents and articles. [1] The following general formula (1) A hydrocarbon terminal group-containing compound represented by the formula (wherein R is a monovalent hydrocarbon group having 1 to 60 carbon atoms, Z is a divalent linked functional group containing at least one independently selected from an oxygen atom, a nitrogen atom, a sulfur atom, and a silicon atom, Y is independently a divalent hydrocarbon group having 1 to 30 carbon atoms, W is a carbon atom, a silicon atom, a nitrogen atom, or a 3 to 5 valent organic group, A is a monovalent reactive group, k1 is an integer from 1 to 3, and k2 is an integer from 2 to 4.) [2] In the above formula (1), A is a cyclic ether group, and the following general formula (2) (In the formula, R 1 ) is an alkyl group or phenyl group having 1 to 4 carbon atoms independently, X is an alkyl group or hydrolyzable group independently, and n is an integer from 1 to 3. ) A hydroxyl group-containing silyl group or hydrolyzable silyl group represented by the following general formula (3) A hydrocarbon terminal group-containing compound according to [1], wherein the silazane group is represented by (wherein n'' is a number from 0 to 3, and n' is (3-n'') / 2). [3] A hydrocarbon terminal group-containing compound according to [2], wherein in formula (2) above, X is selected from the group consisting of a hydroxyl group, an alkoxy group having 1 to 10 carbon atoms, an alkoxyalkoxy group having 2 to 10 carbon atoms, an acyloxy group having 1 to 10 carbon atoms, an alkenyloxy group having 2 to 10 carbon atoms, a halogen group, and a dialkylamino group having 2 to 10 carbon atoms. [4] A hydrocarbon terminal group-containing compound according to any one of [1] to [3] above, wherein in formula (1) above, R is a monovalent hydrocarbon group having 3 to 32 carbon atoms, which may be linear, branched, cyclic, or a combination thereof. [5] A hydrocarbon terminal group-containing compound according to any one of [1] to [4], wherein Z is independently 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, diorganosilylene group, and a divalent organopolysiloxane residue having 2 to 10 silicon atoms in a linear chain or 3 to 10 silicon atoms in a branched or cyclic configuration. [6] A hydrocarbon terminal group-containing compound according to any one of [1] to [4], wherein Y is independently the following general formula (4) (In the formula, R 2 R is an independent monovalent hydrocarbon group having 1 to 10 carbon atoms. 3 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 (4) 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 compound according to any one of [1] to [5], which is a group represented by ). [7] In the above formula (1), W is a carbon atom, a silicon atom, a nitrogen atom, a trivalent or tetravalent cyclic hydrocarbon group having 6 to 8 carbon atoms, -SiR 8 = (R 8is 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 9 = (R 9 is 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 [1] to [6] The hydrocarbon terminal group-containing compound according to any one of [1] to [6]. [8] In the above formula (1), k1 is 1 and R is represented by the following general formula (5) (In the formula, R 4 is a methyl group, a cyclic alkyl group or a phenyl group. R 3 is a divalent cyclic hydrocarbon group having 3 to 10 carbon atoms which may independently have a substituent. y is an integer of 0 or more, h is an integer of 0 to 6, and the sum of y and h is an integer such that the total number of carbon atoms in the formula (5) is 60 or less. Each repeating unit shown in the parentheses with y and h may be randomly bonded.) is a monovalent hydrocarbon group represented by [1] to [7] The hydrocarbon terminal group-containing compound according to any one of [1] to [7]. [9] In the above formula (1), the hydrocarbon terminal group-containing compound according to any one of [k1 is 2 or 3] [1] to [8].

[10] A surface treatment agent containing the hydrocarbon terminal group-containing compound according to any one of [1] to [9].

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

[10] .

[0012] The article surface-treated with the surface treatment agent containing the hydrocarbon terminal group-containing compound of the present invention is excellent in water repellency, slipperiness, dirt removability, abrasion resistance, and alkali resistance.

[0013] [Hydrocarbon terminal group-containing compound] The hydrocarbon terminal group-containing compound of the present invention is represented by the following general formula (1). (In the formula, R is a monovalent hydrocarbon group having 1 to 60 carbon atoms, Z is a divalent linked functional group independently containing at least one atom selected from oxygen, nitrogen, sulfur, and silicon, Y is independently a divalent hydrocarbon group having 1 to 30 carbon atoms, W is a carbon atom, silicon atom, nitrogen atom, or a 3 to 5 valent organic group, A is a monovalent reactive group, k1 is an integer from 1 to 3, and k2 is an integer from 2 to 4.)

[0014] The hydrocarbon-terminated compound of the present invention has a monovalent hydrocarbon group (hydrocarbon terminator, R in formula (1)) having 1 to 60 carbon atoms, preferably 3 to 32 carbon atoms, more preferably 8 to 30 carbon atoms at the end of the molecular chain, and has 2 to 4 reactive groups (substrate-adhering groups, A in formula (1)) that exhibit substrate adhesion at the other end of the molecular chain, and the linking group connecting the hydrocarbon terminator and the substrate-adhering group is a linking group (-(Z-Y in formula (1))) containing a divalent linking functional group (Z in formula (1)) that includes at least one selected from an oxygen atom, a nitrogen atom, a sulfur atom, and a silicon atom. k1 -W(-Y-) k2 The above-mentioned linking functional group is a characteristic feature. The introduction of the above-mentioned linking functional group improves the molecular mobility of the above-mentioned compound, starting from the linking functional group. In addition, the orientation of the monovalent hydrocarbon group (hereinafter also referred to as hydrocarbon chain) is determined by the linking functional group, and due to intermolecular interactions between hydrocarbon chains and between linking functional groups, the hydrocarbon chains on the surface of the cured film tend to be oriented in one direction. As a result, the cured film of the surface treatment agent containing the above-mentioned compound has excellent water repellency, slipperiness, dirt wiping properties, abrasion resistance, and alkali resistance. Furthermore, the presence of two or more substrate adhesion groups improves adhesion to the substrate, resulting in excellent abrasion resistance and alkali resistance.

[0015] In formula (1) above, R is a monovalent hydrocarbon group having 1 to 60 carbon atoms, preferably 3 to 32 carbon atoms, and more preferably 8 to 30 carbon atoms. When R has 3 or more carbon atoms, it may be linear, branched, cyclic, or a combination thereof. Examples of R include the following: (In the formula, x is an integer between 0 and 59, preferably between 2 and 31, 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 60 or less.)

[0016] R is more preferably a monovalent hydrocarbon group represented by the following general formula (5), and particularly preferably an alkyl group. (In the formula, R 4 R is a methyl group, a cyclic alkyl group, or a phenyl group. 3 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, more preferably 0, and the sum of y and h is an integer such that the total number of carbon atoms in formula (5) is 60 or less, preferably 3 to 32, more preferably 8 to 30. Each repeating unit shown in parentheses with y and h may be randomly coupled.

[0017] In the above formula (5), R 4 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.

[0018] In the above formula (5), R 3 R is a divalent cyclic hydrocarbon group having 3 to 10 carbon atoms, which may independently have substituents. 3 Examples of divalent cyclic hydrocarbon groups represented by the formula are listed below. (In the formula, R 6 (These are alkyl groups having 1 to 4 carbon atoms, such as methyl and ethyl groups.)

[0019] In formula (1) above, Z is a linking group that, together with Y and W, links the hydrocarbon chain at the end of the molecular chain (R in formula (1)) to the reactive 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, and is a characteristic component of the present invention. 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, urea groups, and amide groups.

[0020] 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 5 (E is an integer from 1 to 9.)

[0021] Here, R 5 R is independently a hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms. Examples of monovalent hydrocarbon groups having 1 to 10 carbon atoms include alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, neopentyl, cyclopentyl, 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. 5If the number of carbon atoms is 3 or more, it may be linear, branched, cyclic, or a combination thereof. 5 Preferably, the elements are a hydrogen atom, a methyl group, or a phenyl group.

[0022] 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 reactive group (A in formula (1)), and is independently a divalent hydrocarbon group having 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms, more preferably 1 to 11 carbon atoms, and even more preferably 1 to 4 carbon atoms. When Y has 3 or more carbon atoms, it may be linear, branched, cyclic, or a combination thereof. Examples of Y include the group represented by the following formula (4). (In the formula, R 2 R is an independent monovalent hydrocarbon group having 1 to 10 carbon atoms. 3 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 (4) is 1 to 30. Each repeating unit shown in parentheses with a, b, c, and d may be randomly combined.

[0023] In the above formula (4), R 2 R is an independent monovalent hydrocarbon group having 1 to 10 carbon atoms. 2 If the carbon number is three or more, it may be linear, branched, cyclic, or a combination thereof. Specific examples of monovalent hydrocarbon groups 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. 2 The following formula is preferred. (In the formula, g is an integer between 0 and 4.)

[0024] In the above formula (4), R3 R is a divalent cyclic hydrocarbon group having 3 to 10 carbon atoms, which may independently have substituents, and is the R of formula (5) described above. 3 It is the same as, and examples similar to those exemplified above can be given.

[0025] In formula (4) 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 (4) is 1 to 30, preferably from 1 to 10. Furthermore, the repeating units shown in the parentheses of a, b, c, and d may be combined randomly.

[0026] 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 W, A, or Z. (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.)

[0027] In formula (1) above, W is 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 cyclic hydrocarbon group with 6 to 8 carbon atoms and a 3 or 4 valent status, -SiR 8 = (R 8 (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 9 = (R 9Examples 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).

[0028] 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.

[0029] Examples of such W include those shown below. In the structure below, the leftmost connection is connected to the Y enclosed in the brackets k1, and the other connections are connected to the Y enclosed in the brackets k2. (In the formula, f is an integer between 2 and 4.)

