WO2025211106A1 - Hydrocarbon-terminal-group-containing compound, surface treatment agent, and article - Google Patents

Abstract

Intermolecular interactions and molecular chain mobility are improved when a hydrocarbon-terminal-group-containing compound represented by formula (1) is used as a surface protective agent for a non-fluorine-based material, and a surface treatment agent containing the compound can form a cured coating film having excellent water repellency, slipperiness, ease of soil removal, and abrasion resistance, in particular, steel wool abrasion resistance. (R is a C1-60 monovalent hydrocarbon group, Z is a divalent connecting functional group containing at least one selected from O, N, S, and Si, Y is a C1-30 divalent hydrocarbon group, A is a monovalent reactive group, and k is 1-3.)

Description

Hydrocarbon end group-containing compounds, surface treatment agents and articles

The present invention relates to hydrocarbon end group-containing compounds, and more specifically to hydrocarbon end group-containing compounds, particularly alkyl end group-containing compounds, that form coatings with excellent water repellency, slipperiness, dirt wiping properties, and abrasion resistance, as well as surface treatment agents containing such compounds and articles that have been surface-treated with such surface treatment agents.

In recent years, the use of touch panels in displays, such as smartphones and in-car displays, has accelerated. However, because the screen of a touch panel is exposed and is often in direct contact with fingers or cheeks, it is prone to becoming soiled with sebum and other contaminants, creating a problem. Therefore, to improve appearance and visibility, there is an increasing demand every year for technology that makes it difficult for fingerprints to appear on the display surface, and technology that makes it easier to clean, and there is a desire to develop materials that can meet these demands. Since the surface of touch panel displays is particularly prone to fingerprints, there is a demand for the formation of a water- and oil-repellent layer. However, while conventional water- and oil-repellent layers are highly water- and oil-repellent and easy to wipe clean, they have the problem of not being sufficiently resistant to wear.

In general, fluoropolyether group-containing compounds have extremely low surface free energy, resulting in properties such as water and oil repellency, chemical resistance, lubricity, mold release properties, and stain resistance. Utilizing these properties, they are widely used industrially as water, oil, and stain repellent agents for paper and textiles, lubricants for magnetic recording media, oil repellents for precision instruments, mold release agents, cosmetics, and protective films. However, these properties also mean that they are non-sticky and non-adherent to other substrates, and while they can be applied to the surface of a substrate, it has been difficult to ensure that the coating adheres to it.

Silane coupling agents are well known for bonding organic compounds to the surface of substrates such as glass and cloth, and are widely used as coating agents for various substrate surfaces. Silane coupling agents contain an organic functional group and a reactive silyl group (generally a hydrolyzable silyl group such as an alkoxysilyl group) in each molecule. The hydrolyzable silyl group undergoes a self-condensation reaction in the presence of moisture in the air to form a coating. This coating is durable and strong because the hydrolyzable silyl group chemically and physically bonds with the surface of glass, metal, etc.

In response to this, compositions have been disclosed that use fluoropolyether group-containing polymers, in which hydrolyzable silyl groups have been introduced into fluoropolyether group-containing compounds, to form coatings that adhere easily to substrate surfaces and have water and oil repellency, chemical resistance, lubricity, releasability, and stain resistance (Patent Documents 1 to 6: JP-T-2008-534696, JP-T-2008-537557, JP-A-2012-072272, JP-A-2012-157856, JP-A-2013-136833, JP-A-2015-199906).

However, fluorine-based compounds are difficult to decompose in nature and tend to accumulate in the environment, which has led to a growing demand for the development of surface protection agents for non-fluorine-based materials.

In response, WO 2019/82583 (Patent Document 7) proposes a surface treatment agent that does not use fluorine groups. However, the abrasion resistance of this agent was not sufficient to withstand harsh usage environments.

Special Publication No. 2008-534696 Special Publication No. 2008-537557 JP 2012-072272 A JP 2012-157856 A JP 2013-136833 A Japanese Patent Application Laid-Open No. 2015-199906 WO 2019/82583

The present invention has been made in consideration of the above circumstances, and aims to provide a non-fluorine-based (i.e., no fluorine atoms in the molecule) hydrocarbon end group-containing compound capable of forming a cured coating that has excellent water repellency, slipperiness, dirt wipeability, and abrasion resistance, as well as a substantially non-fluorine-based surface treatment agent containing the compound, and an article that has been surface-treated with the surface treatment agent.

As a result of extensive research to achieve the above-mentioned objectives, the inventors discovered that when a hydrocarbon terminal group-containing compound represented by the general formula (1) described below, which has a hydrocarbon chain having 1 to 60 carbon atoms and a reactive group at the molecular chain terminal and which has 1 to 3 linking functional groups in the linking group (molecular chain) connecting the hydrocarbon chain and the reactive group, is used as a surface protective agent for the above-mentioned non-fluorinated materials, it improves intermolecular interactions and molecular chain mobility, and a surface treatment agent containing this compound can form a cured coating that is excellent in water repellency, slipperiness, dirt wipeability, and abrasion resistance, particularly steel wool abrasion resistance, thereby completing the present invention.

Accordingly, the present invention provides the following hydrocarbon terminal group-containing compound, surface treatment agent, and article.
[1]
The following general formula (1)
(In the formula, R is a monovalent hydrocarbon group having 1 to 60 carbon atoms, which may be linear, branched, or cyclic, or a combination thereof; Z is independently a divalent linking functional group containing at least one atom selected from oxygen atoms, nitrogen atoms, sulfur atoms, and silicon atoms; Y is independently a divalent hydrocarbon group having 1 to 30 carbon atoms, which may be linear, branched, or cyclic, or a combination thereof; A is a monovalent reactive group; and k is an integer of 1 to 3.)
A hydrocarbon terminal group-containing compound represented by the formula:
[2]
A in the formula (1) is represented by the following general formula (2):
(In the formula, ^R1 is independently an alkyl group having 1 to 4 carbon atoms or a phenyl group, X is independently a hydroxyl group or a hydrolyzable group, and n is an integer of 1 to 3.)
Or the following general formula (3)
(wherein n″ is a number from 0 to 3, and n′ is (3−n″)/2.)
The hydrocarbon terminal group-containing compound according to [1], wherein the hydroxyl group-containing silyl group or hydrolyzable silyl group is represented by the following formula:
[3]
The hydrocarbon terminal group-containing compound according to [2], wherein in the formula (2), 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 any one of [1] to [3], wherein in the formula (1), R is a monovalent hydrocarbon group having 3 to 32 carbon atoms, which may be linear, branched, or cyclic, or a combination thereof.
[5]
The hydrocarbon terminal group-containing compound according to any one of [1] to [4], wherein in the formula (1), Z's are independently a divalent group selected from an ether group, a carbonyl (ketone) group, an ester group, a carbonate group, a thioether group, a sulfinyl group, a sulfonyl group, a thioester group, a thiocarbonate group, a thiocarbamate group, an amino group, an amide group, a carbamate group, a urea group, a divalent nitrogen-containing heterocyclic group, a diorganosilylene group, and a divalent linear organopolysiloxane residue having 2 to 10 silicon atoms or a branched or cyclic organopolysiloxane residue having 3 to 10 silicon atoms.
[6]
In the formula (1), Y independently represents the following general formula (4):
(In the formula, ^R2 independently represents a monovalent hydrocarbon group having 1 to 10 carbon atoms, which may be linear, branched, or cyclic, or a combination thereof. ^R3 independently represents a divalent cyclic hydrocarbon group having 3 to 10 carbon atoms, which may have a substituent. a represents an integer of 0 to 30, b represents an integer of 0 to 15, c represents an integer of 0 to 10, and d represents an integer of 0 to 6, and 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. The repeating units shown in parentheses with a, b, c, and d may be bonded randomly.)
The hydrocarbon terminal group-containing compound according to any one of [1] to [5], wherein the hydrocarbon terminal group is a group represented by the formula:
[7]
In the formula (1), k is 1, and R is represented by the following general formula (5):
(In the formula, ^R4 is a methyl group, a cyclic alkyl group, or a phenyl group. ^R3 is independently a divalent cyclic hydrocarbon group having 3 to 10 carbon atoms, which may 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 formula (5) is 60 or less. The repeating units shown in parentheses with y and h may be bonded randomly.)
The hydrocarbon terminal group-containing compound according to any one of [1] to [6], wherein the hydrocarbon terminal group is a monovalent hydrocarbon group represented by the following formula:
[8]
The hydrocarbon terminal group-containing compound according to any one of [1] to [7], wherein k is 2 or 3 in the formula (1).
[9]
A surface treatment agent comprising the hydrocarbon terminal group-containing compound according to any one of [1] to [8].
[10]
An article surface-treated with the surface treatment agent according to [9].

Articles that have been surface-treated with a surface treatment agent containing the hydrocarbon terminal group-containing compound of the present invention have excellent water repellency, slipperiness, dirt-wiping properties, and abrasion resistance.

[Hydrocarbon end group-containing compounds]
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, which may be linear, branched, or cyclic, or a combination thereof; Z is independently a divalent linking functional group containing at least one atom selected from oxygen atoms, nitrogen atoms, sulfur atoms, and silicon atoms; Y is independently a divalent hydrocarbon group having 1 to 30 carbon atoms, which may be linear, branched, or cyclic, or a combination thereof; A is a monovalent reactive group; and k is an integer of 1 to 3.)

The hydrocarbon end group-containing compound of the present invention has a monovalent hydrocarbon group (hydrocarbon end group, R in formula (1)) at one end of its molecular chain, which may be linear, branched, cyclic, or a combination thereof, and has 1 to 60 carbon atoms, preferably 3 to 32 carbon atoms, and more preferably 8 to 30 carbon atoms, and a reactive group (substrate-adherence group, A in formula (1)) that exhibits substrate adhesion at the other end of its molecular chain, and the linking group connecting the hydrocarbon end group and the substrate-adherence group is a divalent linking group (-(Z-Y)k- in formula (1)) that contains a divalent linking functional group (Z in formula (1)) containing at least one atom selected from oxygen, nitrogen, sulfur, and silicon atoms. The introduction of the linking functional group improves the molecular mobility of the compound, starting from the linking functional group. Furthermore, the orientation of the hydrocarbon chains is determined by the linking functional group, and intermolecular interactions between the hydrocarbon chains and linking functional groups make it easier for the hydrocarbon chains on the surface of the cured coating to be oriented in one direction, resulting in cured coatings of surface treatment agents containing this compound having excellent water repellency, slip resistance, dirt wipeability, and abrasion resistance.

In the above formula (1), 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, which may be linear, branched, or cyclic, or a combination thereof. Examples of R include the following:
(In the formula, x is an integer of 0 to 59, preferably 2 to 31, and more preferably 7 to 29, and y and y′ are each an integer of 0 or more such that the total number of carbon atoms in each structure is 60 or less.)

As R, the following are more preferred.
(In the formula, ^R4 is a methyl group, a cyclic alkyl group, or a phenyl group. ^R3 is independently a divalent cyclic hydrocarbon group having 3 to 10 carbon atoms, which may have a substituent. y is an integer of 0 or more, h is an integer of 0 to 6, preferably 0 or 1, and the sum of y and h is an integer such that the total number of carbon atoms in formula (5) is 60 or less. The repeating units shown in parentheses with y and h may be bonded randomly.)

In the above formula (5), R ⁴ is a cyclic alkyl group such as a methyl group, a cyclopentyl group, a cyclohexyl group, or a phenyl group, and is preferably a methyl group.

In the above formula (5), ^R3 independently represents a divalent cyclic hydrocarbon group having 3 to 10 carbon atoms, which may have a substituent. Examples of the divalent cyclic hydrocarbon group represented by ^R3 include the following:
(wherein ^R6 is an alkyl group having 1 to 4 carbon atoms, such as a methyl group or an ethyl group.)

In the above formula (1), Z, together with Y, is a linking group that 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 a divalent linking functional group that independently contains at least one atom selected from oxygen atoms, nitrogen atoms, sulfur atoms, and silicon atoms, and is a characteristic component of the present invention. The divalent linking functional group containing at least one atom 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, a divalent imidazole group, or a divalent triazole group), a diorganosilylene group, or a linear or branched or cyclic divalent organopolysiloxane residue having 2 to 10 silicon atoms or 3 to 10 silicon atoms. Ether groups, thioether groups, carbamate groups, and urea groups are particularly preferred.

Examples of such Z include the following: In the following structure, the left bond is bonded to R or Y, and the right bond is bonded to Y.
(In the formula, ^R5 is independently a hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms, which may be linear, branched, cyclic, or a combination thereof; and e is an integer from 1 to 9.)

Here, ^R5 is independently a hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms, which may be linear, branched, cyclic, or a combination thereof. Examples of the monovalent hydrocarbon group having 1 to 10 carbon atoms include alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, neopentyl, hexyl, cyclohexyl, octyl, nonyl, and decyl; aryl groups such as phenyl, tolyl, xylyl, and naphthyl; aralkyl groups such as benzyl, phenylethyl, and phenylpropyl; and combinations thereof. ^R5 is preferably a hydrogen atom, a methyl group, or a phenyl group.

In the above formula (1), Y and Z are linking groups that link the hydrocarbon chain (R in formula (1)) at the molecular chain terminal to the reactive group (A in formula (1)), and are independently divalent hydrocarbon groups having 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms, more preferably 2 to 11 carbon atoms, and even more preferably 2 to 4 carbon atoms, which may be linear, branched, or cyclic, or a combination thereof. Examples of Y include groups represented by the following formula (4):
(In the formula, ^R2 independently represents a monovalent hydrocarbon group having 1 to 10 carbon atoms, which may be linear, branched, or cyclic, or a combination thereof. ^R3 independently represents a divalent cyclic hydrocarbon group having 3 to 10 carbon atoms, which may have a substituent. a represents an integer of 0 to 30, b represents an integer of 0 to 15, c represents an integer of 0 to 10, and d represents an integer of 0 to 6, and 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. The repeating units shown in parentheses with a, b, c, and d may be bonded randomly.)

In the above formula (4), ^R2 is independently a monovalent hydrocarbon group having 1 to 10 carbon atoms, which may be linear, branched, or cyclic, or a combination thereof, and specific examples include alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, neopentyl, hexyl, cyclohexyl, octyl, nonyl, and decyl, aryl groups such as phenyl, tolyl, xylyl, and naphthyl, aralkyl groups such as benzyl, phenylethyl, and phenylpropyl, and combinations thereof. ^R2 is preferably represented by the following formula:
(In the formula, g is an integer of 0 to 4.)

In the above formula (4), ^R3 independently represents a divalent cyclic hydrocarbon group having 3 to 10 carbon atoms, which may have a substituent, and is the same as ^R3 in the above formula (5), and examples thereof include those similar to those exemplified above.

In the above formula (4), a is an integer from 0 to 30, preferably an integer from 0 to 20, b is an integer from 0 to 15, preferably an integer from 0 to 5, c is an integer from 0 to 10, preferably an integer from 0 to 5, d is an integer from 0 to 6, preferably 0 or 1, and 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 1 to 10. In addition, the repeating units shown in parentheses with a, b, c, and d may be bonded randomly.

Specific examples of Y include the following: In the following structures, the left bond is bonded to Z, and the right bond is bonded to A or Z.
(In the formula, a1 is an integer of 1 to 30, a2 is an integer of 1 or more, b1 is an integer of 1 to 15, c1 is an integer of 1 to 10, and g is an integer of 0 to 4, with the proviso that the total number of carbon atoms in each structure is 30 or less.)

In the above formula (1), A is a monovalent reactive group, preferably a functional group that exhibits adhesion (bonding) reactivity to the surface of the substrate to be surface-treated, which is made of various materials such as paper, cloth, metals and their oxides, glass, plastics (resins), ceramics, and quartz. Examples of monovalent reactive groups include monovalent groups selected from carbon-carbon double bond-containing groups (limited to groups involved in ionic addition polymerization or curing reactions with active energy rays (light), excluding alkenyl groups (groups that undergo hydrosilylation addition polymerization)), carbon-carbon triple bond-containing groups, cyclic ether groups, hydroxyl group-containing groups (excluding those consisting only of hydroxyl groups), thiol groups, amino groups, azide groups, nitrogen-containing heterocyclic groups, phosphate-containing groups, hydroxyl group-containing silyl groups (silanol groups), and hydrolyzable silyl groups.