[0030] In formula (1) above, A is a monovalent reactive group, preferably a functional group that has adhesion (bonding) reactivity to the surface of a substrate made of various materials such as paper, cloth, metal and its oxides, glass, plastic (resin), ceramic, and quartz, which is the target of surface treatment. Examples of monovalent reactive groups include monovalent groups selected from carbon-carbon double bond-containing groups (however, excluding alkenyl groups (groups that undergo hydrosilylation addition polymerization), and limited to groups involved in ionic addition polymerization or curing reactions by active energy rays (light)), carbon-carbon triple bond-containing groups, cyclic ether groups, hydroxyl group-containing groups, thiol groups, amino groups, azide groups, nitrogen-containing heterocyclic groups, phosphoric acid-containing groups, hydroxyl group-containing silyl groups (silanol groups), and hydrolyzable silyl groups.

[0031] Examples of A include carbon-carbon double bond-containing groups such as cinnamic acid group, sorbic acid group, acryloyl group, methacryloyl group, acryloyloxy group, methacryloyloxy group, acrylamide group, methacrylamide group, vinyl ether group; carbon-carbon triple bond-containing groups such as ethynyl group, propargyl group, 2-methyl-2-propynyl group, 3-butynyl group, 4-pentynyl group, and 5-hexynyl group, which have 2 to 20 carbon atoms, and alkynyloxy groups such as propargyloxy group, 2-methyl-2-propynyloxy group, 3-butynyloxy group, 4-pentynyloxy group, and 5-hexynyloxy group, which have 2 to 20 carbon atoms; cyclic A Examples of monovalent groups include tel groups such as epoxy groups, glycidyl groups, glycidyloxy groups, alicyclic epoxy groups, and oxetanyl groups; hydroxyl group-containing groups such as carboxyl groups and catechol groups; thiol groups; amino groups, alkylamino groups, and dialkylamino groups; azide groups; nitrogen-containing heterocyclic groups such as imidazolyl groups, triazolyl groups, benzotriazolyl groups, tetrazolyl groups, and isocyanate groups; phosphate-containing groups such as phosphate groups, phosphate ester groups, alkyl phosphate groups, and alkyl phosphate ester groups; phosphonic acid-containing groups such as phosphonic acid groups and phosphonic acid ester groups; and monovalent groups such as hydroxyl group-containing silyl groups (silanol groups), hydrolyzable silyl groups, and silazane groups. Among these, cyclic ether groups, hydroxyl group-containing silyl groups (silanol groups), hydrolyzable silyl groups, and silazane groups are preferred.

[0032] The following general formula (2) is used for hydroxyl group-containing silyl groups and hydrolyzable silyl groups. (In the formula, R 1 (wherein C1 is an alkyl group or phenyl group having 1 to 4 carbon atoms, X is an independent hydroxyl group or hydrolyzable group, and n is an integer from 1 to 3.) The silazane group is represented by the following general formula (3) A base represented by (wherein n'' is a number from 0 to 3, and n' is (3 - n'') / 2) is preferred.

[0033] In the above equation (2), R 1 These are independently alkyl groups such as methyl, ethyl, propyl, and butyl groups having 1 to 4 carbon atoms, or phenyl groups, with methyl groups being preferred among them.

[0034] In formula (2) above, X is independently a hydroxyl group or a hydrolyzable group. Examples of such X include: hydroxyl groups; C1-C10 alkoxy groups such as methoxy, ethoxy, propoxy, isopropoxy, and butoxy groups; C2-C10 alkoxyalkoxy groups such as methoxymethoxy and methoxyethoxy groups; C3-C10 alkoxyalkoxy groups such as methoxyethoxyethoxy and ethoxyethoxymethoxy groups; C1-C10 acyloxy groups such as acetoxy groups; C2-C10 alkenyloxy groups such as isopropenoxy and cyclopentenyloxy groups; halogen groups, preferably without a fluorine atom, such as chlorine, bromo, and iodine groups; and C2-C10 dialkylamino groups such as dimethylamino and diethylamino groups. Among these, methoxy, ethoxy, isopropenoxy, and chlorine groups are preferred. X may be the same or different.

[0035] In the above formula (2), n is an integer between 1 and 3, preferably 3.

[0036] In formula (3) above, n'' is a number from 0 to 3 (a positive number less than or equal to 3), preferably n'' < 3, and more preferably n'' is 0. When n'' is 3 in formula (3) above, general formula (1) above represents the molecular formula (structural formula) of the hydrocarbon terminal group-containing compound (monomer monomer), and when n'' < 3 in formula (3) above, general formula (1) above represents the compositional formula of the hydrocarbon terminal group-containing compound (polysilazane compound). In formula (3) above, n' is (3 - n'') / 2, preferably 1.5.

[0037] In formula (1) above, k1 is a number indicating the number of repetitions of -Z-Y-, and is an integer from 1 to 3. When k1 is 1 or greater, molecular mobility is improved by the linking functional group, and when k1 is 3 or less, the intermolecular interactions are large, making it easier for the molecular chains of the cured film to orient in one direction, while also maintaining molecular mobility. Furthermore, from the viewpoint of molecular mobility, it is preferable that k1 be 2 or 3, and when k1 is 1, it is preferable that R in formula (1) above is the following formula (5). (In the formula, R 3 , R 4(The sum of y, h, and y and h is the same as above.)

[0038] In the above formula (1), k2 is an integer between 2 and 4, and is preferably 2 or 3.

[0039] The following structures are examples of hydrocarbon terminal group-containing compounds represented by the above formula (1). By changing the combination of R, Z, Y, W, A, k1, and k2 in the above formula (1), several different hydrocarbon terminal group-containing compounds can be obtained.

[0040]

[0041]

[0042]

[0043]

[0044]

[0045] (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 60 or less, and the total number of carbon atoms in the part corresponding to Y is between 1 and 30.)

[0046] [Method for preparing hydrocarbon-terminated compound] Examples of methods for preparing the hydrocarbon-terminated compound represented by the general formula (1) of the present invention include the following: [Preparation method 1] A hydrocarbon-terminated compound represented by formula (1) (particularly a compound having a hydrolyzable silyl group at the end) can be produced by mixing a hydrocarbon-terminated compound having an alkenyl group at the end with a compound having an SiH group and a hydrolyzable silyl group, and carrying out a hydrosilylation addition reaction in the presence of a hydrosilylation catalyst. If a compound having an SiH group and a hydrolyzable silyl group has a halogen group as the hydrolyzable group, the compound can then be produced by converting the substituent (halogen atom) on the silyl group to another hydrolyzable group.

[0047] Here, examples of hydrocarbon terminal group-containing compounds having an alkenyl group at the terminal include compounds represented by the following formula (1A). (In the formula, R, Z, Y, W, k1, k2 are the same as above. Y 1 (This is a monovalent hydrocarbon group having an alkenyl group with 2 to 30 carbon atoms, preferably 2 to 20 carbon atoms.)

[0048] In the above formula (1A), Y 1 Y is a monovalent hydrocarbon group having an alkenyl group with 2 to 30 carbon atoms, preferably 2 to 20 carbon atoms. 1 If the number of carbon atoms is three or more, it may be linear, branched, cyclic, or a combination thereof. 1 Examples include those having the terminals shown below. (In the formula, R 7 These are independently hydrogen atoms, or each Y 1 (A monovalent hydrocarbon group whose total number of carbon atoms in its structure is 30 or less.)

[0049] Y1 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.)

[0050] Examples of compounds represented by formula (1A) are listed below. (In the formula, x, y, a1, and a' are independently the same as above.)

[0051] The following methods can be used to prepare the compound represented by formula (1A) (a hydrocarbon terminal group-containing compound having an alkenyl group at its terminus). [Method for preparing the compound represented by formula (1A) (1)] A hydrocarbon terminal group-containing compound having a hydroxyl group at its terminus can be mixed with a base, and a compound having a leaving group and an alkenyl group at its terminus can be added and a nucleophilic substitution reaction can be carried out to produce the compound represented by formula (1A) (a hydrocarbon terminal group-containing compound having an alkenyl group at its terminus).

[0052] Examples of hydrocarbon terminal group-containing compounds having a hydroxyl group at the terminal include compounds represented by the following formulas (1a-1) and (1a-2). (In the formula, R, Z, Y, k1, k2 are the same as above. W 2 (This refers to a 3- to 5-valent organic group, where the hydrogen atom enclosed in k2 is bonded to an oxygen atom. p is an integer between 0 and 2.)

[0053] Examples of compounds represented by formula (1a-1) are listed below. (In the equation, x, y, and a1 are independently the same as above.)

[0054] Examples of compounds represented by formula (1a-2) are listed below. (In the formula, x and a1 are the same as above.)

[0055] Methods for preparing compounds represented by formula (1a-1) or (1a-2) include: a method of obtaining the target compound by reacting a compound having a hydroxyl group and a functional group other than a hydroxyl group with a hydrocarbon terminal group containing a functional group, without the hydroxyl group acting as an active group, by reacting the other functional groups with each other; a method of obtaining the target compound by reacting the functional groups of a compound having a protected hydroxyl group and a functional group with a hydrocarbon terminal group containing a functional group, thereby obtaining a hydrocarbon terminal group containing a protected hydroxyl group, and then deprotecting the group that protected the hydroxyl group; and other methods of obtaining the target compound by reduction of a carbonyl compound or hydroboration reaction.

[0056] Furthermore, examples of compounds having a leaving group and an alkenyl group at the terminal include the compound represented by formula (1a-3) below, which can be reacted with the compound represented by formula (1a-1), and the compound represented by formula (1a-4) above, which can be reacted with the compound represented by formula (1a-2). (In the formula, Z, Y, W, Y 1 k2 is the same as above. L is a halogen atom such as fluorine, chlorine, bromine, or iodine, or a leaving group such as mesylate or trilate. q is an integer between 0 and 2, and the sum of p and q is between 0 and 2.

[0057] Examples of compounds represented by the above formula (1a-3) include the compounds represented by the following formulas.

[0058] Examples of compounds represented by the above formula (1a-4) include allyl bromide and 2-methylallyl bromide.

[0059] In the method (1) for preparing the compound represented by formula (1A), the amount of compound having a leaving group and an alkenyl group at the terminal is preferably 1 to 5 mol, particularly 1 to 2 mol, per 1 mol of hydroxyl group in the hydrocarbon terminal group-containing compound having a hydroxyl group at the terminal.

[0060] In the method (1) for preparing the compound represented by formula (1A), the base 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 hydrocarbon terminal group-containing compound having a hydroxyl group at the terminal.

[0061] In the method (1) for preparing the compound represented by formula (1A), 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. The amount of solvent 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.

[0062] In the method (1) for preparing the compound represented by formula (1A), a catalyst can be added to convert the leaving group and the leaving group in the compound having an alkenyl group at its terminus to a more highly leaving group and to promote the reaction. The catalyst that promotes the reaction is not particularly limited, but examples include tetramethylammonium iodide, tetraethylammonium iodide, tetrapropylammonium iodide, tetrabutylammonium iodide, sodium iodide, potassium iodide, rubidium iodide, and cesium iodide. The amount of catalyst used is preferably 0.001 to 1 mol, particularly 0.005 to 0.15 mol, per 1 mol of hydroxyl group in the hydrocarbon terminal group-containing compound having a hydroxyl group at its terminus.

[0063] In the method (1) for preparing the compound represented by formula (1A), the reaction conditions are preferably a temperature of 20 to 100°C, particularly 25 to 60°C, for 0.5 to 72 hours, and especially 1 to 36 hours.

[0064] Further methods for preparing the compound represented by formula (1A) (a hydrocarbon terminal group-containing compound having an alkenyl group at the terminal) include the following: [Method for preparing the compound represented by formula (1A) (2)] A hydrocarbon terminal group-containing compound having an isocyanate group at the terminal and a compound having an NH group and an alkenyl group at the terminal can be mixed to produce the compound represented by formula (1A) (a hydrocarbon terminal group-containing compound having an alkenyl group at the terminal).

[0065] Examples of hydrocarbon terminal group-containing compounds having an isocyanate group at the terminal include compounds represented by the following formula (1a-5). (In the formula, R, Z, and Y are the same as above. p1 is an integer between 0 and 3.)

[0066] The compounds represented by formula (1a-5) are not particularly limited, but examples include octyl isocyanate, octadecyl isocyanate, and compounds represented by the following formula. (In the formula, x and a1 are independently the same as above.)

[0067] Furthermore, examples of compounds having an NH group and an alkenyl group at the terminal include compounds represented by the following formulas (1a-6) or (1a-7). (In the formula, R 5 Z, Y, W, Y 1 k2 is the same as above. q1 is an integer between 0 and 2, and the sum of p1 and q1 is between 0 and 2.

[0068] Examples of compounds represented by formula (1a-6) are listed below. (In the formula, a' is independently the same as above.)

[0069] Examples of compounds represented by formula (1a-7) are listed below. (In the formula, a1 and a' are independently the same as above.)

[0070] In the method (2) for preparing the compound represented by formula (1A), the amount of compound having an NH group and an alkenyl group at the terminal is preferably 1 to 3 mol, particularly 1 to 2 mol, per 1 mol of isocyanate group in the hydrocarbon terminal group-containing compound having an isocyanate group at the terminal.

[0071] In the method (2) for preparing the compound represented by formula (1A), a solvent can be used when carrying out the reaction. Examples of solvents are the same as those exemplified in the solvent for the method (1) for preparing the compound represented by formula (1A). 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 an isocyanate group at the terminal end.

[0072] In the method (2) for preparing the compound represented by formula (1A), 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.

[0073] Further methods for preparing the compound represented by formula (1A) (a hydrocarbon terminal group-containing compound having an alkenyl group at the terminal) include the following: [Method for preparing the compound represented by formula (1A) (3)] A hydrocarbon terminal group-containing compound having an ester group at the terminal and an organometallic compound having an alkenyl group at the terminal can be mixed to produce the compound represented by formula (1A) (a hydrocarbon terminal group-containing compound having an alkenyl group at the terminal).

[0074] Here, examples of hydrocarbon terminal group-containing compounds having an ester group at the terminal include compounds represented by the following formula (1a-8). (In the formula, R, Z, Y, and k1 are the same as above. R 10 (This is a monovalent hydrocarbon group having 1 to 20 carbon atoms, preferably a methyl group or an ethyl group.)

[0075] The compounds represented by formula (1a-8) are not particularly limited, but examples include compounds represented by the following formulas. (In the formula, x, a1, R 10 (This is the same as above.)

[0076] Furthermore, examples of organometallic compounds having an alkenyl group at the terminal include vinyl magnesium bromide, allyl magnesium bromide, 3-butenyl magnesium bromide, and allyl magnesium chloride, although these are not particularly limited.

[0077] In the method (3) for preparing the compound represented by formula (1A), the amount of organometallic compound having an alkenyl group at the terminal is preferably 2 to 10 mol, particularly 2 to 5 mol, per 1 mol of hydrocarbon terminal group-containing compound having an ester group at the terminal.

[0078] In the method for preparing the compound represented by formula (1A) (3), 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, dichloromethane, and 1,2-dichloroethane. The amount of solvent used is preferably 100 to 10,000 parts by mass, and more preferably 120 to 2,000 parts by mass, per 100 parts by mass of the hydrocarbon terminal group-containing compound having an ester group at the terminal end.

[0079] In the method (3) for preparing the compound represented by formula (1A), the reaction conditions are preferably a temperature of -78 to 100°C, particularly -20 to 50°C, for 0.5 to 72 hours, and especially 1 to 24 hours.

[0080] Further methods for preparing the compound represented by formula (1A) (a hydrocarbon terminal group-containing compound having an alkenyl group at its terminus) include the following: [Method for preparing the compound represented by formula (1A) (4)] A hydrocarbon terminal group-containing compound having a hydrolyzable silyl group at its terminus and an organometallic compound having an alkenyl group at its terminus can be mixed to produce the compound represented by formula (1A) (a hydrocarbon terminal group-containing compound having an alkenyl group at its terminus).

[0081] Examples of hydrocarbon-terminal group-containing compounds having a hydrolyzable silyl group at the terminal include compounds represented by the following formula (1a-9). (In the formula, R, R 1Z, Y, and k1 are the same as above. X a n''' is an alkoxy group having 1 to 10 carbon atoms, an alkoxyalkoxy group having 2 to 10 carbon atoms, an alkenyloxy group having 2 to 10 carbon atoms, or a halogen group.

[0082] The compounds represented by formula (1a-9) are not particularly limited, but examples include compounds represented by the following formulas. (In the formula, x, a1, R 1 , X a (n''' is independently the same as above.)

[0083] Furthermore, examples of organometallic compounds having an alkenyl group at the terminal include vinyl magnesium bromide, allyl magnesium bromide, 3-butenyl magnesium bromide, and allyl magnesium chloride, although these are not particularly limited.

[0084] In the method (4) for preparing the compound represented by formula (1A), the amount of organometallic compound having an alkenyl group at the terminal is preferably 3 to 10 mol, particularly 3 to 5 mol, per 1 mol of hydrocarbon terminal group-containing compound having a hydrolyzable silyl group at the terminal.

[0085] In addition, in the method (4) for preparing the compound represented by formula (1A), 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, dichloromethane, and 1,2-dichloroethane. The amount of solvent used is preferably 100 to 10,000 parts by mass, and more preferably 200 to 2,000 parts by mass, per 100 parts by mass of the hydrocarbon-terminal group-containing compound having a hydrolyzable silyl group at the terminal end.

[0086] In the method (4) for preparing the compound represented by formula (1A), the reaction conditions are preferably a temperature of -78 to 100°C, particularly -20 to 50°C, for 0.5 to 72 hours, and especially 1 to 24 hours.

[0087] Further methods for preparing the compound represented by formula (1A) (a hydrocarbon terminal group-containing compound having an alkenyl group at its terminus) include the following: [Method for preparing the compound represented by formula (1A) (5)] A hydrocarbon terminal group-containing compound having a carboxyl group at its terminus and a compound having an NH group and an alkenyl group at its terminus can be mixed and reacted in the presence of a condensing agent to produce the compound represented by formula (1A) (a hydrocarbon terminal group-containing compound having an alkenyl group at its terminus).

[0088] Here, examples of hydrocarbon terminal group-containing compounds having a carboxyl group at the terminal include compounds represented by the following formula (1a-10). (In the formula, R, Z, and Y are the same as above. p1 is an integer between 0 and 3.)

[0089] The compounds represented by formula (1a-10) are not particularly limited, but examples include octyl isocyanate, octadecyl isocyanate, and compounds represented by the following formula. (In the formula, x and a1 are the same as above.)

[0090] Furthermore, examples of compounds having an NH group and an alkenyl group at the terminal include the compounds represented by the following formulas (1a-6) or (1a-7), as exemplified in the preparation method (2) for the compound represented by formula (1A) above. (In the formula, R 5 Z, Y, W, Y 1 k2 is the same as above. q1 is an integer between 0 and 2, and the sum of p1 and q1 is between 0 and 2.

[0091] Examples of compounds represented by formula (1a-6) are listed below. (In the formula, a' is independently the same as above.)

[0092] Examples of compounds represented by formula (1a-7) are listed below. (In the formula, a1 and a' are independently the same as above.)

[0093] In the method (5) for preparing the compound represented by formula (1A), the amount of compound having an NH group and an alkenyl group at the terminal is preferably 1 to 5 mol, particularly 1 to 1.5 mol, per mol of the hydrocarbon terminal group-containing compound having a carboxyl group at the terminal.

[0094] In the method (5) for preparing the compound represented by formula (1A), the condensing agent is not particularly limited, but examples include N,N'-dicyclohexylcarbodiimide, N,N'-diisopropylcarbodiimide, and 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide. The amount of condensing agent used is preferably 1 to 3 mol, particularly 1 to 1.5 mol, per 1 mol of the hydrocarbon terminal group-containing compound having a carboxyl group at the terminal.

[0095] Furthermore, a nucleophilic catalyst can be used in the preparation method (5) for the compound represented by formula (1A). The nucleophilic catalyst is not particularly limited, but examples include pyridine and 4-dimethylaminopyridine. The amount of nucleophilic catalyst used is preferably 0 to 1 mol, particularly 0.05 to 0.2 mol, per mol of the hydrocarbon terminal group-containing compound having a carboxyl group at the terminal end.