A may, for example, be a carbon-carbon double bond-containing group such as a cinnamic acid group, a sorbic acid group, an acryloyl group, a methacryloyl group, an acryloyloxy group, a methacryloyloxy group, an acrylamide group, a methacrylamide group, or a vinyl ether group; a carbon-carbon triple bond-containing group such as an alkynyl group having 2 to 20 carbon atoms, such as an ethynyl group, a propargyl group, a 2-methyl-2-propynyl group, a 3-butynyl group, a 4-pentynyl group, or a 5-hexynyl group, or a propargyloxy group, a 2-methyl-2-propynyloxy group, a 3-butynyloxy group, a 4-pentynyloxy group, or a 5-hexynyloxy group. Examples of such groups include alkynyloxy groups having 2 to 20 carbon atoms; cyclic ether groups such as epoxy groups, glycidyl 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; and monovalent groups such as hydroxyl group-containing silyl groups (silanol groups) and hydrolyzable silyl groups. Of these, hydroxyl group-containing silyl groups (silanol groups) and hydrolyzable silyl groups are preferred.

The hydroxyl group-containing silyl group and the hydrolyzable silyl group are those represented by the following general formula (2):
(In the formula, ^R1 is independently an alkyl group having 1 to 4 carbon atoms or a phenyl group, X is independently a hydroxyl group or a hydrolyzable group, and n is an integer of 1 to 3.)
Or the following general formula (3)
(wherein n″ is a number from 0 to 3, and n′ is (3−n″)/2.)
A group represented by the following formula is preferred.

In the above formula (2), R ¹ independently represents an alkyl group having 1 to 4 carbon atoms, such as a methyl group, an ethyl group, a propyl group, or a butyl group, or a phenyl group, with a methyl group being preferred.

In the above formula (2), X is independently a hydroxyl group or a hydrolyzable group. Examples of X include hydroxyl groups; alkoxy groups having 1 to 10 carbon atoms, such as methoxy, ethoxy, propoxy, isopropoxy, and butoxy; alkoxyalkoxy groups having 2 to 10 carbon atoms, such as methoxymethoxy and methoxyethoxy; acyloxy groups having 1 to 10 carbon atoms, such as acetoxy; alkenyloxy groups having 2 to 10 carbon atoms, such as isopropenoxy and cyclopentenyloxy; halogen groups, such as chlorine, bromine, and iodo; and dialkylamino groups having 2 to 10 carbon atoms, such as dimethylamino and diethylamino. Among these, methoxy, ethoxy, isopropenoxy, and chlorine groups are preferred. X may be the same or different.

In the above formula (2), n is an integer from 1 to 3, preferably 3.

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

In the above formula (1), k is an integer of 1 to 3. When k is 1 or greater, molecular mobility is improved by the linking functional group, and when k is 3 or less, intermolecular interactions are strong, making it easier for the molecular chains of the cured coating to be oriented in one direction while maintaining molecular mobility. Furthermore, when k is 1, it is more preferable that R in the above formula (1) is represented by the following formula (5):
(wherein R ³ , R ⁴ , y, h, and the sum of y and h are the same as above.)

The following structure can be given as an example of the structure of the hydrocarbon terminal group-containing compound represented by the above formula (1). By changing the combination of R, Z, Y, A, and k in the above formula (1), several different hydrocarbon terminal group-containing compounds can be obtained.

(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 portion corresponding to R in formula (1) is 60 or less, and the total number of carbon atoms in the portion corresponding to Y is 1 to 30.)

[Method for preparing hydrocarbon end group-containing compounds]
The hydrocarbon terminal group-containing compound represented by general formula (1) of the present invention can be prepared, for example, by the following method.
[Preparation method 1]
A hydrocarbon terminal group-containing compound (particularly a compound having a terminal hydrolyzable silyl group) represented by formula (1) can be produced by mixing a hydrocarbon terminal group-containing compound having an alkenyl group at the terminal with a compound having an SiH group and a hydrolyzable silyl group, and then carrying out a hydrosilylation addition reaction in the presence of a hydrosilylation reaction catalyst. When a compound having an SiH group and a hydrolyzable silyl group in which the hydrolyzable group is a halogen group is used, the compound can be produced by subsequently converting the substituent (halogen atom) on the silyl group to another hydrolyzable group.

Here, examples of hydrocarbon terminal group-containing compounds having an alkenyl group at the end include compounds represented by the following formula (1A).
(In the formula, R, Z, Y, and k are the same as above. ^Y1 is a monovalent hydrocarbon group having an alkenyl group having 2 to 30 carbon atoms, preferably 2 to 20 carbon atoms, which may be linear, branched, or cyclic, or a combination thereof.)

In the above formula (1A), ^Y1 is a monovalent hydrocarbon group having an alkenyl group and having 2 to 30 carbon atoms, preferably 2 to 20 carbon atoms, which may be linear, branched, or cyclic, or a combination thereof, and examples thereof include those having the terminal groups shown below.
(In the formula, ^R7 is independently a hydrogen atom or a monovalent hydrocarbon group which may be linear, branched, cyclic, or a combination thereof, and the total number of carbon atoms in each ^Y1 structure is 30 or less.)

As ^Y1 , the following is preferred.
(In the formula, g is the same as above, a' is independently an integer of 0 or more, and the total number of carbon atoms in each of the above structures is 30 or less.)

Examples of the compound represented by formula (1A) include the compounds shown below.
(In the formula, x, y, a1, a', and g are each independently the same as above, and the sum of a' and g is an integer such that the total number of carbon atoms in ^Y1 in formula (1A) is 2 to 30.)

The compound represented by formula (1A) (a hydrocarbon terminal group-containing compound having an alkenyl group at the terminal) can be prepared by the following method.
[Method (1) for preparing a compound represented by formula (1A)]
A compound represented by formula (1A) (a compound containing a hydrocarbon terminal group having an alkenyl group at its terminal) can be produced by mixing a hydrocarbon terminal group-containing compound having a hydroxyl group at its terminal with a base, adding a compound having a leaving group and an alkenyl group at its terminal, and carrying out a nucleophilic substitution reaction.

Here, examples of hydrocarbon terminal group-containing compounds having a hydroxyl group at the end include compounds represented by the following formula (1a-1):
(In the formula, R, Z, and Y are the same as above, and m is an integer of 0 to 2.)

Examples of the compound represented by formula (1a-1) include the compounds shown below.
(In the formula, x and a1 are independently the same as above.)

In the compound represented by formula (1a-1), when m is 1 or 2, examples of preparation methods include a method in which a compound having a hydroxyl group and a functional group other than a hydroxyl group reacts with a hydrocarbon terminal group-containing compound having a functional group, without the hydroxyl group acting as an activating group, to obtain the target compound; a method in which a compound having a protected hydroxyl group and a functional group reacts with the functional groups of a hydrocarbon terminal group-containing compound having a functional group to obtain a hydrocarbon terminal group-containing compound with a protected hydroxyl group introduced therein, and then deprotecting the group that protected the hydroxyl group to obtain the target compound; and other methods in which the target compound is obtained by reduction of a carbonyl compound or a hydroboration reaction.

Examples of compounds having a leaving group and an alkenyl group at the terminal include compounds represented by the following formula (1a-2) or (1a-3).
(In the formula, Z, Y, and ^Y1 are 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 0 or 1, and the sum of m and q is 0 or 1.)

Specific examples of the compound represented by formula (1a-2) or (1a-3) include allyl bromide, 2-methylallyl bromide, 1-bromodecane, and compounds represented by the following formula:

In the preparation method (1) of the compound represented by formula (1A), the amount of the compound having a leaving group and a terminal alkenyl group used is preferably 1 to 5 mol, and particularly 1 to 2 mol, per 1 mol of hydroxyl groups in the hydrocarbon terminal group-containing compound having a terminal hydroxyl group.

In the preparation method (1) of the compound represented by formula (1A), the base is not particularly limited, but examples thereof include lithium hydroxide, sodium hydride, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, cesium carbonate, and potassium tert-butoxide.
The amount of base used is preferably 1 to 3 mol, particularly 1 to 1.5 mol, per mol of hydroxyl groups in the hydrocarbon terminal group-containing compound having terminal hydroxyl groups.

In the preparation method (1) of the compound represented by formula (1A), a solvent can be used during the reaction. Examples of the solvent 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 the 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 compound containing a hydrocarbon terminal group having a terminal hydroxyl group.

In the preparation method (1) of the compound represented by formula (1A), a catalyst can be added that converts the leaving group in the compound having a terminal alkenyl group into one with higher leaving ability, thereby promoting the reaction. The catalyst for promoting the reaction is not particularly limited, but examples thereof 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 groups in the hydrocarbon terminal group-containing compound having terminal hydroxyl groups.

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

Further examples of the method for preparing the compound represented by formula (1A) (a hydrocarbon terminal group-containing compound having an alkenyl group at the terminal) include the following methods.
[Method (2) for preparing a compound represented by formula (1A)]
A hydrocarbon terminal group-containing compound having an isocyanate group at its terminal and a compound having a hydroxyl group and an alkenyl group at its terminal are mixed and reacted in the presence of a catalyst, whereby a compound represented by formula (1A) (a hydrocarbon terminal group-containing compound having an alkenyl group at its terminal) can be produced.

Here, the hydrocarbon terminal group-containing compound having an isocyanate group at the end is not particularly limited, but examples include octyl isocyanate and octadecyl isocyanate.

Examples of compounds having a hydroxyl group and an alkenyl group at their terminals include compounds represented by the following formula (1a-4) or (1a-5).
(wherein Z, Y, and ^Y1 are the same as above, and q is 0 or 1.)

Examples of the compounds represented by formula (1a-4) and (1a-5) include the compounds shown below.
(In the formula, a1 and a' are independently the same as above.)

In the preparation method (2) of the compound represented by formula (1A), the amount of the compound having a terminal hydroxyl group and an alkenyl group used is preferably 1 to 3 mol, and more preferably 1 to 1.5 mol, per 1 mol of isocyanate groups in the hydrocarbon terminal group-containing compound having an isocyanate group at the terminal.

In the preparation method (2) of the compound represented by formula (1A), examples of the catalyst include titanium compounds such as tetrakis(2-ethylhexyl) orthotitanate, tetra n-butyl titanate, and tetra n-propyl titanate; zirconium compounds such as tetra n-butyl zirconate and tetra n-propyl zirconate; tin compounds such as dibutyltin dimethoxide and dibutyltin dilaurate; bismuth compounds such as bismuth tris(2-ethylhexanoate); and amine catalysts such as diazabicycloundecene.
The amount of catalyst used is preferably 0.01 to 100 parts by mass, particularly 0.1 to 20 parts by mass, per 100 parts by mass of the hydrocarbon terminal group-containing compound having an isocyanate group at the end.

In the preparation method (2) of the compound represented by formula (1A), a solvent can be used when carrying out the reaction. Examples of the solvent include the same solvents as those used in the preparation method (1) of the compound represented by formula (1A).
The amount of the solvent used is preferably 0 to 1,000 parts by weight, particularly 50 to 200 parts by weight, per 100 parts by weight of the hydrocarbon terminal group-containing compound having an isocyanate group at the end.

In the preparation method (2) of the compound represented by formula (1A), the reaction conditions are preferably a temperature of 20 to 100°C, particularly 23 to 60°C, and a time of 0.5 to 72 hours, particularly 1 to 36 hours.

Further examples of the method for preparing the compound represented by formula (1A) (a hydrocarbon terminal group-containing compound having an alkenyl group at the terminal) include the following methods.
[Method (3) for preparing a compound represented by formula (1A)]
A compound represented by formula (1A) (a compound containing a hydrocarbon terminal group having an alkenyl group at its terminal) can be produced by mixing a hydrocarbon terminal group-containing compound having an NH group at its terminal with a compound having a carboxy group and an alkenyl group at its terminal, and reacting them in the presence of a condensing agent.

Here, examples of hydrocarbon terminal group-containing compounds having an NH group at the terminal include compounds represented by the following formula (1a-6):
(wherein R, R ⁵ , Z, Y, and m are the same as above.)

Examples of the compound represented by formula (1a-6) include the compounds shown below.
(wherein x is the same as above).

Examples of compounds having a carboxy group and an alkenyl group at the terminals include compounds represented by the following formula (1a-7) or (1a-8).
(wherein Z, Y, Y ¹ and q are the same as above, and the sum of m and q is 0 or 1.)

Examples of the compound represented by formula (1a-7) include the compounds shown below.
(In the formula, a' is independently the same as above.)

In the preparation method (3) of the compound represented by formula (1A), the amount of the compound having a terminal carboxy group and an alkenyl group used is preferably 1 to 5 mol, and particularly 1 to 1.5 mol, per 1 mol of the hydrocarbon terminal group-containing compound having an NH group at its terminal.

In the preparation method (3) of the compound represented by formula (1A), the condensing agent is not particularly limited, but examples thereof include N,N'-dicyclohexylcarbodiimide, N,N'-diisopropylcarbodiimide, and 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide.
The amount of the condensing agent used is preferably 1 to 3 mol, particularly preferably 1 to 1.5 mol, per mol of the hydrocarbon terminal group-containing compound having an NH group at the terminal.

In the preparation method (3) of the compound represented by formula (1A), a nucleophilic catalyst can be used. The nucleophilic catalyst is not particularly limited, but examples thereof include pyridine and 4-dimethylaminopyridine.
The amount of the nucleophilic catalyst used is preferably 0 to 1 mol, particularly 0.05 to 0.2 mol, per mol of the compound containing a hydrocarbon terminal group having an NH group at the terminal.

In the preparation method (3) of the compound represented by formula (1A), a solvent can be used during the reaction. Examples of the solvent 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 the solvent used is preferably 100 to 10,000 parts by mass, more preferably 500 to 2,000 parts by mass, per 100 parts by mass of the hydrocarbon terminal group-containing compound having an NH group at the end.

In the preparation method (3) of the compound represented by formula (1A), the reaction conditions are preferably a temperature of 20 to 100°C, particularly 20 to 50°C, and a time of 0.5 to 72 hours, particularly 1 to 24 hours.

Further examples of the method for preparing the compound represented by formula (1A) (a hydrocarbon terminal group-containing compound having an alkenyl group at the terminal) include the following methods.
[Method (4) for preparing a compound represented by formula (1A)]
The compound represented by formula (1A) (a hydrocarbon terminal group-containing compound having an alkenyl group at its terminal) can be produced by carrying out the oxazole synthesis described in Reference [X] using a hydrocarbon terminal group-containing compound having an aldehyde group at its terminal and a compound having a leaving group and an alkenyl group at its terminal.
Reference [X] Synlett 2009(3): 500-504.

Here, examples of hydrocarbon terminal group-containing compounds having an aldehyde group at the terminal include compounds represented by the following formula (1a-9):
(In the formula, R, Z, Y, and m are the same as above.)

Examples of the compound represented by formula (1a-9) include the compounds shown below.
(wherein x is the same as above).

Examples of compounds having a leaving group and an alkenyl group at the terminal include compounds represented by the following formula (1a-10) or (1a-11).
(In the formula, Z, Y, and ^Y1 are 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 0 or 1, and the sum of m and q is 0 or 1.)

Specific examples of the compounds represented by the following formulas (1a-10) and (1a-11) include allyl bromide, 2-methylallyl bromide, and compounds represented by the following formulas:

In the preparation method (4) of the compound represented by formula (1A), the amount of the compound having a leaving group and an alkenyl group at its terminal is preferably 1 to 5 mol, and more preferably 1 to 1.5 mol, per 1 mol of the hydrocarbon terminal group-containing compound having an aldehyde group at its terminal.

In the preparation method (4) of the compound represented by formula (1A), a base can be used. The base is not particularly limited, but examples thereof include sodium hydroxide, potassium hydroxide, sodium carbonate, and potassium carbonate.
The amount of base used is preferably 1 to 5 mol, particularly 1 to 3 mol, per mol of the hydrocarbon terminal group-containing compound having an aldehyde group at the terminal.

In the preparation method (4) of the compound represented by formula (1A), a solvent can be used during the reaction. Examples of the solvent 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 particularly preferred imidazolium salts such as 1-butyl-3-methylimidazolium bromide, 1-ethyl-3-methylimidazolium chloride and 1-ethyl-3-methylimidazolium bromide.
The amount of the solvent used is preferably 100 to 10,000 parts by mass, particularly 1,000 to 7,000 parts by mass, per 100 parts by mass of the hydrocarbon terminal group-containing compound having an aldehyde group at the end.

In the preparation method (4) of the compound represented by formula (1A), the reaction conditions are preferably a temperature of 20 to 150°C, particularly 25 to 100°C, and a time of 0.5 to 72 hours, particularly 6 to 24 hours.

Further examples of the method for preparing the compound represented by formula (1A) (a hydrocarbon terminal group-containing compound having an alkenyl group at the terminal) include the following methods.
[Method (5) for preparing a compound represented by formula (1A)]
A hydrocarbon terminal group-containing compound having an azide group at its terminal and a compound having an alkynyl group and an alkenyl group at its terminal are mixed and reacted in the presence of a catalyst to produce a compound represented by formula (1A) (a hydrocarbon terminal group-containing compound having an alkenyl group at its terminal).

Here, examples of hydrocarbon terminal group-containing compounds having an azide group at the end include compounds represented by the following formula (1a-12):
(In the formula, R, Z, Y, and m are the same as above.)

Examples of the compound represented by formula (1a-12) include the compounds shown below.
(wherein x is the same as above).

Examples of compounds having an alkynyl group and an alkenyl group at the terminal include compounds represented by the following formula (1a-13) or (1a-14).
(wherein Z, Y, and ^Y1 are the same as above; q is 0 or 1; and the sum of m and q is 0 or 1.)

Examples of the compound represented by formula (1a-13) include the compounds shown below.
(wherein x is the same as above).

In the preparation method (5) of the compound represented by formula (1A), the amount of the compound having an alkynyl group and an alkenyl group at its terminal is preferably 1 to 5 mol, and more preferably 1 to 1.2 mol, per 1 mol of the hydrocarbon terminal group-containing compound having an azide group at its terminal.

In the preparation method (5) of the compound represented by formula (1A), the catalyst is not particularly limited, but examples thereof include copper(I) iodide, copper(II) sulfate pentahydrate (cupric sulfate pentahydrate), chloro(pentamethylcyclopentadienyl)(cyclooctadiene)ruthenium(II), and pentamethylcyclopentadienylbis(triphenylphosphine)ruthenium(II) chloride.
The amount of catalyst used is preferably 0.001 to 10 mol, particularly preferably 0.1 to 1 mol, per mol of the hydrocarbon terminal group-containing compound having an azide group at the end.

In the preparation method (5) of the compound represented by formula (1A), when copper(II) sulfate pentahydrate (cupric sulfate pentahydrate) is used as the catalyst, a co-catalyst is used to generate copper(I) in the system. The co-catalyst is not particularly limited, but examples thereof include sodium ascorbate.
The amount of the co-catalyst used is preferably 0.002 to 20 mol, particularly preferably 0.2 to 2 mol, per mol of the hydrocarbon terminal group-containing compound having an azide group at the end.

In the preparation method (5) of the compound represented by formula (1A), a solvent can be used during the reaction. Examples of the solvent 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, water, alcohols such as methanol and tert-butanol, and mixed solvents of water and the alcohols in any ratio.
The amount of the solvent used is preferably 0 to 3,000 parts by mass, particularly 50 to 1,500 parts by mass, per 100 parts by mass of the hydrocarbon terminal group-containing compound having an azide group at the end.

In the preparation method (5) of the compound represented by formula (1A), the reaction conditions are preferably a temperature of 20 to 100°C, particularly 23 to 60°C, and a reaction time of 0.5 to 72 hours, particularly 6 to 24 hours.

In Preparation Method 1, examples of compounds having a SiH group and a hydrolyzable silyl group include trimethoxysilane, triethoxysilane, triacetoxysilane, and trichlorosilane.

In Preparation Method 1, the amount of the compound having a SiH group and a hydrolyzable silyl group used is preferably 1 to 10 mol, and more preferably 5 to 10 mol, per 1 mol of alkenyl group in the hydrocarbon terminal group-containing compound having an alkenyl group at the terminal.

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. Platinum compounds such as vinylsiloxane coordination compounds are preferred. The platinum compounds are preferably used by dissolving them in a solvent such as toluene, a lower alcohol, a higher alcohol, or a silicone-based solvent.
The amount of the hydrosilylation reaction catalyst used is preferably an amount that provides 0.001 to 1,000 ppm, and more preferably 0.01 to 100 ppm, in terms of transition metal (by mass), relative to the mass of the hydrocarbon terminal group-containing compound having an alkenyl group at the terminal.

In Preparation Method 1, a cocatalyst that activates the hydrosilylation reaction or a cocatalyst that prevents inversion of the alkenyl group can be used. Examples of cocatalysts that activate the hydrosilylation reaction include acetic acid, formic acid, and propionic acid. Examples of cocatalysts that prevent inversion of the alkenyl group include formamide, acetamide, and acetonitrile.
When these co-catalysts are blended, the amount used is preferably an amount equivalent to 10 to 1,000,000 ppm, more preferably 100 to 10,000 ppm, based on the mass of the hydrocarbon terminal group-containing compound having an alkenyl group at the terminal.

A solvent can be used during the reaction in Preparation Method 1. Examples of the solvent 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 the solvent used is preferably 0 to 1,000 parts by mass, more preferably 50 to 200 parts by mass, per 100 parts by mass of the hydrocarbon terminal group-containing compound having an alkenyl group at the end.

In Preparation Method 1, the reaction conditions for the hydrocarbon terminal group-containing compound having an alkenyl group at the end and the compound having a 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, particularly 1 to 36 hours.

In Preparation Method 1, when a compound having a SiH group and a hydrolyzable silyl group, such as trichlorosilane, in which the hydrolyzable group is a halogen group (a compound containing a SiH group and a halogenated silyl group) is used, the substituent (halogen atom) on the silyl group can then be converted to another hydrolyzable group, for example, an alkoxy group such as 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 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 halogenated silyl group-containing compound.

In Preparation Method 1, the reaction conditions for converting the substituent (halogen atom) on the silyl group to another hydrolyzable group are preferably a temperature of 0 to 80°C, particularly 20 to 60°C, for 0.5 to 72 hours, particularly 1 to 36 hours.

Other methods for preparing the hydrocarbon terminal group-containing compound represented by general formula (1) of the present invention include the following methods.
[Preparation method 2]
A hydrocarbon terminal group-containing compound having a terminal SiH group and a compound having a reactive group such as an alkenyl group and a hydrolyzable silyl group are mixed together, and the mixture is subjected to a hydrosilylation addition reaction in the presence of a hydrosilylation reaction catalyst, thereby producing a hydrocarbon terminal group-containing compound represented by formula (1) (particularly a compound having a terminal hydrolyzable silyl group).

Here, examples of hydrocarbon terminal group-containing compounds having SiH groups at their terminals include compounds represented by the following formula (1B):
(wherein R, Z, Y, and k are the same as above. ^Z1 is a diorganosilylene group or a linear divalent organopolysiloxane residue having 2 to 10 silicon atoms or a branched or cyclic divalent organopolysiloxane residue having 3 to 10 silicon atoms.)

In the above formula (1B), ^Z1 is a diorganosilylene group or a linear divalent organopolysiloxane residue having 2 to 10 silicon atoms, particularly 2 to 8 silicon atoms, or a branched or cyclic divalent organopolysiloxane residue having 3 to 10 silicon atoms, particularly 3 to 8 silicon atoms, examples of which are shown below: In the following structure, the bond on the left is bonded to Y and the bond on the right is bonded to H.
(wherein e is the same as above.)

Examples of the compound represented by formula (1B) include the compounds shown below.
(In the formula, x, a1, and e are the same as above.)

Furthermore, among compounds having reactive groups such as an alkenyl group and a hydrolyzable silyl group, examples of compounds having an alkenyl group and a hydrolyzable silyl group include vinyltrimethoxysilane, allyltrimethoxysilane, and octenyltrimethoxysilane.
Furthermore, examples of compounds having a reactive group other than an alkenyl group and a hydrolyzable silyl group include allyl glycidyl ether.

In Preparation Method 2, the amount of compound having a reactive group such as an alkenyl group or a hydrolyzable silyl group used is preferably 1 to 5 mol, and more preferably 1 to 3 mol, per 1 mol of SiH groups in the hydrocarbon terminal group-containing compound having SiH groups at the terminals.

In Preparation Method 2, examples of the hydrosilylation catalyst include the same as those in Preparation Method 1. Preferred are platinum compounds such as vinylsiloxane coordination compounds. The platinum compounds are preferably used by dissolving them in a solvent such as toluene, a lower alcohol, a higher alcohol, or a silicone solvent.
The amount of the hydrosilylation reaction catalyst used is preferably an amount that provides 0.001 to 1,000 ppm, and more preferably 0.01 to 100 ppm, in terms of transition metal (by mass), relative to the mass of the hydrocarbon terminal group-containing compound having a terminal SiH group.

A co-catalyst that activates the hydrosilylation reaction can be used in Preparation Method 2. Examples of the co-catalyst that activates the hydrosilylation reaction include acetic acid, formic acid, and propionic acid.
The amount of the cocatalyst that activates the hydrosilylation reaction is preferably an amount that is 10 to 1,000,000 ppm, and more preferably 100 to 10,000 ppm, based on the mass of the hydrocarbon terminal group-containing compound having a terminal SiH group.

In Preparation Method 2, a solvent can be used when carrying out the reaction. Examples of the solvent include the same solvents as those in Preparation Method 1.
The amount of the solvent used is preferably 0 to 1,000 parts by mass, more preferably 50 to 200 parts by mass, per 100 parts by mass of the hydrocarbon terminal group-containing compound having a terminal SiH group.

In Preparation Method 2, the reaction conditions are preferably a temperature of 20 to 120°C, particularly 60 to 100°C, and a time of 0.5 to 72 hours, particularly 1 to 36 hours.

Other methods for preparing the hydrocarbon terminal group-containing compound represented by general formula (1) of the present invention include the following methods.
[Preparation method 3]
A hydrocarbon terminal group-containing compound represented by formula (1) (particularly a compound having an amino group-containing silyl group at its terminal and/or a polysilazane compound which is a polymer thereof) can be produced by mixing a hydrocarbon terminal group-containing compound having an alkenyl group at its terminal with trichlorosilane and reacting them in the presence of a hydrosilylation reaction catalyst, and then reacting the resulting compound with ammonia gas.

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

In Preparation Method 3, the amount of ammonia gas used is preferably 1 to 300 cc/min, and particularly 30 to 200 cc/min.

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 with trichlorosilane and ammonia gas. Examples of the solvent include the same solvents as those used in Preparation Method 1.
The amount of the 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 compound containing a hydrocarbon terminal group having an alkenyl group at the end.

In Preparation Method 3, the reaction conditions for the reaction of ammonia gas with a hydrocarbon terminal group-containing compound having an alkenyl group at the end and trichlorosilane are preferably room temperature (23±15°C, the same applies below), particularly 20 to 30°C, for 2 to 36 hours, particularly 4 to 12 hours.

Other methods for preparing the hydrocarbon terminal group-containing compound represented by general formula (1) of the present invention include the following methods.
[Preparation method 4]
A hydrocarbon terminal group-containing compound having a terminal hydroxyl group and a compound having an isocyanate group and a reactive group (e.g., a hydrolyzable silyl group or a (meth)acryloyloxy group) is mixed and reacted in the presence of a catalyst to produce a hydrocarbon terminal group-containing compound represented by formula (1) (particularly a compound having a reactive group such as a hydrolyzable silyl group or a (meth)acryloyloxy group at the terminal via a urethane bond). In the present invention, the (meth)acryloyloxy group refers to an acryloyloxy group or a methacryloyloxy group.

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

Examples of the compound represented by formula (1C) include the compounds shown below.
(In the formula, x and a1 are independently the same as above.)

The compound represented by formula (1C) (a hydrocarbon terminal group-containing compound having a terminal hydroxyl group) can be prepared by the following method.
[Method (1) for preparing a compound represented by formula (1C)]
A hydrocarbon terminal group-containing compound represented by formula (1C) (particularly a hydrocarbon terminal group-containing compound having a terminal hydroxyl group) can be produced by mixing and reacting a hydrocarbon terminal group-containing compound having an isocyanate group at its terminal with a compound having an NH group and a hydroxyl group at its terminal.

Here, the hydrocarbon terminal group-containing compound having an isocyanate group at the end is not particularly limited, but examples include octyl isocyanate and octadecyl isocyanate.

Examples of compounds having an NH group and a hydroxyl group at their terminals include compounds represented by the following formula (1c-1) or (1c-2).
(wherein Z, Y, and ^R5 are the same as above, and p is an integer of 0 to 2.)

Examples of the compounds represented by formula (1c-1) and (1c-2) include the compounds shown below.
(In the formula, a1 is independently the same as above.)

In the preparation method (1) of the compound represented by formula (1C), the amount of the compound having an NH group and a hydroxyl group at its terminal is preferably 1 to 3 mol, and more preferably 1 to 1.5 mol, per 1 mol of isocyanate groups in the hydrocarbon terminal group-containing compound having an isocyanate group at its terminal.

In the preparation method (1) of the compound represented by formula (1C), a solvent can be used when carrying out the reaction. Examples of the solvent include the same solvents as those used in the preparation method (1) of the compound represented by formula (1A).
The amount of the solvent used is preferably 100 to 10,000 parts by mass, particularly 500 to 2,000 parts by mass, per 100 parts by mass of the hydrocarbon terminal group-containing compound having an isocyanate group at the end.

In the preparation method (1) of the compound represented by formula (1C), the reaction conditions are preferably a temperature of 20 to 100°C, particularly 23 to 60°C, and a time of 0.5 to 72 hours, particularly 1 to 36 hours.

Further examples of the method for preparing the compound represented by formula (1C) (a hydrocarbon terminal group-containing compound having a terminal hydroxyl group) include the following methods.
[Method (2) for preparing a compound represented by formula (1C)]
A compound represented by formula (1C) (a compound containing a hydrocarbon terminal group having a terminal hydroxyl group) can be produced by mixing a hydrocarbon terminal group-containing compound having an alkenyl group at the terminal with a borane compound, hydroborating the resulting mixture, and then oxidizing the resulting mixture with hydrogen peroxide and a base.

Examples of hydrocarbon terminal group-containing compounds having an alkenyl group at the end include compounds represented by the following formula (1c-3) or (1c-4).
(In the formula, R, Z, Y, ^Y1 , and m are the same as above. R' is a monovalent hydrocarbon group having 1 to 58 carbon atoms, which may be linear, branched, or cyclic, or a combination thereof.)

Here, R' is a monovalent hydrocarbon group having 1 to 58 carbon atoms, which may be linear, branched, or cyclic, or a combination thereof, and examples thereof include the following:
(wherein x' is an integer from 0 to 57.)

Examples of the compounds represented by formula (1c-3) and (1c-4) include the compounds shown below.
(wherein x, x'a1, and a' are the same as above.)

Here, the compound represented by formula (1c-4) can be prepared by a method similar to preparation method (1) or (2) for the compound represented by formula (1A).

In the preparation method (2) of the compound represented by formula (1C), the borane compound is not particularly limited, but examples thereof include tetrahydrofuran-borane, dimethyl sulfide-borane, catecholborane, pinacolborane, and 9-borabicyclo[3.3.1]nonane.
The amount of the borane compound used is preferably 1 to 5 mol, particularly 1 to 1.5 mol, per mol of the hydrocarbon terminal group-containing compound having an alkenyl group at the terminal.

In the preparation method (2) of the compound represented by formula (1C), the amount of hydrogen peroxide used is preferably 1 to 20 mol, and particularly preferably 10 to 15 mol, per 1 mol of the hydrocarbon terminal group-containing compound having an alkenyl group at the terminal.

In the preparation method (2) of the compound represented by formula (1C), the base is not particularly limited, but examples thereof include lithium hydroxide, sodium hydride, sodium hydroxide, potassium hydroxide, sodium bicarbonate, sodium carbonate, potassium bicarbonate, and potassium carbonate.
The amount of base used is preferably 2 to 40 mol, particularly 5 to 20 mol, per mol of the hydrocarbon terminal group-containing compound having an alkenyl group at the terminal.

In the preparation method (2) of the compound represented by formula (1C), a solvent can be used during the reaction. Examples of the solvent include chain ether compounds such as diethyl ether and dibutyl ether, and cyclic ether compounds such as tetrahydrofuran and dioxane.
The amount of the solvent used is preferably 0 to 1,000 parts by mass, particularly 100 to 200 parts by mass, per 100 parts by mass of the hydrocarbon terminal group-containing compound having an alkenyl group at the end.

In the preparation method (2) of the compound represented by formula (1C), the reaction conditions are preferably a temperature of 20 to 100°C, particularly 23 to 50°C, and a time of 0.5 to 72 hours, particularly 1 to 9 hours.

Furthermore, in Preparation Method 4, examples of compounds having an isocyanate group and a reactive group include 3-isocyanatopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, and 1,1-(bisacryloyloxymethyl)ethyl isocyanate.

In Preparation Method 4, the amount of the compound having an isocyanate group and a reactive group used is preferably 1 to 3 mol, and more preferably 1 to 1.5 mol, per 1 mol of hydroxyl groups in the hydrocarbon terminal group-containing compound having a terminal hydroxyl group.