[0096] In addition, in the method (5) for preparing the compound represented by formula (1A), 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, dichloromethane, and 1,2-dichloroethane. The amount of solvent used is preferably 100 to 10,000 parts by mass, and more preferably 500 to 2,000 parts by mass, per 100 parts by mass of the hydrocarbon terminal group-containing compound having a carboxyl group at the terminal end.

[0097] In the method (5) for preparing the compound represented by formula (1A), the reaction conditions are preferably a temperature of 20 to 100°C, particularly 20 to 50°C, for 0.5 to 72 hours, and especially 1 to 24 hours.

[0098] Examples of compounds having an SiH group and a hydrolyzable silyl group in preparation method 1 include trimethoxysilane, triethoxysilane, triacetoxysilane, and trichlorosilane.

[0099] In preparation method 1, the amount of compound having an SiH group and a hydrolyzable silyl group used is preferably 1 to 10 mol, particularly 5 to 10 mol, per 1 mol of alkenyl group in the hydrocarbon terminal group-containing compound having an alkenyl group at the terminal end.

[0100] In preparation method 1, examples of the hydrosilylation reaction catalyst include platinum black, chloroplatinic acid, alcohol-modified chloroplatinic acid, complexes of chloroplatinic acid with olefins, aldehydes, vinylsiloxanes, acetylene alcohols, etc., and platinum group metal catalysts such as tetrakis(triphenylphosphine)palladium and chlorotris(triphenylphosphine)rhodium. Preferably, it is a platinum-based compound such as a vinylsiloxane coordination compound. It is preferable to dissolve the platinum-based compound in a solvent such as toluene, lower alcohol, higher alcohol, or silicone-based solvent before use. The amount of hydrosilylation reaction catalyst used is preferably 0.001 to 1,000 ppm 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.

[0101] In preparation method 1, a co-catalyst to activate the hydrosilylation reaction and a co-catalyst 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.

[0102] In preparation method 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. The amount of solvent 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.

[0103] In preparation method 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 36 hours.

[0104] In preparation method 1, if a compound having a SiH group and a hydrolyzable silyl group is used, such as trichlorosilane, in which the hydrolyzable group is a halogen group (a compound containing an SiH group and a silyl halogen group), the substituent (halogen atom) on the silyl group can then be converted to another hydrolyzable group, such as an alkoxy group like a methoxy group. Examples of compounds that can be used to convert the substituent (halogen atom) on the silyl group to another hydrolyzable group include methanol, ethanol, isopropanol, ethylene glycol monomethyl ether, and trimethyl orthoformate. 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.

[0105] In preparation method 1, the reaction conditions for converting substituents (halogen atoms) on the silyl group to other hydrolyzable groups are preferably a temperature of 0 to 80°C, particularly 20 to 60°C, for 0.5 to 72 hours, and especially 1 to 36 hours.

[0106] Other methods for preparing hydrocarbon terminal group-containing compounds represented by the general formula (1) of the present invention include the following: [Preparation Method 2] A hydrocarbon terminal group-containing compound having an SiH group at the terminal end can be mixed with a compound having a reactive group such as 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 compound represented by formula (1) (particularly a compound having a hydrolyzable silyl group at the terminal end).

[0107] 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 1 These are linear or branched or cyclic organopolysiloxane residues with 2 to 10 silicon atoms, or with 3 to 10 silicon atoms, and are 3 to 5 valent.

[0108] In the above formula (1B), W 1 These are linear organopolysiloxane residues with 2 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.

[0109] Examples of compounds represented by formula (1B) are listed below. (In the formula, x and a1 are independently the same as above.)

[0110] Furthermore, among compounds having reactive groups such as alkenyl groups and hydrolyzable silyl groups, examples of compounds having alkenyl groups and hydrolyzable silyl groups include vinyltrimethoxysilane, allyltrimethoxysilane, and octenyltrimethoxysilane. Examples of compounds having reactive groups other than alkenyl groups and hydrolyzable silyl groups include allylglycidyl ether.

[0111] In preparation method 2, the amount of compound having reactive groups such as alkenyl groups and hydrolyzable silyl groups used is preferably 1 to 20 mol, and particularly 1 to 10 mol, per 1 mol of SiH groups in the hydrocarbon terminal group-containing compound having an SiH group at the terminal end.

[0112] In preparation method 2, the hydrosilylation reaction catalyst can be the same as that exemplified in the hydrosilylation reaction catalyst of preparation method 1 above. 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.

[0113] In preparation method 2, a co-catalyst to activate the hydrosilylation reaction and a co-catalyst 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.

[0114] In preparation method 2, a solvent can be used when carrying out the reaction. Examples of solvents are the same as those exemplified in the solvent for preparation method 1 above. The amount of solvent 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.

[0115] In preparation method 2, the reaction conditions are preferably a temperature of 20 to 120°C, particularly 60 to 100°C, for 0.5 to 72 hours, and especially 1 to 36 hours.

[0116] Other methods for preparing the hydrocarbon terminal group-containing compound represented by the general formula (1) of the present invention include the following: [Preparation Method 3] A hydrocarbon terminal group-containing compound having an alkenyl group at the terminal and trichlorosilane are mixed and reacted in the presence of a hydrosilylation catalyst, and then the resulting compound is reacted with ammonia gas to produce a hydrocarbon terminal group-containing compound represented by formula (1) (particularly a compound having an amino group-containing silyl group at the terminal and / or a polysilazane compound which is a polymer thereof).

[0117] Here, the reaction product of the hydrocarbon-terminal group-containing compound having an alkenyl group at its terminus and trichlorosilane can be prepared in the same manner as in Preparation Method 1.

[0118] In preparation method 3, the amount of ammonia gas used is preferably 1 to 300 cc / min, and more preferably 30 to 200 cc / min.

[0119] In preparation method 3, a solvent can be used when reacting the reaction product of the hydrocarbon terminal group-containing compound having an alkenyl group at the terminal end and trichlorosilane with ammonia gas. Examples of solvents are the same as those exemplified in preparation method 1 above. The amount of solvent used is preferably 0 to 1,000 parts by mass, particularly 50 to 300 parts by mass, per 100 parts by mass of the reaction product of the hydrocarbon terminal group-containing compound having an alkenyl group at the terminal end and trichlorosilane.

[0120] In preparation method 3, the reaction conditions for the reaction product of the hydrocarbon terminal group-containing compound having an alkenyl group at the terminal end and trichlorosilane with ammonia gas are preferably at room temperature (23 ± 15°C, the same applies hereinafter), particularly 20 to 30°C, for 2 to 36 hours, and especially 4 to 12 hours.

[0121] Other methods for preparing the hydrocarbon terminal group-containing compound represented by the general formula (1) of the present invention include the following: [Preparation Method 4] A hydrocarbon terminal group-containing compound having a hydroxyl group at the terminal end can be mixed with phosphorus oxychloride and reacted, and then water can be added and reacted to produce a hydrocarbon terminal group-containing compound represented by formula (1) (particularly a compound having a reactive group such as a phosphate group at the terminal end).

[0122] Examples of hydrocarbon terminal group-containing compounds having a hydroxyl group at the terminal include the compounds represented by formulas (1a-1) and (1a-2) described in the preparation method (1) for the compound represented by formula (1A).

[0123] In preparation method 4, the amount of phosphorus oxychloride used is preferably 1 to 4 mol, particularly 1 to 2 mol, per 1 mol of hydroxyl groups in the hydrocarbon-terminal group-containing compound having a hydroxyl group at the terminal end.

[0124] In preparation method 4, a solvent can be used when reacting a hydrocarbon end group-containing compound having a hydroxyl group at its terminal with phosphorus oxychloride. Examples of solvents are the same as those exemplified in preparation method 1 above. The amount of solvent used is preferably 0 to 1,000 parts by mass, particularly 50 to 500 parts by mass, per 100 parts by mass of the hydrocarbon end group-containing compound having a hydroxyl group at its terminal.

[0125] In preparation method 4, the reaction conditions for the hydrocarbon terminal group-containing compound having a hydroxyl group at its terminus and phosphorus oxychloride are preferably a temperature of 0 to 80°C, particularly 15 to 50°C, for 0.5 to 72 hours, and especially 1 to 36 hours.

[0126] In preparation method 4, the amount of water used is preferably 50 to 1,000 parts by mass, and particularly preferably 100 to 500 parts by mass, per 100 parts by mass of the hydrocarbon terminal group-containing compound having a hydroxyl group at its end.

[0127] In preparation method 4, the reaction conditions for the reaction product of a hydrocarbon terminal group-containing compound having a hydroxyl group at its terminus and phosphorus oxychloride with water are preferably a temperature of 0 to 80°C, particularly 15 to 50°C, for 0.5 to 72 hours, and especially 1 to 36 hours.

[0128] [Surface Treatment Agent] The present invention further provides a non-fluorine surface treatment agent containing a hydrocarbon terminal group-containing compound represented by formula (1) above (i.e., a compound that does not have a fluorine atom in its molecule). The surface treatment agent only needs to contain the hydrocarbon terminal group-containing compound represented by formula (1), and may also contain unreacted raw materials and reaction intermediates before the introduction of the reactive group of the hydrocarbon terminal group-containing compound represented by formula (1). Furthermore, it is preferable to use a surface treatment agent in which the reactive group of the hydrocarbon terminal group-containing compound is a hydrolyzable silyl group, and in this case, the surface treatment agent may also contain a partially hydrolyzed condensate obtained by partially hydrolyzing and condensing the hydrolyzable silyl group by a known method.

[0129] When the reactive group of the hydrocarbon-terminal group-containing compound is a hydrolyzable silyl group, 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. The amount of hydrolysis condensation catalyst added is a catalytic amount, usually 0.001 to 5 parts by mass, particularly 0.1 to 1 part by mass, per 100 parts by mass of the hydrocarbon-terminal group-containing compound (and / or its partially hydrolyzed condensate).