In Preparation Method 4, examples of the catalyst include titanium compounds such as tetrakis(2-ethylhexyl) orthotitanate, tetra n-butyl titanate, and tetra n-propyl titanate; zirconium compounds such as tetra n-butyl zirconate and tetra n-propyl zirconate; tin compounds such as dibutyltin dimethoxide and dibutyltin dilaurate; bismuth compounds such as bismuth tris(2-ethylhexanoate); and amine catalysts such as diazabicycloundecene.
The amount of the catalyst used is preferably 0.01 to 100 parts by mass, particularly preferably 0.1 to 20 parts by mass, per 100 parts by mass of the compound containing a hydrocarbon terminal group having a terminal hydroxyl group.

In Preparation Method 4, a solvent can be used when carrying out the reaction. Examples of the solvent include the same solvents as those in Preparation Method 1.
The amount of the 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 compound containing a hydrocarbon terminal group having a terminal hydroxyl group.

In Preparation Method 4, the reaction conditions are preferably a temperature of 20 to 100°C, particularly 30 to 60°C, and a time of 0.5 to 72 hours, particularly 1 to 36 hours.

Other methods for preparing the hydrocarbon terminal group-containing compound represented by general formula (1) of the present invention include the following methods.
[Preparation method 5]
A hydrocarbon terminal group-containing compound having a terminal hydroxyl group and phosphorus oxychloride are mixed and reacted, and then water is 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).

Here, examples of hydrocarbon terminal group-containing compounds having a terminal hydroxyl group include compounds represented by formula (1C) in Preparation Method 4 above, in which m is other than 0 (i.e., m is 1 or 2). Specific examples include the compounds shown below.
(In the formula, x and a1 are independently the same as above.)

In Preparation Method 5, the amount of phosphorus oxychloride used is preferably 1 to 4 mol, and more preferably 1 to 2 mol, per 1 mol of hydroxyl groups in the hydrocarbon end group-containing compound having a terminal hydroxyl group.

In Preparation Method 5, a solvent can be used when reacting the hydrocarbon terminal group-containing compound having a terminal hydroxyl group with phosphorus oxychloride. Examples of the solvent include the same solvents as those used in Preparation Method 1.
The amount of the 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 compound containing a hydrocarbon terminal group having a terminal hydroxyl group.

In Preparation Method 5, the reaction conditions for the hydrocarbon terminal group-containing compound having a terminal hydroxyl group with phosphorus oxychloride are preferably a temperature of 0 to 80°C, particularly 15 to 50°C, for 0.5 to 72 hours, particularly 1 to 36 hours.

In Preparation Method 5, the amount of water used is preferably 50 to 1,000 parts by weight, and more preferably 100 to 500 parts by weight, per 100 parts by weight of the hydrocarbon terminal group-containing compound having a terminal hydroxyl group.

In Preparation Method 5, the reaction conditions for the reaction of the reaction product of a hydrocarbon terminal group-containing compound having a terminal hydroxyl group with phosphorus oxychloride and water are preferably a temperature of 0 to 80°C, particularly 15 to 50°C, for 0.5 to 72 hours, particularly 1 to 36 hours.

Other methods for preparing the hydrocarbon terminal group-containing compound represented by general formula (1) of the present invention include the following methods.
[Preparation method 6]
A hydrocarbon terminal group-containing compound represented by formula (1) (particularly a compound having a reactive group such as a hydrolyzable silyl group or a (meth)acryloyloxy group at its terminal via a urea bond) can be produced by mixing and reacting a hydrocarbon terminal group-containing compound having an NH group at its terminal with a compound having an isocyanate group and a reactive group (for example, a hydrolyzable silyl group or a (meth)acryloyloxy group).

Here, examples of hydrocarbon terminal group-containing compounds having an NH group at the terminal include compounds represented by the following formula (1D).
(wherein R, R ⁵ , Z, Y, and m are the same as above.)

Examples of the compound represented by formula (1D) include the compounds shown below.
(wherein x and a1 are the same as above.)

The compound represented by formula (1D) (a hydrocarbon terminal group-containing compound having an NH group at the terminal) can be prepared by the following method.
[Method (1) for preparing a compound represented by formula (1D)]
A compound represented by formula (1D) (a compound containing a hydrocarbon terminal group having an NH group at its terminal) can be produced by mixing an acid with a hydrocarbon terminal group-containing compound having an NH group at its terminal protected with a tert-butoxycarbonyl protecting group.

Here, examples of hydrocarbon terminal group-containing compounds having an NH group at the terminal protected with a tert-butoxycarbonyl protecting group include compounds represented by the following formula (1d-1):
(wherein R, R ⁵ , Z, Y, and m are the same as above, and ^t Bu is a tert-butyl group.)

Here, examples of the compound represented by formula (1d-1) include those shown below.
(wherein x and a1 are the same as above, and ^t Bu is a tert-butyl group.)

In the preparation method (1) of the compound represented by formula (1D), the acid is not particularly limited. Examples of the acid include organic acids such as trifluoroacetic acid and trimethylsilyl triflate, and examples of other acids such as hydrochloric acid and sulfuric acid.
The amount of acid used is preferably 1 to 100 mol, particularly preferably 1 to 10 mol, per mol of tert-butoxycarbonyl protecting group in the hydrocarbon terminal group-containing compound having an NH group at its terminal protected by a tert-butoxycarbonyl protecting group.

In the preparation method (1) of the compound represented by formula (1D), a solvent can be used during the reaction. Examples of the solvent include dichloromethane, 1,2-dichloroethane, and acetonitrile when an organic acid is used, and water, methanol, 1,4-dioxane, or a mixture thereof when another acid is used.
The amount of the solvent used is preferably 0 to 100,000 parts by mass, particularly 500 to 1,000 parts by mass, per 100 parts by mass of the hydrocarbon terminal group-containing compound having an NH group at its terminal protected with a tert-butoxycarbonyl protecting group.

In the preparation method (1) of the compound represented by formula (1D), the reaction conditions are preferably a temperature of 20 to 100°C, particularly 25 to 65°C, and a time of 0.5 to 72 hours, particularly 1 to 24 hours.

Further examples of the method for preparing the compound represented by formula (1D) (a hydrocarbon terminal group-containing compound having an NH group at the terminal) include the following methods.
[Method (2) for preparing a compound represented by formula (1D)]
A compound represented by formula (1D) (a compound containing a hydrocarbon terminal group having an NH group at its terminal) can be produced by reducing a hydrocarbon terminal group-containing compound having an amide group at its terminal with a base.

Here, examples of hydrocarbon terminal group-containing compounds having an amide group at the terminal include compounds represented by the following formula (1d-2).
(wherein R, R ⁵ , Z, Y, Y ¹ and m are the same as above.)

Here, examples of the compound represented by formula (1d-2) include those shown below.
(wherein x and a' are the same as above.)

In the preparation method (2) of the compound represented by formula (1D), the base is not particularly limited, but examples thereof include lithium aluminum hydride and sodium bis(2-methoxyethoxy)aluminum hydride.
The amount of base used is preferably 1 to 10 mol, particularly 2 to 5 mol, per mol of amide group in the hydrocarbon terminal group-containing compound having an amide group at the terminal.

In the preparation method (2) of the compound represented by formula (1D), a solvent can be used during the reaction. Examples of the solvent 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 the solvent used is preferably 100 to 10,000 parts by mass, particularly 500 to 1,000 parts by mass, per 100 parts by mass of the hydrocarbon terminal group-containing compound having an amide group at the end.

In the preparation method (2) of the compound represented by formula (1D), the reaction conditions are preferably a temperature of 0 to 40°C, particularly 0 to 25°C, and a time of 0.5 to 72 hours, particularly 1 to 24 hours.

Furthermore, in Preparation Method 6, examples of compounds having an isocyanate group and a reactive group include 3-isocyanatopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, 2-(acryloyloxy)ethyl isocyanate, and 2-isocyanatoethyl methacrylate.

In Preparation Method 6, the amount of the compound having an isocyanate group and a reactive group used is preferably 1 to 3 mol, and more preferably 1 to 1.5 mol, per 1 mol of the hydrocarbon terminal group-containing compound having an NH group at its terminal.

In Preparation Method 6, a solvent can be used when carrying out the reaction. Examples of the solvent include the same solvents as those in Preparation Method 1.
The amount of the solvent used is preferably 0 to 1,000 parts by mass, more preferably 50 to 1,000 parts by mass, and even more preferably 50 to 200 parts by mass, per 100 parts by mass of the hydrocarbon terminal group-containing compound having an NH group at the terminal.

In Preparation Method 6, the reaction conditions are preferably a temperature of 0 to 100°C, particularly 20 to 60°C, and a time of 0.5 to 72 hours, particularly 1 to 36 hours.

Other methods for preparing the hydrocarbon terminal group-containing compound represented by general formula (1) of the present invention include the following methods.
[Preparation method 7]
The hydrocarbon terminal group-containing compound represented by formula (1) can be produced by mixing a hydrocarbon terminal group-containing compound having an alkenyl group at its terminal with a silane compound having a thiol group at its terminal, or a hydrocarbon terminal group-containing compound having a thiol group at its terminal with a silane compound having an alkenyl group at its terminal, and reacting them in the presence of a polymerization initiator.

Here, examples of hydrocarbon terminal group-containing compounds having an alkenyl group at the terminal include compounds represented by the following formula (1E-1) or (1E-2).
(In the formula, R, Z, Y, ^Y1 , and m are the same as above. R' is a monovalent hydrocarbon group having 1 to 58 carbon atoms, which may be linear, branched, or cyclic, or a combination thereof.)

Here, R' is a monovalent hydrocarbon group having 1 to 58 carbon atoms, which may be linear, branched, or cyclic, or a combination thereof, and examples thereof include the following:
(wherein x' is an integer from 0 to 57.)

Examples of the compounds represented by formula (1E-1) and (1E-2) include the compounds shown below.
(wherein x, x', a1, and a' are the same as above.)

Here, the compound represented by formula (1E-2) can be prepared by a method similar to preparation method (1) or (2) for the compound represented by formula (1A).

Furthermore, examples of silane compounds having a thiol group at the terminal include compounds represented by the following formula (1F).
(In the formula, Z, Y, and A are the same as above. p is an integer of 0 to 2, and the sum of m and p is an integer of 0 to 2.)

Examples of the compound represented by formula (1F) include the compounds shown below.
(wherein a1 is the same as above.)

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

Examples of the compound represented by formula (1G) include the compounds shown below.
(wherein x is the same as above).

Here, examples of preparation methods for compounds represented by formula (1G) where m is 1 or 2 include a method in which a compound having a thiol group and a functional group other than a thiol group reacts with a hydrocarbon terminal group-containing compound having a functional group, without the thiol group acting as an active group, to obtain the target compound; and a method in which a compound having a protected thiol group and a functional group reacts with the functional groups of a hydrocarbon terminal group-containing compound having a functional group to obtain a hydrocarbon terminal group-containing compound into which a protected thiol group has been introduced, and then the group protecting the thiol group is deprotected to obtain the target compound.

In the preparation method 7, an example of the silane compound having an alkenyl group at the terminal is a compound represented by the following formula (1H).
(wherein Y ¹ , Z, Y, A, and p are the same as above.)

Examples of the compound represented by formula (1H) include the compounds shown below.
(wherein a' is the same as above.)

In Preparation Method 7, the amount of the silane compound having a terminal thiol group to be used is preferably 1 to 5 mol, particularly 1 to 3 mol, per mol of the hydrocarbon terminal group-containing compound having an alkenyl group at its terminal.
The amount of the silane compound having an alkenyl group at its terminal is preferably 1 to 5 mol, particularly 1 to 3 mol, per mol of the hydrocarbon terminal group-containing compound having a thiol group at its terminal.

In Preparation Method 7, examples of the polymerization initiator include peroxide compounds such as azo compounds such as 2,2'-azobisisobutyronitrile and 2,2'-azobis(isobutyrate)dimethyl, diacyl peroxides such as benzoyl peroxide and lauroyl peroxide, dialkyl peroxides such as dicumyl peroxide and di-tert-butyl peroxide, peroxycarbonates such as diisopropyl peroxydicarbonate and bis(4-tert-butylcyclohexyl)peroxydicarbonate, and alkyl peresters such as t-butyl peroxyoctoate and tert-butyl peroxybenzoate.
The amount of the polymerization initiator used is preferably 0.01 to 3 mol, particularly preferably 0.1 to 1.5 mol, per mol of alkenyl group in the hydrocarbon terminal group-containing compound having an alkenyl group at the terminal or thiol group in the hydrocarbon terminal group-containing compound having a thiol group at the terminal.

In Preparation Method 7, a solvent can be used when carrying out the reaction. Examples of the solvent include the same solvents as those used in Preparation Method 1.
The amount of the solvent used is preferably 0 to 1,000 parts by mass, particularly 50 to 800 parts by mass, per 100 parts by mass of the hydrocarbon terminal group-containing compound having an alkenyl group at the end or the hydrocarbon terminal group-containing compound having a thiol group at the end.

In Preparation Method 7, the reaction conditions are preferably a temperature of 20 to 100°C, particularly 40 to 80°C, and a time of 0.5 to 72 hours, particularly 1 to 36 hours.

Other methods for preparing the hydrocarbon terminal group-containing compound represented by general formula (1) of the present invention include the following methods.
[Preparation method 8]
A hydrocarbon terminal group-containing compound represented by formula (1) (particularly a compound having a reactive group such as a hydrolyzable silyl group or a (meth)acryloyloxy group at the terminal via an amide bond) can be produced by reacting a hydrocarbon terminal group-containing compound having an acid halide at the terminal with a silane compound having an amino group at the terminal.

Here, examples of hydrocarbon terminal group-containing compounds having an acid halide at the terminal include compounds represented by the following formula (1I).
(In the formula, R, Z, Y, and m are the same as above. W is a halogen atom such as fluorine, chlorine, bromine, or iodine.)

Examples of the compound represented by formula (1I) include the compounds shown below.
(wherein x is the same as above).

Furthermore, examples of silane compounds having an amino group at the terminal include compounds represented by the following formula (1J).
(In the formula, Z, Y, A, and p are the same as above.)

Examples of the compound represented by formula (1J) include the compounds shown below.
(In the formula, a1 is independently the same as above.)

In Preparation Method 8, the amount of silane compound having an amino group at its terminal is preferably 1 to 5 mol, and more preferably 1 to 3 mol, per 1 mol of the hydrocarbon terminal group-containing compound having an acid halide at its terminal.

In Preparation Method 8, a base can be added to neutralize hydrogen chloride generated during the reaction. The base is not particularly limited, but examples include triethylamine, tributylamine, 4-dimethylaminopyridine, N-ethyldiisopropylamine, 1,4-diazabicyclo[2.2.2]octane, and 1,8-diazabicyclo[5.4.0]-7-undecene.
When a base is added, the amount used is preferably 1 to 3 mol, particularly 1 to 1.5 mol, per mol of the hydrocarbon terminal group-containing compound having an acid halide at the terminal.

A solvent can be used when carrying out the reaction in Preparation Method 8. Examples of the solvent include the same solvents as those in Preparation Method 1.
The amount of the solvent used is preferably 0 to 1,000 parts by mass, more preferably 50 to 400 parts by mass, per 100 parts by mass of the compound not having a terminal silyl group.

In Preparation Method 8, the reaction conditions are preferably a temperature of 20 to 100°C, particularly 20 to 70°C, and a time of 0.5 to 72 hours, particularly 1 to 36 hours.

[Surface treatment agent]
The present invention further provides a substantially fluorine-free surface treatment agent containing, as a main component, a non-fluorine-containing (i.e., fluorine-free) hydrocarbon terminal group-containing compound represented by the above formula (1). The surface treatment agent need only contain, as a main component, a hydrocarbon terminal group-containing compound represented by formula (1), and may also contain unreacted raw materials or reaction intermediates prior to the introduction of the reactive group of the hydrocarbon terminal group-containing compound represented by formula (1). Furthermore, the surface treatment agent preferably uses a hydrocarbon terminal group-containing compound in which the reactive group is a hydrolyzable silyl group. In this case, the surface treatment agent may contain a partial (hydrolyzed) condensate in which the hydrolyzable silyl group has been partially hydrolyzed and condensed in advance by a known method.

If necessary, the surface treatment agent may contain a hydrolysis condensation catalyst, such as an organic tin compound (dibutyltin dimethoxide, dibutyltin dilaurate, etc.), an organic titanium compound (tetra n-butyl titanate, tetra n-propyl titanate, etc.), an organic zirconium compound (tetra n-butyl zirconate, tetra n-propyl zirconate, etc.), an organic acid (acetic acid, methanesulfonic acid, carboxylic acid, etc.), an inorganic acid (hydrochloric acid, sulfuric acid, etc.), or an organic base (amine, trialkylamine, nitrogen-containing cyclic compound, etc.). Of these, acetic acid, tetra n-butyl titanate, dibutyltin dilaurate, etc. are particularly desirable.
When a hydrolysis and condensation catalyst is added, the amount added is a catalytic amount, which is usually 0.001 to 5 parts by mass, particularly 0.1 to 1 part by mass, per 100 parts by mass of the hydrocarbon terminal group-containing compound (and/or its partial (hydrolysis) condensate).

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

Two or more of the above solvents may be mixed, and it is preferable to uniformly dissolve the hydrocarbon terminal group-containing compound (and its partial (hydrolyzed) condensate). The optimal concentration of the hydrocarbon terminal group-containing compound (and its partial (hydrolyzed) condensate) to be dissolved in the solvent varies depending on the processing method, and any amount that is easy to weigh may be used. However, in the case of direct coating, a concentration of 0.01 to 100 parts by mass, and especially 0.05 to 30 parts by mass, per 100 parts by mass of the solvent and hydrocarbon terminal group-containing compound (and its partial (hydrolyzed) condensate) is preferred. In the case of vapor deposition processing, a concentration of 1 to 100 parts by mass, and especially 3 to 50 parts by mass, per 100 parts by mass of the solvent and hydrocarbon terminal group-containing compound (and its partial (hydrolyzed) condensate) is preferred. In either case, 100 parts by mass refers to direct coating without the use of a solvent.

The surface treatment agent of the present invention can be applied to a substrate by known methods such as brushing, dipping, spraying, and vapor deposition. The heating method during vapor deposition may be either resistance heating or electron beam heating, and is not particularly limited. The curing temperature varies depending on the curing method. For example, in the case of direct coating (brushing, dipping, spraying, etc.), it is preferably 25 to 200°C, particularly 25 to 150°C, for 30 minutes to 36 hours, particularly 1 to 24 hours. In the case of application by vapor deposition, it is desirable to apply it at a temperature in the range of 20 to 200°C for 1 to 24 hours. Curing may also be carried out under humid conditions.
Furthermore, when using a compound containing a hydrocarbon terminal group having a hydrolyzable silyl group, for example, if the compound is diluted in an organic solvent to which water has been added in advance and then spray-coated after hydrolysis, i.e., generation of Si—OH, then the compound will harden quickly after coating.

The thickness of the cured coating is selected appropriately depending on the type of substrate, but is typically 0.1 to 100 nm, and particularly 1 to 20 nm. The thickness can be measured, for example, by spectral reflectance measurement, X-ray reflectance measurement, spectroscopic ellipsometry measurement, or X-ray fluorescence measurement.

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, metal and its oxides, glass, plastic, ceramic, quartz, etc. _SiO2- treated glass and film are particularly preferred.

The surface treatment agent of the present invention can form a cured coating that has high levels of water repellency, slip resistance, dirt wipeability, and abrasion resistance.

[Goods]
Examples of articles that can be treated with the surface treatment agent of the present invention include optical articles and electronic components such as car navigation systems, mobile phones, smartphones, digital cameras, digital video cameras, PDAs, portable audio players, car audio, game machines, eyeglass lenses, camera lenses, lens filters, sunglasses, medical devices such as gastroscopes, copiers, PCs, liquid crystal displays, organic EL displays, plasma displays, touch panel displays, protective films, and anti-reflection films. The surface treatment agent of the present invention can impart scratch resistance to the above-mentioned articles, and is therefore particularly useful as a water-repellent layer for touch panel displays, anti-reflection films, eyeglass lenses, etc.

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 window glass or tempered glass of automobiles, trains, aircraft, etc., and headlamp covers; a water-repellent coating for exterior wall building materials; a stain-resistant coating for kitchen building materials; an anti-fouling coating for telephone booths and to prevent posters and graffiti; a coating that provides stain resistance to artworks, etc.; and a stain-resistant coating for compact discs, DVDs, etc.
The hydrocarbon terminal group-containing compound of the present invention can also be suitably used as a mold release agent for molds, a paint additive, a resin modifier, a flowability modifier or dispersibility modifier for inorganic fillers, or a lubricity improver for tapes, films, etc.

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 these examples. In the following examples, the molar amount of a compound is a value calculated by dividing the measured mass of the target compound by the molecular weight of the polymer identified by ¹ H-NMR analysis. Furthermore, the film thickness is a value measured by spectroscopic ellipsometry using a spectroscopic ellipsometer. The room temperature is 23°C.

[Synthesis Example 1]
In a reaction vessel, the following formula (A)
5.00 g (1.76× ¹⁰ mol) of the compound represented by the formula (I), 10.0 g of tetrahydrofuran, and 3.62 g (1.76× ¹⁰ mol) of 3-isocyanatopropyltrimethoxysilane were mixed and aged for 1 hour at 50° C. Thereafter, the solvent and unreacted materials were distilled off under reduced pressure to obtain 8.50 g of a product.

The resulting compound was confirmed by ¹ H-NMR to have a structure represented by the following formula (B):

[Synthesis Example 2]
5.00 g (1.86 × ¹⁰ mol) of octadecylamine, 10.00 g of tetrahydrofuran, and 3.81 g (1.86 × ¹⁰ mol) of 3-isocyanatopropyltrimethoxysilane were mixed in a reaction vessel and aged for 1 hour at 50° C. Thereafter, the solvent and unreacted materials were distilled off under reduced pressure to obtain 8.64 g of a product.

The resulting compound was confirmed by ¹ H-NMR to have a structure represented by the following formula (C):

[Synthesis Example 3]
5.00 g (1.85 × 10 ^-2 mol) of 1-octadecanol, 10.00 g of tetrahydrofuran, 3.79 g (1.85 × 10 ^-2 mol) of 3-isocyanatopropyltrimethoxysilane, and 1.03 × 10 ^-2 g (1.82 × 10 ^-5 mol) of tetrakis(2-ethylhexyl) orthotitanate were mixed in a reaction vessel and aged for 2 hours at 50° C. Thereafter, the solvent and unreacted materials were distilled off under reduced pressure to obtain 8.39 g of product.

The resulting compound was confirmed by ¹ H-NMR to have a structure represented by the following formula (D):

[Synthesis Example 4]
A reaction vessel was charged with the following formula (E):
5.00 g (1.65×10 ⁻² mol) of the compound represented by the formula (I), 20.00 g of tetrahydrofuran, 3.55 g (1.98×10 ⁻² mol) of 3-aminopropyltrimethoxysilane, and 2.50 g (2.48×10 ⁻² mol) of triethylamine were mixed and aged for 17 hours at 25° C. Thereafter, the solvent and unreacted materials were distilled off under reduced pressure to obtain 6.95 g of a product.

The resulting compound was confirmed by ¹ H-NMR to have a structure represented by the following formula (F):

[Synthesis Example 5]
5.00 g (1.98× ¹⁰ mol) of 1-octadecene, 40.00 g of toluene, 4.28 g (2.18× ¹⁰ mol) of 3-thiolpropyltrimethoxysilane, and 4.56× ¹⁰ mol (1.98× ¹⁰ mol) of dimethyl 2,2'-azobis(isobutyrate) were mixed in a reaction vessel and aged for 8 hours at 50° C. Thereafter, the solvent and unreacted materials were distilled off under reduced pressure to obtain 6.93 g of product.

The resulting compound was confirmed by ¹ H-NMR to have a structure represented by the following formula (G):

[Synthesis Example 6]
A reaction vessel was charged with the following formula (H):
5.00 g (1.69× ¹⁰ mol) of a compound represented by the formula (I), 5.00 g of toluene, 10.30 g (8.43× ¹⁰ mol) of trimethoxysilane, 2.60× ¹⁰ mol of a toluene solution of chloroplatinic acid/vinylsiloxane complex (containing 8.05× ¹⁰ mol as Pt), and 3.15× ¹⁰ mol (5.25× ¹⁰ mol) of acetic acid were mixed and aged for 24 hours at 80° C. Thereafter, the solvent and unreacted materials were distilled off under reduced pressure to obtain 6.96 g of product.

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

[Synthesis Example 7-1]
5.00 g (1.69 × 10 ^-2 mol) of octadecyl isocyanate, 10.00 g of tetrahydrofuran, 1.18 g (2.03 × 10 ^-2 mol) of allyl alcohol, and 1.03 × 10 ^-2 g (1.82 × 10 ^-5 mol) of tetrakis(2-ethylhexyl) orthotitanate were mixed in a reaction vessel and aged for 3 hours at 50° C. After treatment with activated carbon, the solvent and unreacted materials were distilled off under reduced pressure to obtain 5.27 g of product.

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

[Synthesis Example 7-2]
A reaction vessel was charged with the following formula (J):
5.00 g (1.41 × 10 ^-2 mol) of a compound represented by the formula (I), 5.00 g of toluene, 8.65 g (7.08 × 10 ^-2 mol) of trimethoxysilane, 2.60 × 10 ^-3 g of a toluene solution of chloroplatinic acid/vinylsiloxane complex (containing 8.05 × 10 ^-9 mol of Pt as simple substance), and 3.15 × 10 ^-3 g (5.25 × 10 ^-5 mol) of acetic acid were mixed and aged for 24 hours at 80° C. Thereafter, the solvent and unreacted materials were distilled off under reduced pressure to obtain 5.90 g of product.

The resulting compound was confirmed by ¹ H-NMR to have a structure represented by the following formula (K):

[Synthesis Example 8-1]
10.00 g (3.71 × ¹⁰ mol) of 1-octadecylamine, 200.00 g of 1,2-dichloroethane, 3.83 g (4.45 × ¹⁰ mol) of 3-butenoic acid, 9.95 g (5.19 × ¹⁰ mol) of 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride, and 9.10 × ¹⁰ mol (7.42 × ¹⁰ mol) of 4-dimethylaminopyridine were mixed in a reaction vessel and aged at 50°C for 24 hours. 10.00 g of 2M hydrochloric acid was added to the resulting solution, and the aqueous layer was extracted three times with 1,2-dichloroethane. The combined organic layer was washed with purified water and saturated brine and dried over magnesium sulfate. The mixture was then treated with activated carbon, and the solvent and unreacted materials were distilled off under reduced pressure to obtain 5.27 g of product.

The resulting compound was confirmed by ¹ H-NMR to have a structure represented by the following formula (L):

[Synthesis Example 8-2]
In a reaction vessel, the following formula (L)
5.00 g (1.48× ¹⁰ mol) of a compound represented by the formula (I), 5.00 g of toluene, ^9.04 g (7.40×10 mol) of trimethoxysilane, 2.60× ¹⁰ mol of a toluene solution of chloroplatinic acid/vinylsiloxane complex (containing 8.05× ¹⁰ mol as Pt), and 3.30× ¹⁰ mol (7.33× ¹⁰ mol) of formamide were mixed and aged for 24 hours at 80° C. Thereafter, the solvent and unreacted materials were distilled off under reduced pressure to obtain 5.93 g of product.

The resulting compound was confirmed by ¹ H-NMR to have a structure represented by the following formula (M):

[Synthesis Example 9]
A reaction vessel was charged with 5.00 g (1.98× ¹⁰ mol) of 1-octadecene, 38.50 g of toluene, 38.50 g (1.98× ¹⁰ mol) of 1,4-bis(dimethylsilyl)benzene, 2.60× ¹⁰ mol of a toluene solution of chloroplatinic acid/vinylsiloxane complex (containing 8.05× ¹⁰ mol of Pt), and 3.30× ¹⁰ mol (7.33×10 ^mol ) of formamide, and the mixture was aged for 1 hour at 80° C. The solvent and unreacted materials were then distilled off under reduced pressure, yielding 6.11 g of product.

The resulting compound was confirmed by ¹ H-NMR to have a structure represented by the following formula (N):

In a reaction vessel, the following formula (N)
5.00 g (1.12× ¹⁰ mol) of a compound represented by the formula (I), 5.00 g of toluene, 1.82 g (1.12× ¹⁰ mol) of allyltrimethoxysilane, 2.60× ¹⁰ mol of a toluene solution of chloroplatinic acid/vinylsiloxane complex (containing 8.05× ¹⁰ mol as Pt), and 3.15× ¹⁰ mol (5.25× ¹⁰ mol) of acetic acid were mixed and aged for 24 hours at 80° C. Thereafter, the solvent and unreacted materials were distilled off under reduced pressure to obtain 5.15 g of a product.

The resulting compound was confirmed by ¹ H-NMR to have a structure represented by the following formula (O).

[Synthesis Example 10]
A reaction vessel was charged with 5.00 g (1.98× ¹⁰ mol) of 1-octadecene, 38.50 g of toluene, 26.60 g (1.98× ¹⁰ mol) of tetramethyldisiloxane, 2.60× ¹⁰ mol of a toluene solution of chloroplatinic acid/vinylsiloxane complex (containing 8.05× ¹⁰ mol of Pt), and 3.30× ¹⁰ mol (7.33× ¹⁰ mol) of formamide, and the mixture was aged for 2 hours at 80° C. The solvent and unreacted materials were then distilled off under reduced pressure, yielding 6.33 g of product.

The resulting compound was confirmed by ¹ H-NMR to have a structure represented by the following formula (P):

A reaction vessel was charged with the following formula (P):
5.00 g (1.29× ¹⁰ mol) of a compound represented by the formula (I), 5.00 g of toluene, 2.09 g (1.29× ¹⁰ mol) of allyltrimethoxysilane, 2.60× ¹⁰ mol of a toluene solution of chloroplatinic acid/vinylsiloxane complex (containing 8.05× ¹⁰ mol as Pt), and 3.15× ¹⁰ mol (5.25× ¹⁰ mol) of acetic acid were mixed and aged for 24 hours at 80° C. Thereafter, the solvent and unreacted materials were distilled off under reduced pressure to obtain 5.31 g of a product.

The resulting compound was confirmed by ¹ H-NMR to have a structure represented by the following formula (Q).

[Synthesis Example 11]
A reaction vessel was charged with 5.00 g (1.98× ¹⁰ mol) of 1-octadecene, 38.50 g of toluene, 45.65 g (1.98× ¹⁰ mol) of bis(dimethylsilyl)octane, 2.60× ¹⁰ mol of a toluene solution of chloroplatinic acid/vinylsiloxane complex (containing 8.05× ¹⁰ mol of Pt), and 3.30× ¹⁰ mol (7.33× ¹⁰ mol) of formamide, and the mixture was aged for 24 hours at 80° C. The solvent and unreacted materials were then distilled off under reduced pressure, yielding 9.56 g of product.

The resulting compound was confirmed by ¹ H-NMR to have a structure represented by the following formula (R):

In a reaction vessel, the following formula (R)
5.00 g (1.04× ¹⁰ mol) of a compound represented by the formula (I), 5.00 g of toluene, 1.68 g (1.04× ¹⁰ mol) of allyltrimethoxysilane, 2.60× ¹⁰ mol of a toluene solution of chloroplatinic acid/vinylsiloxane complex (containing 8.05× ¹⁰ mol as Pt), and 3.15× ¹⁰ mol (5.25× ¹⁰ mol) of acetic acid were mixed and aged for 24 hours at 80° C. Thereafter, the solvent and unreacted materials were distilled off under reduced pressure to obtain 5.51 g of a product.

The resulting compound was confirmed by ¹ H-NMR to have a structure represented by the following formula (S):

[Synthesis Example 12]
A reaction vessel was charged with the following formula (T):
10.00 g (2.88 × 10 ^-2 mol) of a compound represented by the formula (I) and 50.00 g of toluene were mixed and stirred at 0°C. 12.50 g of a toluene solution of sodium bis(2-methoxyethoxy)aluminum hydride (containing 4.32 × 10 ^-2 mol of simple aluminum) was added dropwise thereto, and the mixture was aged at 0°C for 1 hour. 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 layer was washed with pure water and saturated saline, and dried over magnesium sulfate. The mixture was then powdered using activated carbon and Kyoward 500, and the solvent and unreacted materials were removed by distillation under reduced pressure, yielding 8.94 g of product.

The resulting compound was confirmed by ¹ H-NMR to have a structure represented by the following formula (U):

A reaction vessel was charged with the following formula (U):
5.00 g (1.60× ¹⁰ mol) of a compound represented by the formula (I), 5.00 g of toluene, 2.86 g (1.76× ¹⁰ mol) of allyltrimethoxysilane, 2.60× ¹⁰ mol of a toluene solution of chloroplatinic acid/vinylsiloxane complex (containing 8.05× ¹⁰ mol as Pt), and 3.15× ¹⁰ mol (5.25× ¹⁰ mol) of acetic acid were mixed and aged for 24 hours at 80° C. Thereafter, the solvent and unreacted materials were distilled off under reduced pressure to obtain 7.03 g of a product.