[0130] 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 tert-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 tert-butyl ether, ethylene glycol dimethyl ether, propyl acetate, butyl acetate, and propylene glycol monomethyl ether acetate are preferred in terms of solubility, wettability, etc.

[0131] The above solvents may be mixed in two or more forms, and it is preferable to uniformly dissolve the hydrocarbon end group-containing compound. The optimal concentration of the hydrocarbon end group-containing compound 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 compound. 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 compound. In either coating case, 100 parts by mass refers to the case where no solvent is used and the coating is performed directly.

[0132] The surface treatment agent of the present invention can be applied to a substrate by known methods such as brush application, dipping, spraying, and vapor deposition. The heating method during vapor deposition can be either resistance heating or electron beam heating, and is not particularly limited. The curing conditions vary depending on the curing method, but for example, in the case of direct coating (brush application, dipping, spraying, etc.), it is preferable to use 25 to 200°C, particularly 25 to 150°C, for 30 minutes to 36 hours, and especially 1 to 24 hours, while in the case of application by vapor deposition, it is desirable to use a temperature range of 20 to 200°C for 1 to 24 hours. Curing may also be performed under humid conditions. Furthermore, for example, when using a hydrocarbon terminal group-containing compound having a hydrolyzable silyl group, in spray coating, diluting it in an organic solvent with water added beforehand and performing hydrolysis, i.e., generating Si-OH, before spray coating will result in faster curing after coating.

[0133] 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.

[0134] 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.

[0135] The surface treatment agent of the present invention can form a cured film with high levels of water repellency, slipperiness, dirt-wiping properties, abrasion resistance, and alkali resistance.

[0136] [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.

[0137] 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.

[0138] The present invention will be described in more detail below with reference to synthesis examples, examples, and comparative examples, but the present invention is not limited to the following examples. In the following examples, the mol amount of the compound is, with respect to the measured mass of the target compound, 1 The value was calculated by dividing by the molecular weight of the polymer identified by 1H-NMR analysis. Furthermore, the film thickness was measured using spectroscopic ellipsometry with a spectroscopic ellipsometer. The room temperature was 25°C.

[0139] [Synthesis Example 1] Synthesis Example 1-1 In a reaction vessel, the following formula (A) 10.00 g (5.95 × 10) of the compound represented by -2 mol), tetrahydrofuran 20.00 g, and octadecylamine 16.02 g (5.95 x 10 -2 The mixture (mol) was aged at 50°C for 1 hour. Then, 11.56 g of diallylamine (1.19 x 10) was added. -1(mol) was added dropwise, and the mixture was aged at 50°C for 1 hour. Then, the solvent and unreacted materials were removed by reduced pressure distillation, and the mixture was purified by column chromatography to obtain 10.42 g of the product.

[0140] The resulting compound was 1 ¹H-NMR confirmed that the structure is represented by the following formula (C).

[0141] Synthesis Example 1-2 In the reaction vessel, the following formula (C) obtained in Synthesis Example 1-1 5.00 g (9.35 × 10) of the compound represented by -3 mol), toluene 5.00g, trimethoxysilane 11.42g (9.35 x 10 -2 mol), 2.60 × 10¹³ toluene solution of chloroplatinic acid / vinylsiloxane complex -3 g (8.05 × 10 as Pt alone) -9 (containing mol), and acetic acid 3.15 × 10 -3 g (5.25 x 10 -5 The mixture (mol) was aged at 80°C for 24 hours. After that, the solvent and unreacted materials were removed by reduced pressure distillation to obtain 6.50 g of product.

[0142] The resulting compound was 1 ¹H-NMR confirmed that the structure is represented by the following formula (D).

[0143] [Synthesis Example 2] Synthesis Example 2-1 Put 5.00 g of octadecyl isocyanate (1.69 × 10) into a reaction vessel. -2 mol), tetrahydrofuran 10.00 g, allyl alcohol 1.18 g (2.03 x 10 -2 mol), and tetrakis(2-ethylhexyl) orthotitanate 1.03 × 10 -2 g (1.82 × 10 -5 The mixture (mol) was aged at 50°C for 3 hours. After treatment with activated carbon, the solvent and unreacted materials were removed by vacuum distillation to obtain 5.27 g of product.

[0144] The resulting compound was 1 ¹H-NMR confirmed that the structure is represented by the following formula (E).

[0145] Synthesis Example 2-2: In a reaction vessel, 5.00 g (1.41×10 mol) of the compound represented by the following formula (E) obtained in Synthesis Example 2-1, 36.70 g of toluene, 34.01 g (1.41×10 -2 mol) of the compound represented by the following formula (F), 2.60×10 g of a toluene solution of chloroplatinic acid / vinylsiloxane complex (containing 8.05×10 -1 mol of platinum metal), and 3.30×10 -3 g (7.33×10 -9 mol) of formamide were mixed and aged at 80°C for 24 hours. Then, the solvent and unreacted substances were distilled off under reduced pressure to obtain 7.12 g of the product. -3 g (7.33×10 -5 mol) of formamide were mixed and aged at 80°C for 24 hours. Then, the solvent and unreacted substances were distilled off under reduced pressure to obtain 7.12 g of the product.

[0146] The obtained compound was 1 confirmed to have a structure represented by the following formula (G) by 1H-NMR.

[0147] Synthesis Example 2-3: In a reaction vessel, 5.00 g (8.42×10 mol) of the compound represented by the following formula (G) obtained in Synthesis Example 2-2, 5.00 g of toluene, 4.51 g (2.78×10 -3 mol) of allyltrimethoxysilane, 2.60×10 -2 g of a toluene solution of chloroplatinic acid / vinylsiloxane complex (containing 8.05×10 -3 mol of platinum metal), and 3.15×10 -9 g (5.25×10 -3 mol) of acetic acid were mixed and aged at 80°C for 24 hours. Then, the solvent and unreacted substances were distilled off under reduced pressure to obtain 8.28 g of the product. -5 mol) of acetic acid were mixed and aged at 80°C for 24 hours. Then, the solvent and unreacted substances were distilled off under reduced pressure to obtain 8.28 g of the product.

[0148] The obtained compound was 1 confirmed to have a structure represented by the following formula (H) by 1H-NMR.

[0149] [Synthesis Example 3] Synthesis Example 3-1: In a reaction vessel, 5.00 g (1.69×10<00mol), 100.00 g of tetrahydrofuran, and 1.09 g (1.78×10 -2 mol) of 2-aminoethanol were mixed and aged at 50°C for 1 hour. Then, the solvent and unreacted substances were distilled off under reduced pressure to obtain 5.96 g of the product.

[0150] The obtained compound 1 was confirmed to have the structure represented by the following formula (I) by 1H-NMR.

[0151] Synthesis Example 3-2 In a reaction vessel, 5.00 g (1.40×10 mol) of the compound represented by the following formula (I) obtained in Synthesis Example 3-1, 75.00 g of tetrahydrofuran, 5.18×10 -2 g (1.40×10 -1 mol) of tetrabutylammonium iodide, and 1.73 g (1.54×10 -3 mol) of potassium tert-butoxide were mixed and aged at 50°C for 1 hour. Then, 5.30 g (2.80×10 -2 mol) of the compound represented by the following formula (J) was added dropwise, and the mixture was aged at 50°C for 24 hours. 10.00 g of 2M hydrochloric acid was added to the obtained solution, and the aqueous layer was extracted 3 times with toluene. The combined organic layers were washed with pure water and saturated brine and dried over magnesium sulfate. Then, activated carbon treatment was performed, and the solvent and unreacted substances were distilled off under reduced pressure to obtain 4.16 g of the product. The obtained compound -2 was confirmed to have the structure represented by the following formula (K) by 1H-NMR.

[0152] The obtained compound 1 was confirmed to have the structure represented by the following formula (K) by 1H-NMR.

[0153] Synthesis Example 3-3 In a reaction vessel, 4.00 g (8.61×10 mol) of the compound represented by the following formula (K) obtained in Synthesis Example 3-2, 5.00 g of toluene, 10.51 g (8.61×10 -3 mol) of trimethoxysilane, and 2.60×10 -2 g of a toluene solution of chloroplatinic acid / vinylsiloxane complex (8.05×10 -3 g 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 24 hours. After that, the solvent and unreacted materials were removed by reduced pressure distillation to obtain 5.43 g of product.

[0154] The resulting compound was 1 ¹H-NMR confirmed that the structure is represented by the following formula (L).

[0155] [Synthesis Example 4] Synthesis Example 4-1 Put 5.00 g of octadecyl isocyanate (1.69 x 10) into a reaction vessel. -2 mol), tetrahydrofuran 10.00 g, ethylene glycol monoallyl ether 1.81 g (1.78 x 10) -2 mol), and tetrakis(2-ethylhexyl) orthotitanate 1.03 × 10 -2 g (1.82 × 10 -5 The mixture (mol) was aged at room temperature for 24 hours. After removing the solvent and unreacted materials under reduced pressure, the mixture was treated with activated carbon, and the solvent was removed under reduced pressure to obtain 5.30 g of the product.

[0156] The resulting compound was 1 ¹H-NMR confirmed that the structure is represented by the following formula (M).

[0157] Synthesis Example 4-2 In the reaction vessel, the following formula (M) obtained in Synthesis Example 4-1 5.00 g (1.26 × 10) of the compound represented by -2 mol), toluene 5.00 g, trichlorosilane 11.17 g (1.38 x 10 -2 mol), 2.60 × 10¹³ toluene solution of chloroplatinic acid / vinylsiloxane complex -3 g (8.05 × 10 as Pt alone) -9 (containing mol), and acetic acid 3.15 × 10 -3 g (5.25 x 10 -5 The mixture (mol) was aged at 80°C for 24 hours. After that, the solvent and unreacted materials were removed by vacuum distillation to obtain 5.37 g of product.

[0158] The resulting compound was 1¹H-NMR confirmed that the structure is represented by the following formula (N).