The resulting compound was confirmed by ¹ H-NMR to have a structure represented by the following formula (V).

[Synthesis Example 13-1]
5.00 g (1.69 × ¹⁰ mol) of octadecyl isocyanate, 10.00 g of tetrahydrofuran, 1.81 g (1.78 × ¹⁰ mol) of ethylene glycol monoallyl ether, and 1.03 × ¹⁰ g (1.82 × ¹⁰ mol) of tetrakis(2-ethylhexyl) orthotitanate were mixed in a reaction vessel and aged at room temperature for 24 hours. The solvent and unreacted materials were distilled off under reduced pressure, and the mixture was treated with activated carbon and the solvent was distilled off under reduced pressure to obtain 5.30 g of product.

The resulting compound was confirmed by ¹ H-NMR to have a structure represented by the following formula (W).

[Synthesis Example 13-2]
A reaction vessel was charged with the following formula (W):
5.00 g (1.26× ¹⁰ mol) of a compound represented by the formula (I), 5.00 g of toluene, ^7.68 g (6.29×10 mol) of trimethoxysilane, 2.60× ¹⁰ mol of a toluene solution of chloroplatinic acid/vinylsiloxane complex (containing 8.05× ¹⁰ mol as Pt), and 3.30× ¹⁰ mol (7.33× ¹⁰ mol) of formamide were mixed and aged for 24 hours at 80° C. Thereafter, the solvent and unreacted materials were distilled off under reduced pressure to obtain 3.78 g of product.

The resulting compound was confirmed by ¹ H-NMR to have a structure represented by the following formula (X).

[Synthesis Example 14-1]
5.00 g (1.69 × 10 ^-2 mol) of octadecyl isocyanate, 100.00 g of tetrahydrofuran, and 1.09 g (1.78 × 10 ^-2 mol) of 2-aminoethanol were mixed in a reaction vessel and aged for 1 hour at 50° C. Thereafter, the solvent and unreacted materials were distilled off under reduced pressure to obtain 5.96 g of a product.

The resulting compound was confirmed to have a structure represented by the following formula (Y) by ¹ H-NMR.

[Synthesis Example 14-2]
A reaction vessel was charged with the following formula (Y):
5.00 g (1.40 × 10 ^-2 mol) of a compound represented by the formula (I), 75.00 g of tetrahydrofuran, 4.65 × 10 ^-1 g (1.26 × 10 ^-3 mol) of tetrabutylammonium iodide, and 1.56 g (1.39 × 10 ^-2 mol) of potassium tert-butoxide were mixed and aged at 50°C for 1 hour. Then, 3.05 g (2.52 × 10 ^-2 mol) of allyl bromide 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 resulting solution, and the aqueous layer was extracted three times with toluene. The combined organic layer was washed with pure water and saturated saline and dried over magnesium sulfate. Then, the mixture was treated with activated carbon, and the solvent and unreacted materials were distilled off under reduced pressure, yielding 3.43 g of product.

The resulting compound was confirmed by ¹ H-NMR to have a structure represented by the following formula (Z):

[Synthesis Example 14-3]
A reaction vessel was charged with the following formula (Z):
5.00 g (1.26× ¹⁰ mol) of a compound represented by the formula (I), 5.00 g of toluene, ^7.69 g (6.29×10 mol) of trimethoxysilane, 2.60× ¹⁰ mol of a toluene solution of chloroplatinic acid/vinylsiloxane complex (containing 8.05× ¹⁰ mol as Pt), and 3.30× ¹⁰ mol (7.33× ¹⁰ mol) of formamide were mixed and aged for 24 hours at 80° C. Thereafter, the solvent and unreacted materials were distilled off under reduced pressure to obtain 6.50 g of product.

The resulting compound was confirmed by ¹ H-NMR to have a structure represented by the following formula (AA).

[Synthesis Example 15-1]
5.00 g (1.85 × 10 ^-2 mol) of octadecyl alcohol, 50.00 g of tetrahydrofuran, 6.80 × 10 ^-1 g (1.85 × 10 ^-3 mol) of tetrabutylammonium iodide, and 2.28 g (2.03 × 10 ^-2 mol) of potassium tert-butoxide were mixed in a reaction vessel and aged at 50°C for 1 hour. Then, 4.48 g (3.70 × 10 ^-2 mol) of allyl bromide was added dropwise, and the mixture was aged at 50°C for 24 hours. 2.00 g of 2M hydrochloric acid was added to the resulting solution, and the aqueous layer was extracted three times with toluene. The combined organic layer was washed with pure water and saturated saline and dried over magnesium sulfate. The mixture was then treated with activated carbon, and the solvent and unreacted materials were distilled off under reduced pressure to obtain 5.51 g of product.

The resulting compound was confirmed to have a structure represented by the following formula (AB) by ¹ H-NMR.

[Synthesis Example 15-2]
A reaction vessel was charged with the following formula (AB):
5.00 g (1.61× ¹⁰ mol) of a compound represented by the formula (I), 5.00 g of toluene, 9.84 g ( ^8.05 ×10 mol) of trimethoxysilane, 2.60× ¹⁰ mol of a toluene solution of chloroplatinic acid/vinylsiloxane complex (containing 8.05× ¹⁰ mol as Pt), and 3.30× ¹⁰ mol (7.33× ¹⁰ mol) of formamide were mixed and aged for 24 hours at 80° C. Thereafter, the solvent and unreacted materials were distilled off under reduced pressure to obtain 5.73 g of a product.

The resulting compound was confirmed by ¹ H-NMR to have a structure represented by the following formula (AC).

[Synthesis Example 16-1]
5.00 g (1.53 × 10 ^-2 mol) of behenyl alcohol, 50.00 g of tetrahydrofuran, 5.65 × 10 ^-1 g (1.53 × 10 ^-3 mol) of tetrabutylammonium iodide, and 2.23 g (1.99 × 10 ^-2 mol) of potassium tert-butoxide were mixed in a reaction vessel and aged at 50°C for 1 hour. Then, 3.70 g (3.06 × 10 ^-2 mol) of allyl bromide 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 resulting solution, and the aqueous layer was extracted three times with toluene. The combined organic layer was washed with pure water and saturated saline and dried over magnesium sulfate. The mixture was then treated with activated carbon, and the solvent and unreacted materials were distilled off under reduced pressure to obtain 5.79 g of product.

The resulting compound was confirmed to have a structure represented by the following formula (AD) by ¹ H-NMR.

[Synthesis Example 16-2]
A reaction vessel was charged with the following formula (AD):
5.00 g (1.36× ¹⁰ mol) of a compound represented by the formula (I), 5.00 g of toluene, ^8.32 g (6.81×10 mol) of trimethoxysilane, 2.60× ¹⁰ mol of a toluene solution of chloroplatinic acid/vinylsiloxane complex (containing 8.05× ¹⁰ mol as Pt), and 3.30× ¹⁰ mol (7.33× ¹⁰ mol) of formamide were mixed and aged for 24 hours at 80° C. Thereafter, the solvent and unreacted materials were distilled off under reduced pressure to obtain 6.25 g of product.

The resulting compound was confirmed to have a structure represented by the following formula (AE) by ¹ H-NMR.

[Synthesis Example 17-1]
5.00 g (1.85 × 10 ^-2 mol) of octadecyl alcohol, 50.00 g of tetrahydrofuran, 6.80 × 10 ^-1 g (1.85 × 10 ^-3 mol) of tetrabutylammonium iodide, and 2.28 g (2.03 × 10 ^-2 mol) of potassium tert-butoxide were mixed in a reaction vessel and aged at 50°C for 1 hour. 5.06 g (3.70 × 10 ^-2 mol) of 2-methylallylbromide was then added dropwise, and the mixture was aged at 50°C for 24 hours. 10.00 g of 2M 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 saline and dried over magnesium sulfate. The mixture was then treated with activated carbon, and the solvent and unreacted materials were distilled off under reduced pressure to obtain 5.38 g of product.

The resulting compound was confirmed to have a structure represented by the following formula (AF) by ¹ H-NMR.

[Synthesis Example 17-2]
A reaction vessel was charged with a compound represented by the following formula (AF):
5.00 g (1.54× ¹⁰ mol) of a compound represented by the formula (I), 5.00 g of toluene, 18.81 g (1.54× ¹⁰ mol) of trimethoxysilane, 2.60× ¹⁰ mol of a toluene solution of chloroplatinic acid/vinylsiloxane complex (containing 8.05× ¹⁰ mol as Pt), and 3.15× ¹⁰ mol (5.25× ¹⁰ mol) of acetic acid were mixed and aged for 24 hours at 80° C. Thereafter, the solvent and unreacted materials were distilled off under reduced pressure to obtain 4.81 g of product.

The resulting compound was confirmed by ¹ H-NMR to have a structure represented by the following formula (AG).

[Synthesis Example 18-1]
5.00 g (1.14 × 10 ^-2 mol) of myricyl alcohol, 50.00 g of tetrahydrofuran, 4.21 × 10 ^-1 g (1.14 × 10 ^-3 mol) of tetrabutylammonium iodide, and 1.92 g (1.71 × 10 ^-2 mol) of potassium tert-butoxide were mixed in a reaction vessel and aged at 50°C for 1 hour. Then, 3.08 g (2.28 × 10 ^-2 mol) of 2-methylallyl bromide 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 resulting solution, and the aqueous layer was extracted three times with toluene. The combined organic layer was washed with pure water and saturated saline and dried over magnesium sulfate. The mixture was then treated with activated carbon, and the solvent and unreacted materials were distilled off under reduced pressure to obtain 4.49 g of product.

The resulting compound was confirmed to have a structure represented by the following formula (AH) by ¹ H-NMR.

[Synthesis Example 18-2]
A reaction vessel was charged with the following formula (AH):
5.00 g (1.01 × ¹⁰ mol) of a compound represented by the formula (I), 5.00 g of toluene, 8.33 g (5.07 × ¹⁰ mol) of triethoxysilane, and 2.60 × 10 ³ g of a toluene solution of chloroplatinic acid/vinylsiloxane complex (containing 8.05 × ¹⁰ mol as Pt) were mixed and aged for 24 hours at 80° C. Thereafter, the solvent and unreacted materials were distilled off under reduced pressure to obtain 5.33 g of product.

The resulting compound was confirmed to have a structure represented by the following formula (AI) by ¹ H-NMR.

[Synthesis Example 19-1]
5.00 g (4.90 × 10 ^-2 mol) of ethylene glycol monoallyl ether, 10.00 g of 1,2-dichloroethane, and 9.80 g (5.14 × 10 ^-2 mol) of tosyl chloride were mixed in a reaction vessel and stirred at 0°C. 5.20 g (5.14 × 10 ^-2 mol) of triethylamine was added dropwise, and the mixture was aged at 25°C for 24 hours. 50 mL of saturated aqueous sodium bicarbonate solution was added to the resulting solution, followed by phase separation. The organic layer was washed with 50 mL of pure water and 50 mL of 2 M hydrochloric acid. This washing process was repeated twice. The organic layer was dried over magnesium sulfate, and the solvent and unreacted materials were removed by distillation under reduced pressure to obtain 8.84 g of product.

The resulting compound was confirmed to have a structure represented by the following formula (AJ) by ¹ H-NMR.

[Synthesis Example 19-2]
A reaction vessel was charged with a compound represented by the following formula (AJ):
5.00 g (1.95×10 ⁻² mol) of the compound represented by the formula (I) was mixed with 50.00 g of acetone and 2.54 g (2.93×10 ⁻² mol) of lithium bromide, and the mixture was aged for 24 hours at 25° C. The resulting solution was distilled to obtain 2.25 g of a product.

The resulting compound was confirmed to have a structure represented by the following formula (AK) by ¹ H-NMR.

[Synthesis Example 19-3]
5.00 g (1.85×10 ⁻² mol) of octadecyl alcohol, 50.00 g of tetrahydrofuran, 6.80×10 ⁻¹ g (1.85×10 ⁻³ mol) of tetrabutylammonium iodide, and 2.28 g (2.03×10 ⁻² mol) of potassium tert-butoxide were mixed in a reaction vessel and aged at 50° C. for 1 hour.
6.11 g (3.70 × 10 ^-2 mol) of a compound represented by the formula (I) was added dropwise to the resulting solution, and the mixture was aged at 50°C for 24 hours. 2.00 g of 2M 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 saline, and dried over magnesium sulfate. Then, the mixture was treated with activated carbon, and the solvent and unreacted materials were distilled off under reduced pressure, yielding 5.25 g of product.

The resulting compound was confirmed to have a structure represented by the following formula (AL) by ¹ H-NMR.

[Synthesis Example 19-4]
In a reaction vessel, a compound represented by the following formula (AL)
5.00 g (1.41× ¹⁰ mol) of a compound represented by the formula (I), 5.00 g of toluene, ^23.16 g (1.41×10 mol) of triethoxysilane, 2.60× ¹⁰ mol of a toluene solution of chloroplatinic acid/vinylsiloxane complex (containing 8.05× ¹⁰ mol as Pt), and 3.30× ¹⁰ mol (7.33× ¹⁰ mol) of formamide were mixed and aged for 24 hours at 80° C. Thereafter, the solvent and unreacted materials were distilled off under reduced pressure to obtain 4.90 g of product.

The resulting compound was confirmed by ¹ H-NMR to have a structure represented by the following formula (AM).

[Synthesis Example 20]
In a reaction vessel, a compound of the following formula (AL) obtained in the same manner as in Synthesis Example 19-3 was placed.
5.00 g (1.41 × 10 ^-2 mol) of the compound represented by the formula (I), 40.00 g of toluene, 3.05 g (1.55 × 10 ^-2 mol) of 3-thiolpropyltrimethoxysilane, and 3.25 × 10 ^-1 g (1.41 × 10 ^-3 mol) of dimethyl 2,2'-azobis(isobutyrate) were mixed and aged for 8 hours at 50° C. Thereafter, the solvent and unreacted materials were distilled off under reduced pressure, yielding 5.67 g of product.

The resulting compound was confirmed to have a structure represented by the following formula (AN) by ¹ H-NMR.

[Synthesis Example 21-1]
25.00 g (1.55 × ¹⁰ mol) of 2-(tert-butoxycarbonylamino)-1-ethanol, 50.00 g of 1,2-dichloroethane, and 31.03 g (1.63 × ¹⁰ mol) of tosyl chloride were mixed in a reaction vessel and stirred at 0°C. 16.49 g (1.63 × ¹⁰ mol) of triethylamine was added dropwise, and the mixture was aged at 25°C for 24 hours. 50 mL of saturated aqueous sodium bicarbonate solution was added to the resulting solution, followed by phase separation. The organic layer was washed with 50 mL of pure water and 50 mL of 2 M hydrochloric acid. This washing process was repeated twice. The organic layer was dried over magnesium sulfate, and the solvent and unreacted materials were removed by distillation under reduced pressure to obtain 37.65 g of product.

The resulting compound was confirmed to have a structure represented by the following formula (AO) by ¹ H-NMR.

In a reaction vessel, a compound represented by the following formula (AO)
37.00 g (1.17×10 ⁻¹ mol) of a compound represented by the formula (I) above, 250.00 g of acetone, and 15.28 g (1.76×10 ⁻¹ mol) of lithium bromide were mixed and aged for 24 hours at 25° C. The resulting solution was distilled to obtain 11.60 g of a product.

The resulting compound was confirmed by ¹ H-NMR to have a structure represented by the following formula (AP).

[Synthesis Example 21-2]
5.00 g (1.85×10 ⁻² mol) of octadecyl alcohol, 50.00 g of tetrahydrofuran, 6.80×10 ⁻¹ g (1.85×10 ⁻³ mol) of tetrabutylammonium iodide, and 2.28 g (2.03×10 ⁻² mol) of potassium tert-butoxide were mixed in a reaction vessel and aged at 50° C. for 1 hour.
8.29 g (3.70 × 10 ^-2 mol) of a compound represented by the formula (I) was added dropwise to the resulting solution, 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 saline, and dried over magnesium sulfate. Then, the mixture was treated with activated carbon, and the solvent and unreacted materials were distilled off under reduced pressure, yielding 7.65 g of product.

The resulting compound was confirmed to have a structure represented by the following formula (AQ) by ¹ H-NMR.

In a reaction vessel, a compound represented by the following formula (AQ)
7.00 g (1.69×10 ⁻² mol) of the compound represented by the formula (I), 70.00 g of 1,2-dichloroethane, and 19.29 g (1.69×10 ⁻¹ mol) of trifluoroacetic acid were mixed and aged for 24 hours at 25° C. The solvent and unreacted materials were distilled off under reduced pressure to obtain 5.13 g of a product.