[0159] Synthesis Example 4-3 Add 6.30 g of bis(dimethylsilyl) ether (4.69 x 10) to the reaction vessel. -2 Mix 40.0 g of tetrahydrofuran (mol) and 40.0 g of 1.2 M hydrochloric acid and stir at -10°C for 1 hour. Then, the following formula (N) obtained in Synthesis Example 4-2 5.00 g (9.38 × 10) of the compound represented by -3 The solution was added dropwise over 1 hour while maintaining the internal temperature between 0°C and 5°C. After the addition was complete, the mixture was stirred at 0°C for 2 hours. 50.00 g of pure water 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. The solvent and unreacted materials were then removed by vacuum distillation to obtain 5.51 g of product.

[0160] The resulting compound was 1 ¹H-NMR confirmed that the structure is represented by the following formula (O).

[0161] Synthesis Example 4-4 In the reaction vessel, the following formula (O) obtained in Synthesis Example 4-3 5.00 g of the compound represented by (7.67 × 10) -3 mol), toluene 5.00g, allyltrimethoxysilane 4.48g (2.76 x 10 -2 mol), 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 24 hours. After that, the solvent and unreacted materials were removed by vacuum distillation to obtain 7.86 g of the product.

[0162] The resulting compound was 1 ¹H-NMR confirmed that the structure is represented by the following formula (P).

[0163] [Synthesis Example 5] Synthesis Example 5-1 Put 5.00 g of octadecyl isocyanate (1.69 × 10) into a reaction vessel. -2 mol), tetrahydrofuran 10.00 g, 3,4,5-trimethoxybenzyl alcohol 3.35 g (1.69 x 10 -2 mol), and tetrakis(2-ethylhexyl) orthotitanate 1.03 × 10 -2 g (1.82 × 10 -5 The mixture (mol) was aged at 50°C for 3 hours. After treatment with activated carbon, the solvent and unreacted materials were removed by vacuum distillation to obtain 7.01 g of product.

[0164] The resulting compound was 1 ¹H-NMR confirmed that the structure is represented by the following formula (Q).

[0165] Synthesis Example 5-2 In the reaction vessel, the following formula (Q) obtained in Synthesis Example 5-1 7.00 g (1.42 × 10) of the compound represented by -2 Mix 1.24 × 10¹⁴ mol) and 7.00 g of dichloroethane and stir at -78°C. Add 30.97 g of boron tribromide (1.24 × 10¹⁴ mol) to the mixture. -1 The solution was added dropwise and aged at -78°C for 1 hour. The temperature was then raised to 25°C and aged for a further 24 hours. 50.00 g of pure water was added to the resulting solution and the solution was separated. The aqueous layer was extracted three times with ethyl acetate. The combined organic layers were washed with pure water and saturated brine and dried over magnesium sulfate. The solvent and unreacted substances were removed by reduced pressure distillation, and the target product was separated by column chromatography to obtain 2.63 g of the product.

[0166] The resulting compound was 1 ¹H-NMR confirmed that the structure is represented by the following formula (R).

[0167] Synthesis Example 5-3 In the reaction vessel, the following formula (R) obtained in Synthesis Example 5-2 2.50 g of the compound represented by (5.54 x 10) -3 mol), 5.00 g of tetrahydrofuran, and 2.41 g of potassium carbonate (1.74 x 10⁻¹⁰) -2The mixture (mol) was heated at 50°C for 1 hour. After that, the reaction solution was cooled to 0°C and 2.21 g of allyl bromide (1.83 x 10) was added. -2 A mol (mol) solution was added dropwise. The mixture was then aged at 25°C for 24 hours. 10.00 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. After that, the mixture was treated with activated carbon, and the solvent and unreacted materials were removed by vacuum distillation to obtain 2.15 g of product.

[0168] The resulting compound was 1 ¹H-NMR confirmed that the structure is represented by the following formula (S).

[0169] Synthesis Example 5-4 In the reaction vessel, the following formula (S) obtained in Synthesis Example 5-3 2.00 g (3.50 x 10) of the compound represented by -3 mol), toluene 2.00g, trimethoxysilane 12.82g (1.05 x 10) -1 mol), 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 24 hours. After that, the solvent and unreacted materials were removed by reduced pressure distillation to obtain 2.73 g of product.

[0170] The resulting compound was 1 ¹H-NMR confirmed that the structure is represented by the following formula (T).

[0171] [Synthesis Example 6] Synthesis Example 6-1 In a reaction vessel, add 5.00 g of ethylene glycol monoallyl ether (4.90 x 10 -2 10.00 g of 1,2-dichloroethane (mol), and 9.80 g of tosyl chloride (5.14 x 10) -2 Mix mol) and stir at 0°C, then add 5.20 g of triethylamine (5.14 x 10 -2A mol (unit of sodium bicarbonate) was added dropwise, and the mixture was allowed to mature at 25°C for 24 hours. 50 mL of saturated sodium bicarbonate aqueous solution was added to the resulting solution and separated. The organic layer was washed with 50 mL of pure water and 50 mL of 2 M hydrochloric acid. This washing was repeated twice. After drying the organic layer over magnesium sulfate, the solvent and unreacted materials were removed by vacuum distillation to obtain 8.74 g of product.

[0172] The resulting compound was 1 ¹H-NMR confirmed that the structure is represented by the following formula (U).

[0173] Synthesis Example 6-2 In the reaction vessel, the following formula (U) obtained in Synthesis Example 6-1 5.00 g (1.95 x 10) of the compound represented by -2 mol), 50.00 g of acetone, and 2.54 g of lithium bromide (2.93 x 10) -2 The mixture (mol) was aged at 25°C for 24 hours. The resulting solution was distilled to obtain 2.15 g of product.

[0174] The resulting compound was 1 ¹H-NMR confirmed that the structure is represented by the following formula (V).

[0175] Synthesis Example 6-3 In a reaction vessel, add 5.00 g of octadecyl alcohol (1.85 x 10⁻¹⁵ -2 mol), tetrahydrofuran 50.00 g, tetrabutylammonium iodide 6.80 x 10 -1 g (1.85 x 10 -3 mol), and potassium tert-butoxide 2.28 g (2.03 x 10⁻¹⁰) -2 The mixture (mol) was aged at 50°C for 1 hour. Then, the following formula (V) obtained in Synthesis Example 6-2 was obtained. 6.11 g (3.70 × 10) of the compound represented by this compound -2 A mol (hydrochloric acid) was added dropwise, and the mixture was aged at 50°C for 24 hours. 2.00 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 5.11 g of product.

[0176] The resulting compound was1 H-NMR confirmed that the structure is represented by the following formula (W).

[0177] Synthesis Example 6-4 In the reaction vessel, the following formula (W) obtained in Synthesis Example 6-3 5.00 g (1.41 × 10) of the compound represented by -2 mol), 36.70 g of toluene, the following formula (F) 34.01 g (1.41 × 10) of the compound represented by -1 mol), 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 24 hours. After that, the solvent and unreacted materials were removed by vacuum distillation to obtain 7.47 g of product.

[0178] The resulting compound was 1 ¹H-NMR confirmed that the structure is represented by the following formula (X).

[0179] Synthesis Example 6-5 In the reaction vessel, the following formula (X) obtained in Synthesis Example 6-4 5.00 g (8.40 x 10) of the compound represented by -3 mol), toluene 5.00g, allyl glycidyl ether 2.88 x 10 1 g (2.52 x 10 -1 mol), 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 24 hours. After that, the solvent and unreacted materials were removed by vacuum distillation to obtain 6.75 g of product.

[0180] The resulting compound was 1 H-NMR confirmed that the structure is represented by the following formula (Y).

[0181] [Synthesis Example 7] Synthesis Example 7-1 The following formula (W), obtained in the same manner as in Synthesis Example 6-3, is used in the reaction vessel. 5.00 g (1.41 × 10) of the compound represented by -2 mol), toluene 10.00g, trichlorosilane 2.10g (1.55 x 10 -2 mol), 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 24 hours. After that, the solvent and unreacted materials were removed by reduced pressure distillation to obtain 6.29 g of product.

[0182] The resulting compound was 1 H-NMR confirmed that the structure is represented by the following formula (Z).

[0183] Synthesis Example 7-2 In the reaction vessel, the following formula (Z) obtained in Synthesis Example 7-1 5.00 g (1.02 × 10) of the compound represented by -2 Mix mol) and 10.00 g of tetrahydrofuran and stir at 0°C. Then add 25.3 mL (5.05 × 10) of allyl magnesium chloride (2.0 M tetrahydrofuran solution). -2 A mol (unit of volume) was added dropwise, and the mixture was aged at 25°C for 24 hours. 20.00 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 3.57 g of product.

[0184] The resulting compound was 1 ¹H-NMR confirmed that the structure is represented by the following formula (AA).

[0185] Synthesis Example 7-3 In the reaction vessel, the following formula (AA) obtained in Synthesis Example 7-2 3.00 g (5.92 x 10) of the compound represented by -3mol), toluene 3.00g, trimethoxysilane 19.39g (1.59 x 10) -1 mol), 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 24 hours. After that, the solvent and unreacted materials were removed by vacuum distillation to obtain 4.19 g of the product.

[0186] The resulting compound was 1 ¹H-NMR confirmed that the structure is represented by the following formula (AB).

[0187] [Synthesis Example 8] Synthesis Example 8-1 Put 10.00 g of docosanol (3.06 x 10) into a reaction vessel. -2 mol), tetrahydrofuran 50.00 g, tetrabutylammonium iodide 1.13 g (3.06 x 10 -3 mol), and potassium tert-butoxide 5.15 g (4.59 x 10) -2 The mixture (mol) was added and aged at 50°C for 1 hour. Then, 7.67 g of ethyl bromoethyl (4.59 x 10) was added. -2 A mol (unit of volume) was added dropwise, and the mixture was aged at 50°C for 24 hours. 30.00 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 7.07 g of product.

[0188] The resulting compound was 1 ¹H-NMR confirmed that the structure is represented by the following formula (AC).