The resulting compound was confirmed by ¹ H-NMR to have a structure represented by the following formula (AR):

[Synthesis Example 21-3]
A reaction vessel was charged with the following formula (AR):
5.00 g (1.59 × 10 ^-2 mol) of the compound represented by the formula (I), 10.0 g of tetrahydrofuran, and 3.27 g (1.59 × 10 ^-2 mol) of 3-isocyanatopropyltrimethoxysilane were mixed and aged for 1 hour at 50° C. Thereafter, the solvent and unreacted materials were distilled off under reduced pressure to obtain 8.25 g of a product.

The resulting compound was confirmed to have a structure represented by the following formula (AS) by ¹ H-NMR.

[Synthesis Example 22-1]
10.00 g (3.38 × 10 ^-2 mol) of octadecyl isocyanate, 10.00 g of tetrahydrofuran, 5.72 g (3.55 × 10 ^-2 mol) of 2-(tert-butoxycarbonylamino)-1-ethanol, and 1.03 × 10 ^-2 g (1.82 × 10 ^-5 mol) of tetrakis(2-ethylhexyl) orthotitanate were mixed in a reaction vessel and aged for 24 hours at 50° C. Thereafter, the solvent and unreacted materials were distilled off under reduced pressure to obtain 13.52 g of product.

The resulting compound was confirmed to have a structure represented by the following formula (AT) by ¹ H-NMR.

A reaction vessel was charged with the following formula (AT):
10.00 g (2.19×10 ⁻² mol) of the compound represented by the formula (I) above, 50.00 g of 1,2-dichloroethane, and 24.97 g (2.19×10 ⁻¹ mol) of trifluoroacetic acid were mixed and aged for 24 hours at 25° C. The solvent and unreacted materials were distilled off under reduced pressure to obtain 7.34 g of a product.

The resulting compound was confirmed by ¹ H-NMR to have a structure represented by the following formula (AU).

[Synthesis Example 22-2]
A reaction vessel was charged with the following formula (AU):
5.00 g (1.40 × 10 ^-2 mol) of the compound represented by the formula (I), 10.0 g of tetrahydrofuran, and 2.88 g (1.40 × 10 ^-2 mol) of 3-isocyanatopropyltrimethoxysilane were mixed and aged for 24 hours at 50° C. Thereafter, the solvent and unreacted materials were distilled off under reduced pressure to obtain 7.25 g of a product.

The resulting compound was confirmed to have a structure represented by the following formula (AV) by ¹ H-NMR.

[Synthesis Example 23-1]
5.00 g (1.69 × ¹⁰ mol) of octadecyl isocyanate, 10.00 g of tetrahydrofuran, and 2.85 g (1.78 × ¹⁰ mol) of N-(tert-butoxycarbonyl)-1,2-diaminoethane were mixed in a reaction vessel and aged for 1 hour at 50° C. Thereafter, the solvent and unreacted materials were distilled off under reduced pressure to obtain 7.63 g of a product.

The resulting compound was confirmed by ¹ H-NMR to have a structure represented by the following formula (AW).

A reaction vessel was charged with a compound represented by the following formula (AW):
7.00 g (1.54×10 ⁻² mol) of the compound represented by the formula (I), 70.00 g of 1,2-dichloroethane, and 17.51 g (1.54×10 ⁻¹ mol) of trifluoroacetic acid were mixed and aged for 24 hours at 25° C. The solvent and unreacted materials were distilled off under reduced pressure to obtain 5.26 g of a product.

The resulting compound was confirmed to have a structure represented by the following formula (AX) by ¹ H-NMR.

[Synthesis Example 23-2]
A reaction vessel was charged with the following formula (AX):
5.00 g (1.41 × 10 ^-2 mol) of the compound represented by the formula (I), 50.0 g of tetrahydrofuran, and 2.89 g (1.41 × 10 ^-2 mol) of 3-isocyanatopropyltrimethoxysilane were mixed and aged for 24 hours at 50° C. Thereafter, the solvent and unreacted materials were distilled off under reduced pressure to obtain 7.65 g of a product.

The resulting compound was confirmed to have a structure represented by the following formula (AY) by ¹ H-NMR.

[Synthesis Example 24-1]
In a reaction vessel, a compound of the following formula (L) obtained in the same manner as in Synthesis Example 8-1 was added.
5.00 g (1.48 × 10 ^-2 mol) of the compound represented by the formula (I) and 50.00 g of tetrahydrofuran were mixed and stirred at 0°C. 2.96 mL (2.96 × 10 ^-2 mol) of a 1 M diisobutylaluminum hydride n-hexane solution was added thereto, and the mixture was aged at 25°C for 8 hours. While the resulting solution was cooled to 0°C, 20.00 g of pure water and 20.00 g of methanol were added, and the mixture was separated. The aluminum salt was filtered and washed with 20.00 g of methanol. The combined organic layer was washed with pure water and saturated brine, and dried over magnesium sulfate. The mixture was then treated with activated carbon, and the solvent was distilled off, yielding 3.73 g of product.

The resulting compound was confirmed to have a structure represented by the following formula (AZ) by ¹ H-NMR.

[Synthesis Example 24-2]
A reaction vessel was charged with a compound represented by the following formula (AZ):
3.00 g (9.27 × ¹⁰ mol) of a compound represented by the formula (I), 5.00 g of toluene, 7.62 g (4.64 × ¹⁰ mol) of triethoxysilane, and 2.60 × ¹⁰ mol of a toluene solution of a chloroplatinic acid/vinylsiloxane complex (containing 8.05 × ¹⁰ mol as Pt) were mixed and aged for 24 hours at 80° C. Thereafter, the solvent and unreacted materials were distilled off under reduced pressure to obtain 3.84 g of a product.

The resulting compound was confirmed to have a structure represented by the following formula (BA) by ¹ H-NMR.

[Synthesis Example 25-1]
In a reaction vessel, a compound of the following formula (AL) obtained in the same manner as in Synthesis Example 19-3 was placed.
5.00 g (1.41 × 10 ^-2 mol) of a compound represented by the formula (I) and 10.00 g of tetrahydrofuran were mixed and stirred at 0°C. 36.7 mL of a 9-borabicyclo[3.3.1]nonane/tetrahydrofuran solution (containing 2.24 g (1.83 × 10 ^-2 mol) of 9-borabicyclo[3.3.1]nonane) was added dropwise thereto, and the mixture was aged at 25°C for 6 hours. 15 mL of 30% by mass aqueous hydrogen peroxide and 90 mL (9.43 × 10 ^-2 mol) of saturated aqueous sodium hydrogen carbonate solution were then added, and the mixture was aged at 25°C for 1 hour. A saturated aqueous sodium thiosulfate solution was added to the resulting solution to terminate the reaction. The layers were separated, and the aqueous layer was extracted three times with ethyl acetate. The combined organic layers were dried over magnesium sulfate. The solvent and unreacted materials were distilled off under reduced pressure, and the mixture was washed with toluene to obtain 3.36 g of product.

The resulting compound was confirmed to have a structure represented by the following formula (BB) by ¹ H-NMR.

[Synthesis Example 25-2]
A reaction vessel was charged with the following formula (BB):
3.00 g (8.05× ¹⁰ mol) of a compound represented by the formula (I), 6.00 g of tetrahydrofuran, 1.65 g (8.05× ¹⁰ mol) of 3-isocyanatopropyltrimethoxysilane, and 1.03×10 ² g (1.82× ¹⁰ mol) of tetrakis(2-ethylhexyl) orthotitanate were mixed and aged for 24 hours at 50° C. Thereafter, the solvent and unreacted materials were distilled off under reduced pressure to obtain 3.86 g of a product.

The resulting compound was confirmed by ¹ H-NMR to have a structure represented by the following formula (BC).

[Synthesis Example 26-1]
5.00 g (1.69 × 10 ^-2 mol) of octadecyl isocyanate, 10.00 g of tetrahydrofuran, 1.75 g (2.03 × 10 ^-2 mol) of 4-penten-1ol, and 1.03 × 10 ^-2 g (1.82 × 10 ^-5 mol) of tetrakis(2-ethylhexyl) orthotitanate were mixed in a reaction vessel and aged for 3 hours at 50° C. After treatment with activated carbon, the solvent and unreacted materials were distilled off under reduced pressure to obtain 6.08 g of product.

The resulting compound was confirmed to have a structure represented by the following formula (BD) by ¹ H-NMR.

[Synthesis Example 26-2]
A reaction vessel was charged with the following formula (BD):
5.00 g (1.31 × 10 ^-2 mol) of a compound represented by the formula (I), 5.00 g of toluene, 8.00 g (6.55 × 10 ^-2 mol) of trimethoxysilane, 2.60 × 10 ^-3 g of a toluene solution of chloroplatinic acid/vinylsiloxane complex (containing 8.05 × 10 ^-9 mol of Pt as simple substance), and 3.15 × 10 ^-3 g (5.25 × 10 ^-5 mol) of acetic acid were mixed and aged for 24 hours at 80° C. Thereafter, the solvent and unreacted materials were distilled off under reduced pressure to obtain 5.21 g of product.

The resulting compound was confirmed by ¹ H-NMR to have a structure represented by the following formula (BE).

[Synthesis Example 27-1]
5.00 g (1.69 × 10 ^-2 mol) of octadecyl isocyanate, 10.00 g of tetrahydrofuran, 1.46 g (2.03 × 10 ^-2 mol) of 4-butene-1ol, and 1.03 × 10 ^-2 g (1.82 × 10 ^-5 mol) of tetrakis(2-ethylhexyl) orthotitanate were mixed in a reaction vessel and aged for 3 hours at 50° C. After treatment with activated carbon, the solvent and unreacted materials were distilled off under reduced pressure to obtain 6.03 g of product.

The resulting compound was confirmed by ¹ H-NMR to have a structure represented by the following formula (BF):

[Synthesis Example 27-2]
A reaction vessel was charged with a compound represented by the following formula (BF)
5.00 g (1.36× ¹⁰ mol) of a compound represented by the formula (I), 5.00 g of toluene, 8.31 g (6.80× ¹⁰ mol) of trimethoxysilane, 2.60× ¹⁰ mol of a toluene solution of chloroplatinic acid/vinylsiloxane complex (containing 8.05× ¹⁰ mol as Pt), and 3.15× ¹⁰ mol (5.25× ¹⁰ mol) of acetic acid were mixed and aged for 24 hours at 80° C. Thereafter, the solvent and unreacted materials were distilled off under reduced pressure to obtain 4.46 g of a product.

The resulting compound was confirmed to have a structure represented by the following formula (BG) by ¹ H-NMR.

[Synthesis Example 28-1]
5.00 g (1.69 × 10 ^-2 mol) of octadecyl isocyanate, 10.00 g of tetrahydrofuran, 3.46 g (2.03 × 10 ^-2 mol) of 10-undecen-1-ol, and 1.03 × 10 ^-2 g (1.82 × 10 ^-5 mol) of tetrakis(2-ethylhexyl) orthotitanate were mixed in a reaction vessel and aged for 3 hours at 50° C. After treatment with activated carbon, the solvent and unreacted materials were distilled off under reduced pressure, and the crude product was washed with methanol to obtain 7.08 g of product.

The resulting compound was confirmed by ¹ H-NMR to have a structure represented by the following formula (BH).

[Synthesis Example 28-2]
A reaction vessel was charged with the following formula (BH):
2.00 g (4.29× ¹⁰ mol) of a compound represented by the formula (I), 2.00 g of toluene, 5.24 g (4.29× ¹⁰ mol) of trimethoxysilane, 2.60× ¹⁰ mol of a toluene solution of chloroplatinic acid/vinylsiloxane complex (containing 8.05× ¹⁰ mol as Pt), and 3.15× ¹⁰ mol (5.25× ¹⁰ mol) of acetic acid were mixed and aged for 24 hours at 80° C. Thereafter, the solvent and unreacted materials were distilled off under reduced pressure to obtain 1.84 g of product.

The resulting compound was confirmed to have a structure represented by the following formula (BI) by ¹ H-NMR.

[Synthesis Example 29]
A reaction vessel was charged with the following formula (BJ):
5.00 g (1.46 × 10 ^-2 mol) of the compound represented by the formula (I), 40.00 g of toluene, 4.07 g (1.75 × 10 ^-2 mol) of trimethoxy(7-octen-1-yl)silane, and 4.56 × 10 ^-1 g (1.98 × 10 ^-3 mol) of dimethyl 2,2'-azobis(isobutyrate) were mixed and aged for 8 hours at 50° C. Thereafter, the solvent and unreacted materials were distilled off under reduced pressure to obtain 6.55 g of product.

The resulting compound was confirmed to have a structure represented by the following formula (BK) by ¹ H-NMR.

[Synthesis Example 30]
A reaction vessel was charged with the following formula (H):
5.00 g (1.69 × 10 ^-2 mol) of a compound represented by the formula (I), 5.00 g of toluene, 6.87 g (5.07 × 10 ^-2 mol) of trichlorosilane, and 2.60 × 10 ^-3 g of a toluene solution of chloroplatinic acid/vinylsiloxane complex (containing 8.05 × 10 ^-9 mol of Pt as simple substance) were mixed and aged at 60°C for 24 hours. The solvent and unreacted materials were then distilled off under reduced pressure. The resulting product was mixed with 15.00 g of toluene and aged for 6 hours at room temperature while bubbling ammonia gas (ammonia gas used at a rate of 40 cc/min). The mixture was then filtered, and the solvent and unreacted materials were distilled off under reduced pressure to obtain 4.21 g of product.

The resulting compound was confirmed to have a structure represented by the following formula (BL) by ¹ H-NMR.

[Synthesis Example 31]
A reaction vessel was charged with a compound of the following formula (Z) obtained in the same manner as in Synthesis Example 14-2.
1.00 g (2.52 × 10 ^-3 mol) of a compound represented by the formula (I), 1.00 g of toluene, 1.02 g (7.56 × 10 ^-3 mol) of trichlorosilane, and 7.54 × 10 ^-3 g of a toluene solution of chloroplatinic acid/vinylsiloxane complex (containing 2.33 × 10 ^-8 mol of Pt as simple substance) were mixed and aged at 60°C for 24 hours. The solvent and unreacted materials were then distilled off under reduced pressure. The resulting product was mixed with 3.00 g of toluene and aged for 6 hours at room temperature while bubbling ammonia gas (ammonia gas used at a rate of 40 cc/min). The mixture was then filtered, and the solvent and unreacted materials were distilled off under reduced pressure to obtain 7.90 × 10 ^-1 g of product.

The resulting compound was confirmed by ¹ H-NMR to have a structure represented by the following formula (BM).

[Synthesis Example 32-1]
5.00 g (3.22 × ¹⁰ mol) of octyl isocyanate, 10.00 g of tetrahydrofuran, 3.45 g (3.38 × ¹⁰ mol) of ethylene glycol monoallyl ether, and 1.03 × ¹⁰ g (1.82 × ¹⁰ mol) of tetrakis(2-ethylhexyl) orthotitanate were mixed in a reaction vessel and aged at room temperature for 24 hours. The solvent and unreacted materials were distilled off under reduced pressure, and the mixture was treated with activated carbon and the solvent was distilled off under reduced pressure to obtain 7.96 g of product.

The resulting compound was confirmed by ¹ H-NMR to have a structure represented by the following formula (BN).

[Synthesis Example 32-2]
In a reaction vessel, a compound represented by the following formula (BN)
5.00 g (1.94× ¹⁰ mol) of a compound represented by the formula (I), 5.00 g of toluene, ^11.87 g (9.71×10 mol) of trimethoxysilane, 2.60× ¹⁰ mol of a toluene solution of chloroplatinic acid/vinylsiloxane complex (containing 8.05× ¹⁰ mol as Pt), and 3.30× ¹⁰ mol (7.33× ¹⁰ mol) of formamide were mixed and aged for 24 hours at 80° C. Thereafter, the solvent and unreacted materials were distilled off under reduced pressure to obtain 5.45 g of product.

The resulting compound was confirmed by ¹ H-NMR to have a structure represented by the following formula (BO):

[Synthesis Example 33]
A reaction vessel was charged with the following formula (BP):
53.17 g (1.98×10 ⁻¹ mol) of a compound represented by the formula (I), 5.00 g (1.98×10 ⁻² mol) of 1-octadecene, 38.50 g of toluene, 2.60×10 ⁻³ g of a toluene solution of chloroplatinic acid/vinylsiloxane complex (containing 8.05×10 ⁻⁹ mol as simple Pt), and 3.30×10 ⁻³ g (7.33×10 ⁻⁵ mol) of formamide were mixed and aged for 1 hour at 80° C. Thereafter, the solvent and unreacted materials were distilled off under reduced pressure, yielding 9.70 g of product.