[0189] Synthesis Example 8-2 In the reaction vessel, the following formula (AC) obtained in Synthesis Example 8-1 7.00 g (1.70 × 10) of the compound represented by -2Mix mol) and 10.00 g of tetrahydrofuran and stir at 0°C. Then add 28.0 mL (5.60 × 10) of allyl magnesium chloride (2.0 M tetrahydrofuran solution). -2 A mol (unit of volume) was added dropwise, and the mixture was aged at 25°C for 24 hours. 30.00 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 5.13 g of product.

[0190] The resulting compound was 1 ¹H-NMR confirmed that the structure is represented by the following formula (AD).

[0191] Synthesis Example 8-3 In the reaction vessel, the following formula (AD) obtained in Synthesis Example 8-2 5.00 g (1.11 × 10) of the compound represented by -2 mol), toluene 5.00g, trimethoxysilane 27.13g (2.22 x 10) -1 mol), 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 24 hours. After that, the solvent and unreacted materials were removed by reduced pressure distillation to obtain 6.94 g of product.

[0192] The resulting compound was 1 ¹H-NMR confirmed that the structure is represented by the following formula (AE).

[0193] [Synthesis Example 9] Synthesis Example 9-1 In a reaction vessel, add 40.00 g of 1-decanethiol (2.29 x 10 -1 mol), 24.80 g of acrylic acid (3.44 x 10 -1 mol), and 10.86 g (3.44 x 10) of tetrabutylammonium fluoride trihydrate. -2The mixture (mol) was aged at 50°C for 24 hours. After that, unreacted material was removed by reduced pressure distillation, and the product was purified by column chromatography to obtain 45.02 g of the product.

[0194] The resulting compound was 1 ¹H-NMR confirmed that the structure is represented by the following formula (AF).

[0195] Synthesis Example 9-2 In the reaction vessel, the following formula (AF) obtained in Synthesis Example 9-1 35.00 g (1.42 × 10) of the compound represented by -1 mol), 200.00 g of 1,2-dichloroethane, the following formula (AG) 28.17 g of the compound represented by (1.70 × 10) -1 mol), 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride 38.11 g (1.99 x 10) -1 mol), and 3.47 g of 4-dimethylaminopyridine (2.84 x 10⁻¹⁰) -2 The mixture (mol) was aged at 50°C for 24 hours. 100.00 g of 2 M hydrochloric acid was added to the resulting solution, and the aqueous layer was extracted three times with 1,2-dichloroethane. 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 46.40 g of product.

[0196] The resulting compound was 1 ¹H-NMR confirmed that the structure is represented by the following formula (AH).

[0197] Synthesis Example 9-3 In the reaction vessel, the following formula (AH) obtained in Synthesis Example 9-2 5.00 g (1.27 × 10) of the compound represented by -2 mol), toluene 5.00g, trimethoxysilane 2.33 x 10 1 g (1.91 × 10 -1 mol), 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 -3g (7.33 × 10 -5 The mixture (mol) was aged at 80°C for 24 hours. After that, the solvent and unreacted materials were removed by vacuum distillation to obtain 8.69 g of the product.

[0198] The resulting compound was 1 1H-NMR confirmed that the structure is represented by the following formula (AI).

[0199] [Example 1] The compound obtained in Synthesis Example 1 (Synthesis Examples 1-3) was dissolved in toluene to a concentration of 0.2% by mass to prepare a surface treatment agent.

[0200] [Example 2] The compound obtained in Synthesis Example 2 (Synthesis Example 2-3) was dissolved in dibutyl ether to a concentration of 0.2% by mass to prepare a surface treatment agent.

[0201] [Example 3] The compound obtained in Synthesis Example 3 (Synthesis Example 3-3) was dissolved in dibutyl ether to a concentration of 0.2% by mass to prepare a surface treatment agent.

[0202] [Example 4] The compound obtained in Synthesis Example 4 (Synthesis Example 4-4) was dissolved in a hexane / isooctane (mass ratio 50 / 50) mixed solution to a concentration of 0.1% by mass to prepare a surface treatment agent.

[0203] [Example 5] The compound obtained in Synthesis Example 5 (Synthesis Example 5-4) was dissolved in isooctane to a concentration of 0.1% by mass to prepare a surface treatment agent.

[0204] [Example 6] The compound obtained in Synthesis Example 6 (Synthesis Example 6-5) was dissolved in propylene glycol monomethyl ether acetate to a concentration of 0.1% by mass to prepare a surface treatment agent.

[0205] [Example 7] The compound obtained in Synthesis Example 7 (Synthesis Example 7-3) was dissolved in isononane to a concentration of 0.2% by mass to prepare a surface treatment agent.

[0206] [Example 8] The compound obtained in Synthesis Example 8 (Synthesis Example 8-3) was dissolved in butyl acetate to a concentration of 0.2% by mass to prepare a surface treatment agent.

[0207] [Example 9] The compound obtained in Synthesis Example 9 (Synthesis Example 9-3) was dissolved in butyl acetate to a concentration of 0.1% by mass to prepare a surface treatment agent.

[0208] [Comparative Example 1] The following formula (A') A surface treatment agent was prepared by dissolving the compound represented by [formula] in toluene to a concentration of 0.1% by mass.

[0209] [Comparative Example 2] The following formula (B') A surface treatment agent was prepared by dissolving the compound represented by [formula] in toluene to a concentration of 0.1% by mass.

[0210] [Comparative Example 3] No surface treatment agent used.

[0211] Formation of a cured film of the surface treatment agent: On a glass (Gorilla, manufactured by Corning) whose outermost surface was coated with SiO2 to a thickness of 10 nm, each of the surface treatment agents prepared in the above examples and comparative examples was spray-coated, and cured for 1 hour in an atmosphere of 80°C and 80% relative humidity, and then for 12 hours in an atmosphere of 25°C and 50% relative humidity to form a cured film with a thickness of 3 to 5 nm.

[0212] The water repellency, slipperiness, dirt-wiping properties, abrasion resistance, and alkali resistance of the glass with a hardened coating were evaluated using the method described below. For Comparative Example 3, a glass (Corning Gorilla) with no surface treatment, but coated with a 10 nm thick layer of SiO2 on its outermost surface, was used and evaluated in the same manner.

[0213] 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 (manufactured by Kyowa Interface Science Co., Ltd.) (droplet: 2 μl, temperature: 25°C, relative humidity: 40%). A contact angle (water repellency) of 85° or higher was considered good. The results (water contact angle) are shown in Table 1.

[0214] Evaluation of Slipperiness The slipperiness of the glass with the hardened coating prepared as described above was evaluated by assessing the coefficient of dynamic friction with the nonwoven fabric using the method described below. The coefficient of dynamic friction of the glass with the hardened coating with the nonwoven fabric was measured in accordance with ASTM D1894 using a surface properties measuring instrument TYPE: 14FW (manufactured by Shinto Kagaku Co., Ltd.) under the conditions of a load of 100 gf and a tensile speed of 500 mm / min. A slipperiness of 0.25 or less was considered good. The results (coefficient of dynamic friction) are shown in Table 1. [Slipperiness Evaluation Conditions] Load: 100 gf Stroke: 100 mm Contact area: 1 × 3 cm 2 Nonwoven fabric: BEMCOT (manufactured by Asahi Kasei Corporation)

[0215] Evaluation of Dirt Removal Properties A 2 cm straight line was drawn on the glass with the hardened film prepared as described above using a Hi-Mackie (manufactured by Zebra Co., Ltd.), the ink was dried, and then the glass was wiped with tissue paper. The number of rubs required to remove the ink was evaluated according to the following criteria. Dirt removal properties rated A or B were considered good. The results are shown in Table 1. [Dirt Removal Evaluation Criteria] A: 4 rubs or less B: 5 rubs or more C: Ink cannot be wiped off

[0216] 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 result of 2,000 or more times the contact angle fell below 80° was considered good. The results (number of times the water contact angle fell below 80°) are shown in Table 1. [Steel Wool Abrasion Resistance Test Conditions] Steel wool: Bonster #0000 Contact area: 1 cm 2 Distance traveled (one way): 40 mm; Speed: 4,800 mm / min; Load: 500 gf / cm 2

[0217] Evaluation of alkali resistance: The glass with the hardened film prepared as described above was immersed in a 0.4% by mass sodium hydroxide aqueous solution and placed in a 55°C oven. Every 30 minutes, the sample was removed and washed with water. The contact angle (water repellency) of the hardened film with respect to water was measured in the same manner as described above, and the time it took for the water contact angle to be less than 80° was recorded to evaluate alkali resistance. Samples with a water contact angle of less than 80° for 2 hours or more were considered good. The results (time it took for the water contact angle to be less than 80°) are shown in Table 1.

[0218]

[0219] The cured coatings of the surface treatment agents in Examples 1 to 9 exhibited water repellency and stain-wiping properties because the molecular chains of the compounds used had hydrocarbon chains with 1 to 60 carbon atoms at their ends, improving the mobility of the molecular chains. Furthermore, the presence of 1 to 3 linking functional groups in the molecular chains of the compounds used improved intermolecular interactions and molecular mobility, resulting in good slipperiness and abrasion resistance. In addition, the presence of two or more hydrolyzable groups improved adhesion to the substrate, resulting in good abrasion resistance and alkali resistance. The cured coating of the surface treatment agent in Comparative Example 1 exhibited water repellency because the molecular chains of the compounds used had hydrocarbon chains with 1 to 60 carbon atoms at their ends, but the absence of linking functional groups in the molecular chains of the compounds used resulted in poor slipperiness, abrasion resistance, and alkali resistance. The cured film of the surface treatment agent in Comparative Example 2 exhibited high water repellency and dirt-wiping properties due to the presence of fluorinated hydrocarbon chains at the molecular chain ends of the compound used. However, because the molecular chain of the compound used did not contain linking functional groups, it was inferior in slipperiness, abrasion resistance, and alkali resistance. Comparative Example 3 was a glass substrate without a surface treatment agent, and since it was not surface-treated, it lacked all of these properties, confirming the effects of the examples. As described above, the surface treatment agents in the examples made it possible to obtain a cured film with excellent water repellency, slipperiness, dirt-wiping properties, abrasion resistance, and alkali resistance at a high level in spray coating, which is an example of wet coating.

[0220] [Example 10] The compound obtained in Synthesis Example 1 (Synthesis Examples 1-3) was dissolved in toluene to a concentration of 20% by mass to prepare a surface treatment agent.

[0221] [Example 11] The compound obtained in Synthesis Example 2 (Synthesis Example 2-3) was dissolved in dibutyl ether to a concentration of 20% by mass to prepare a surface treatment agent.

[0222] [Example 12] The compound obtained in Synthesis Example 3 (Synthesis Example 3-3) was dissolved in dibutyl ether to a concentration of 30% by mass to prepare a surface treatment agent.

[0223] [Example 13] The compound obtained in Synthesis Example 4 (Synthesis Example 4-4) was dissolved in butyl acetate to a concentration of 10% by mass to prepare a surface treatment agent.

[0224] [Example 14] The compound obtained in Synthesis Example 5 (Synthesis Example 5-4) was dissolved in a hexane / isooctane (mass ratio 50 / 50) mixed solution to a concentration of 50% by mass to prepare a surface treatment agent.

[0225] [Example 15] The compound obtained in Synthesis Example 6 (Synthesis Example 6-5) was dissolved in dibutyl ether to a concentration of 10% by mass to prepare a surface treatment agent.

[0226] [Example 16] The compound obtained in Synthesis Example 7 (Synthesis Example 7-3) was dissolved in dibutyl ether to a concentration of 20% by mass to prepare a surface treatment agent.

[0227] [Example 17] The compound obtained in Synthesis Example 8 (Synthesis Example 8-3) was dissolved in dibutyl ether to a concentration of 10% by mass to prepare a surface treatment agent.

[0228] [Example 18] The compound obtained in Synthesis Example 9 (Synthesis Example 9-3) was dissolved in isooctane to a concentration of 30% by mass to prepare a surface treatment agent.

[0229] [Comparative Example 4] A surface treatment agent was prepared by dissolving the compound represented by the above formula (A') in dibutyl ether to a concentration of 10% by mass.

[0230] [Comparative Example 5] A surface treatment agent was prepared by dissolving the compound represented by the above formula (B') in toluene to a concentration of 10% by mass.

[0231] [Comparative Example 6] No surface treatment agent used.

[0232] Formation of a hardened film of the surface treatment agent: On glass (Gorilla, manufactured by Corning) with a 10 nm thick layer of SiO2 coating on the outermost surface, each surface treatment agent prepared in the above examples and comparative examples was vacuum deposited (processing conditions: pressure: 2.0 × 10⁻⁶). -2 A cured film with a thickness of 3-5 nm was formed by curing in an atmosphere of Pa, heating temperature: 700°C, 80°C, and relative humidity 80% for 1 hour, and then in an atmosphere of 25°C and relative humidity 50% for 12 hours.

[0233] The water repellency, slipperiness, dirt-wiping properties, abrasion resistance, and alkali resistance of the glass with a hardened coating were evaluated using the method described below. For Comparative Example 6, a glass (Corning Gorilla) with no surface treatment, but coated with SiO2 to a thickness of 10 nm on its outermost surface, was used and evaluated in the same manner.

[0234] 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 (manufactured by Kyowa Interface Science Co., Ltd.) (droplet: 2 μl, temperature: 25°C, relative humidity: 40%). A contact angle (water repellency) of 85° or higher was considered good. The results (water contact angle) are shown in Table 2.

[0235] Evaluation of Slipperiness The slipperiness of the glass with the hardened coating prepared as described above was evaluated by assessing the coefficient of dynamic friction with the nonwoven fabric using the method described below. The coefficient of dynamic friction of the glass with the hardened coating with the nonwoven fabric was measured in accordance with ASTM D1894 using a surface properties measuring instrument TYPE: 14FW (manufactured by Shinto Kagaku Co., Ltd.) under the conditions of a load of 100 gf and a tensile speed of 500 mm / min. A slipperiness of 0.25 or less was considered good. The results (coefficient of dynamic friction) are shown in Table 2. [Slipperiness Evaluation Conditions] Load: 100 gf Stroke: 100 mm Contact area: 1 × 3 cm 2 Nonwoven fabric: BEMCOT (manufactured by Asahi Kasei Corporation)

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

[0237] 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 result of 2,000 or more times the contact angle fell below 80° was considered good. The results (number of times the water contact angle fell below 80°) are shown in Table 2. [Steel Wool Abrasion Resistance Test Conditions] Steel wool: Bonster #0000 Contact area: 1 cm 2 Distance traveled (one way): 40 mm; Speed: 4,800 mm / min; Load: 500 gf / cm 2

[0238] Evaluation of alkali resistance: The glass with the hardened film prepared as described above was immersed in a 0.4% by mass sodium hydroxide aqueous solution and placed in a 55°C oven. Every 30 minutes, the sample was removed and washed with water. The contact angle (water repellency) of the hardened film with respect to water was measured in the same manner as described above, and the time it took for the water contact angle to be less than 80° was recorded to evaluate alkali resistance. Samples with a water contact angle of less than 80° for 2 hours or more were considered good. The results (time it took for the water contact angle to be less than 80°) are shown in Table 2.

[0239]

[0240] The cured coatings of the surface treatment agents in Examples 10 to 18 exhibited water repellency and stain-wiping properties because the molecular chains of the compounds used had hydrocarbon chains with 1 to 60 carbon atoms at their ends, improving the mobility of the molecular chains. Furthermore, the presence of 1 to 3 linking functional groups in the molecular chains of the compounds used improved intermolecular interactions and molecular mobility, resulting in good slipperiness and abrasion resistance. In addition, the presence of two or more hydrolyzable groups improved adhesion to the substrate, resulting in good abrasion resistance and alkali resistance. The cured coating of the surface treatment agent in Comparative Example 4 exhibited water repellency because the molecular chains of the compounds used had hydrocarbon chains with 1 to 60 carbon atoms at their ends, but the absence of linking functional groups in the molecular chains of the compounds used resulted in poor slipperiness, abrasion resistance, and alkali resistance. The cured film of the surface treatment agent in Comparative Example 5 exhibited high water repellency and dirt-wiping properties due to the presence of fluorinated hydrocarbon chains at the molecular chain ends of the compound used. However, because the molecular chain of the compound used did not contain linking functional groups, it was inferior in slipperiness, abrasion resistance, and alkali resistance. Comparative Example 6 was a glass substrate without a surface treatment agent, and since it was not surface-treated, it lacked all of these properties, confirming the effects of the examples. As described above, the surface treatment agents in the examples were able to produce a cured film with excellent water repellency, slipperiness, dirt-wiping properties, abrasion resistance, and alkali resistance at a high level, even in vapor deposition coating.

Claims

1. The following general formula (1) A hydrocarbon terminal group-containing compound represented by the formula: (wherein R is a monovalent hydrocarbon group having 1 to 60 carbon atoms, Z is a divalent linked functional group independently containing at least one selected from oxygen, nitrogen, sulfur, and silicon atoms, Y is independently a divalent hydrocarbon group having 1 to 30 carbon atoms, W is a carbon atom, silicon atom, nitrogen atom, or a 3 to 5 valent organic group, A is a monovalent reactive group, k1 is an integer from 1 to 3, and k2 is an integer from 2 to 4.) 2. In the above formula (1), A is a cyclic ether group, and the following general formula (2) (In the formula, R 1 ) is an alkyl group or phenyl group having 1 to 4 carbon atoms independently, X is an alkyl group or hydrolyzable group independently, and n is an integer from 1 to 3. ) A hydroxyl group-containing silyl group or hydrolyzable silyl group represented by the following general formula (3) The hydrocarbon terminal group-containing compound according to claim 1, wherein the silazane group is represented by (wherein n'' is a number from 0 to 3, and n' is (3 - n'') / 2).

3. The hydrocarbon terminal group-containing compound according to claim 2, wherein in formula (2) above, X is selected from the group consisting of a hydroxyl group, an alkoxy group having 1 to 10 carbon atoms, an alkoxyalkoxy group having 2 to 10 carbon atoms, an acyloxy group having 1 to 10 carbon atoms, an alkenyloxy group having 2 to 10 carbon atoms, a halogen group, and a dialkylamino group having 2 to 10 carbon atoms.

4. The hydrocarbon terminal group-containing compound according to claim 1, wherein R is a monovalent hydrocarbon group having 3 to 32 carbon atoms, which may be linear, branched, cyclic, or a combination thereof, in formula (1) above.

5. The hydrocarbon terminal group-containing compound according to claim 1, 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.

6. In the above equation (1), Y independently gives the following general equation (4) (In the formula, R 2 R is an independent monovalent hydrocarbon group having 1 to 10 carbon atoms. 3 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 sum of carbon atoms in formula (4) 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 compound according to claim 1, which is a group represented by ).

7. In formula (1) above, W is a carbon atom, a silicon atom, a nitrogen atom, a trivalent or tetravalent cyclic hydrocarbon group having 6 to 8 carbon atoms, -SiR 8 = (R 8 (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 9 = (R 9 The hydrocarbon terminal group-containing compound according to claim 1, 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.

8. In the above formula (1), k1 is 1 and R is the following general formula (5) (wherein, R 4 is a methyl group, a cyclic alkyl group or a phenyl group. R 3 is an optionally substituted divalent cyclic hydrocarbon group having 3 to 10 carbon atoms. y is an integer of 0 or more, h is an integer of 0 to 6, and the sum of y and h is an integer such that the total number of carbon atoms in formula (5) is 60 or less. Each repeating unit shown in parentheses with y and h may be randomly bonded.) The hydrocarbon terminal group-containing compound according to claim 1, which is a monovalent hydrocarbon group represented by 9. The hydrocarbon terminal group-containing compound according to claim 1, wherein k1 is 2 or 3 in formula (1) above.

10. A surface treatment agent comprising a hydrocarbon terminal group-containing compound according to any one of claims 1 to 9.

11. An article surface-treated with the surface treatment agent described in claim 10.

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