The resulting compound was confirmed to have a structure represented by the following formula (BQ) by ¹ H-NMR.

[Synthesis Example 33]
In a reaction vessel, a compound represented by the following formula (BQ)
5.00 g (9.60× ¹⁰ mol) of a compound represented by the formula (I), 5.00 g of toluene, 1.56 g (9.60× ¹⁰ mol) of allyltrimethoxysilane, 2.60× ¹⁰ mol of a toluene solution of chloroplatinic acid/vinylsiloxane complex (containing 8.05× ¹⁰ mol as Pt), and 3.15× ¹⁰ mol (5.25× ¹⁰ mol) of acetic acid were mixed and aged for 24 hours at 80° C. Thereafter, the solvent and unreacted materials were distilled off under reduced pressure to obtain 6.36 g of product.

The resulting compound was confirmed to have a structure represented by the following formula (BR) by ¹ H-NMR.

[Synthesis Example 34-1]
3.38 g (2.79 × 10 ^-2 mol) of allyl bromide, 3.63 g (1.86 × 10 ^-2 mol) of p-toluenesulfonylmethyl isocyanide, 46.5 mL (60.5 g) of 1-butyl-3-methylimidazolium bromide, and 7.72 g (5.59 × 10 ^-2 mol) of potassium carbonate were mixed in a reaction vessel and aged at 50°C for 24 hours. 5.00 g (1.86 × 10 ^-2 mol) of octadecanal was then added dropwise, and the mixture was aged at 25°C for 24 hours. 200 mL of pure water was added to the resulting solution, and the aqueous layer was extracted three times with toluene. The combined organic layer was washed with pure water and saturated saline and dried over magnesium sulfate. The mixture was then treated with activated carbon, and the solvent and unreacted materials were distilled off under reduced pressure. The resulting crude product was washed with methanol, yielding 4.78 g of product.

The resulting compound was confirmed by ¹ H-NMR to have a structure represented by the following formula (BS).

[Synthesis Example 34-2]
A reaction vessel was charged with the following formula (BS):
4.00 g (1.11× ¹⁰ mol) of a compound represented by the formula (I), 4.00 g of toluene, 13.52 g ( ^1.11 ×10 mol) of trimethoxysilane, 2.60× ¹⁰ mol of a toluene solution of chloroplatinic acid/vinylsiloxane complex (containing 8.05× ¹⁰ mol as Pt), and 3.30× ¹⁰ mol (7.33× ¹⁰ mol) of formamide were mixed and aged for 24 hours at 80° C. Thereafter, the solvent and unreacted materials were distilled off under reduced pressure to obtain 4.08 g of a product.

The resulting compound was confirmed to have a structure represented by the following formula (BT) by ¹ H-NMR.

[Synthesis Example 35-1]
A reaction vessel was charged with a compound represented by the following formula (BU):
5.00 g (1.69 × 10 ^-2 mol) of a compound represented by the following formula (BV):
1.34 g (2.03 × 10 ^-2 mol) of a compound represented by the formula (I) and 70 mL (58 g) of a mixed solution of tert-butanol and water (4:1 volume ratio) were mixed and stirred at 25°C. 3.35 g (1.69 × 10 ^-2 mol) of sodium ascorbate and 4.22 g (1.69 × 10 ^-2 mol) of copper (II) sulfate pentahydrate were mixed thereto and aged at 50°C for 24 hours. 100 mL of saturated aqueous ammonium chloride solution was added to the resulting solution, and the aqueous layer was extracted three times with ethyl acetate. The combined organic layer was washed with pure water and saturated saline and dried over magnesium sulfate. The mixture was then treated with activated carbon, and the solvent and unreacted materials were distilled off under reduced pressure. The resulting crude product was washed with methanol, yielding 4.95 g of product.

The resulting compound was confirmed to have a structure represented by the following formula (BW) by ¹ H-NMR.

[Synthesis Example 35-2]
A reaction vessel was charged with the following formula (BW):
4.00 g (1.11×10 ⁻² mol) of a compound represented by the formula (I), 4.00 g of toluene, 13.52 g (1.11×10 ⁻¹ mol) of trimethoxysilane, 2.60×10 ⁻³ g of a toluene solution of chloroplatinic acid/vinylsiloxane complex (containing 8.05×10 ⁻⁹ mol of Pt as simple substance), and 3.30×10 ⁻³ g (7.33×10 ⁻⁵ mol) of formamide were mixed and aged for 24 hours at 80° C. Thereafter, the solvent and unreacted materials were distilled off under reduced pressure to obtain 4.01 g of product.

The resulting compound was confirmed to have a structure represented by the following formula (BX) by ¹ H-NMR.

[Synthesis Example 36]
A reaction vessel was charged with a compound of the following formula (AX) obtained in the same manner as in Synthesis Example 23-2.
5.00 g (1.41 × 10 ^-2 mol) of a compound represented by the formula (I), 10.00 g of tetrahydrofuran, and 2.08 g (1.47 × 10 ^-2 mol) of Karenz AOI (2-(acryloyloxy)ethyl isocyanate) were mixed and aged for 24 hours at 50° C. Thereafter, the solvent and unreacted materials were distilled off under reduced pressure to obtain 6.65 g of a product.

The resulting compound was confirmed to have a structure represented by the following formula (BY) by ¹ H-NMR.

[Synthesis Example 37]
A reaction vessel was charged with a compound of the following formula (Y) obtained in the same manner as in Synthesis Example 14-1.
5.00 g (1.40 × ¹⁰ mol) of a compound represented by the formula (I), 25.00 g of toluene, and 2.36 g (1.54 × ¹⁰ mol) of phosphorus oxychloride were mixed and aged at room temperature for 24 hours. 20.00 g of water was added to the resulting solution, and the mixture was aged at room temperature for 1 hour. Thereafter, the aqueous layer was removed by a separation operation, and the solvent and unreacted materials were distilled off under reduced pressure to obtain 5.20 g of product.

The resulting compound was confirmed by ¹ H-NMR to have a structure represented by the following formula (BZ):

[Synthesis Example 38]
A reaction vessel was charged with the following formula (CA):
5.00 g (1.42 × 10 ^-2 mol) of a compound represented by the formula (I), 5.00 g of toluene, 8.66 g (7.09 × 10 ^-2 mol) of trimethoxysilane, 2.60 × 10 ^-3 g of a toluene solution of chloroplatinic acid/vinylsiloxane complex (containing 8.05 × 10 ^-9 mol of Pt as simple substance), and 3.15 × 10 ^-3 g (5.25 × 10 ^-5 mol) of acetic acid were mixed and aged for 24 hours at 80° C. Thereafter, the solvent and unreacted materials were distilled off under reduced pressure to obtain 6.20 g of product.

The resulting compound was confirmed to have a structure represented by the following formula (CB) by ¹ H-NMR.

[Synthesis Example 39]
A reaction vessel was charged with the following formula (BJ):
5.00 g (1.46×10 ⁻² mol) of the compound represented by the formula (I), 40.00 g of toluene, 2.38 g (1.61×10 ⁻² mol) of vinyltrimethoxysilane, and 4.56×10 ⁻¹ g (1.98×10 ⁻³ mol) of dimethyl 2,2′-azobis(isobutyrate) were mixed and aged for 8 hours at 50° C. Thereafter, the solvent and unreacted materials were distilled off under reduced pressure to obtain 6.98 g of product.

The resulting compound was confirmed by ¹ H-NMR to have a structure represented by the following formula (CC).

[Synthesis Example 40-1]
100.00 g (5.87 × 10 ^-1 mol) of 10-undecen-1-ol, 500.00 g of tetrahydrofuran, 21.68 g (5.87 × 10 ^-2 mol) of tetrabutylammonium iodide, and 98.86 g (8.81 × 10 ^-1 mol) of potassium tert-butoxide were mixed in a reaction vessel and aged at 50°C for 1 hour. Then, 194.82 g (8.81 × 10 ^-1 mol) of 1-bromodecane was added dropwise, and the mixture was aged at 25°C for 24 hours. 400.00 g of saturated aqueous ammonium chloride solution was added to the resulting solution, and the aqueous layer was extracted three times with toluene. The combined organic layer was washed with pure water and saturated saline and dried over magnesium sulfate. The mixture was then treated with activated carbon and Kyoward 500, and the solvent and unreacted materials were distilled off under reduced pressure, yielding 81.55 g of product.

The resulting compound was confirmed to have a structure represented by the following formula (DA) by ¹ H-NMR.

[Synthesis Example 40-2]
A reaction vessel was charged with the following formula (DA):
65.00 g (2.09 × 10 ^-1 mol) of the compound represented by the formula (I), 50.00 g of toluene, 45.20 g (2.30 × 10 ^-1 mol) of 3-thiolpropyltrimethoxysilane, and 4.81 g (2.09 × 10 ^-2 mol) of dimethyl 2,2'-azobis(isobutyrate) were mixed and aged for 3 hours at 75°C. Thereafter, the solvent and unreacted materials were distilled off under reduced pressure to obtain 105.91 g of product.

The resulting compound was confirmed to have a structure represented by the following formula (DB) by ¹ H-NMR.

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

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

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

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

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

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

[Example 7]
The compound obtained in Synthesis Example 7-2 was dissolved in butyl acetate to a concentration of 0.2% by mass to prepare a surface treatment agent.

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

[Example 9]
The compound obtained in Synthesis Example 9 was dissolved in isononane to a concentration of 0.1% by mass to prepare a surface treatment agent.

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

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

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

[Example 13]
The compound obtained in Synthesis Example 13-2 was dissolved in isooctane to a concentration of 0.1% by mass to prepare a surface treatment agent.

[Example 14]
The compound obtained in Synthesis Example 14-3 was dissolved in dibutyl ether to a concentration of 0.2% by mass to prepare a surface treatment agent.

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

[Example 16]
The compound obtained in Synthesis Example 16-2 was dissolved in dibutyl ether to a concentration of 0.1% by mass to prepare a surface treatment agent.

[Example 17]
The compound obtained in Synthesis Example 17-2 was dissolved in butyl acetate to a concentration of 0.2% by mass to prepare a surface treatment agent.

[Example 18]
The compound obtained in Synthesis Example 19-4 was dissolved in dibutyl ether to a concentration of 0.1% by mass to prepare a surface treatment agent.

[Example 19]
The compound obtained in Synthesis Example 21-3 was dissolved in dibutyl ether to a concentration of 0.2% by mass to prepare a surface treatment agent.

[Example 20]
The compound obtained in Synthesis Example 22-2 was dissolved in toluene to a concentration of 0.2% by mass to prepare a surface treatment agent.

[Example 21]
The compound obtained in Synthesis Example 23-2 was dissolved in propylene glycol monomethyl ether acetate to a concentration of 0.1% by mass to prepare a surface treatment agent.

[Example 22]
The compound obtained in Synthesis Example 25-2 was dissolved in isooctane to a concentration of 0.2% by mass to prepare a surface treatment agent.

[Example 23]
The compound obtained in Synthesis Example 28-2 was dissolved in butyl acetate to a concentration of 0.1% by mass to prepare a surface treatment agent.

[Example 24]
The compound obtained in Synthesis Example 29 was dissolved in dibutyl ether to a concentration of 0.2% by mass to prepare a surface treatment agent.

[Example 25]
The compound obtained in Synthesis Example 32-2 was dissolved in dibutyl ether to a concentration of 0.1% by mass to prepare a surface treatment agent.

[Example 26]
The compound obtained in Synthesis Example 38 was dissolved in dibutyl ether to a concentration of 0.2% by mass to prepare a surface treatment agent.

[Example 27]
The compound obtained in Synthesis Example 39 was dissolved in dibutyl ether to a concentration of 0.2% by mass to prepare a surface treatment agent.

[Example 28]
The compound obtained in Synthesis Example 40-2 was dissolved in dibutyl ether to a concentration of 0.2% by mass to prepare a surface treatment agent.

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

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

[Comparative Example 3]
No surface treatment agents.

Preparation of Surface Treatment Agents and Formation of Cured Coatings Surface treatment agents were prepared as in the above Examples and Comparative Examples. Each surface treatment agent was spray-coated onto glass (Gorilla, manufactured by Corning Incorporated) whose outermost surface had been coated with _SiO2 to a thickness of 10 nm, and cured for 1 hour in an atmosphere of 80°C and 80% relative humidity, and then for a further 12 hours in an atmosphere of 25°C and 50% relative humidity to form a cured coating with a thickness of 3 to 5 nm.

The glass on which the cured coating was formed was evaluated for water repellency, slipperiness, ease of wiping, and abrasion resistance using the methods described below. The same evaluations were carried out for Comparative Example 3, which was a glass (Gorilla manufactured by Corning Incorporated) that had not been subjected to any surface treatment and had been coated with _SiO2 to a thickness of 10 nm on its outermost surface.

Evaluation of Water Repellency The contact angle (water repellency) of the cured coating with water was measured for the glass on which the cured coating was formed using a contact angle meter, Drop Master (manufactured by Kyowa Interface Science Co., Ltd.) (droplet: 2 μl, temperature: 25° C., relative humidity: 40%). A contact angle (water repellency) of 85° or more was rated as good. The results (initial water contact angle) are shown in Table 1.
In the initial stage, both the Example and Comparative Examples showed good water repellency.

Evaluation of Slipperiness The glass having the cured coating formed thereon prepared as described above was evaluated for its slipperiness by measuring the coefficient of dynamic friction against nonwoven fabric using the method described below. The coefficient of dynamic friction of the glass having the cured coating formed thereon against nonwoven fabric was measured in accordance with ASTM D1894 using a surface property measuring instrument Type: 14FW (manufactured by Shinto Scientific Co., Ltd.) under conditions of a load of 100 gf and a tensile speed of 500 mm/min. A slipperiness of 0.25 or less was rated as good. The results (coefficient of dynamic friction) are shown in Table 1.
[Slipperiness evaluation conditions]
Load: 100gf
Stroke: 100mm
Contact area: 1 x 3 cm ²
Nonwoven fabric: BEMCOT (manufactured by Asahi Kasei Corporation)

Evaluation of Dirt Wiping Ability A 2 cm straight line was drawn on the glass surface on which the cured coating prepared above was formed using a Hi-Mackey (manufactured by Zebra), the ink was allowed to dry, and the ink was wiped off with tissue paper. The number of times the ink was rubbed until it was wiped off was evaluated according to the following criteria. Dirt wiping ability was rated as good when rated A or B. The results are shown in Table 1.
[Evaluation criteria for dirt wiping ability]
A: Rubbed 4 times or less B: Rubbed 5 times or more C: Ink cannot be wiped off

Evaluation of Abrasion Resistance: The glass on which the cured coating prepared above was formed was rubbed every 500 times using a rubbing tester (manufactured by Shinto Scientific Co., Ltd.) under the following conditions, and the contact angle (water repellency) of the cured coating with water was measured in the same manner as above. The number of times the contact angle became less than 80° was counted and used to evaluate abrasion resistance. The test environmental conditions were 25°C and a relative humidity of 40%. A sample that became less than 80° 2,000 times or more was rated as good. The results (the number of times the water contact angle became less than 80°) are shown in Table 1.
[Steel wool abrasion resistance test conditions]
Steel wool: Bonster #0000
Contact area: ^1cm2
Travel distance (one way): 40 mm
Traveling speed: 4,800mm/min Load: 500gf/1cm ²

The cured coatings of the surface treatment agents of Examples 1 to 28 exhibited water repellency and dirt wiping properties due to the improved mobility of the molecular chains caused by the hydrocarbon chains having 1 to 60 carbon atoms at the molecular chain terminals of the compounds used. Furthermore, the intermolecular interactions and molecular mobility were improved by the presence of 1 to 3 linking functional groups in the molecular chains of the compounds used, resulting in good slip properties and abrasion resistance.
The cured coating of the surface treatment agent of Comparative Example 1 exhibited water repellency due to the presence of a hydrocarbon chain having 1 to 60 carbon atoms at the molecular chain terminal of the compound used, but the absence of a linking functional group in the molecular chain of the compound used resulted in poor slip properties and abrasion resistance. The cured coating of the surface treatment agent of Comparative Example 2 exhibited high water repellency and dirt wipeability due to the presence of a fluorohydrocarbon chain at the molecular chain terminal of the compound used, but the absence of a linking functional group in the molecular chain of the compound used resulted in poor slip properties and abrasion resistance. Comparative Example 3 was a glass substrate that did not use a surface treatment agent, but since it was not surface treated, neither of these properties were observed, and the effects of the Examples could be confirmed.
As described above, with the surface treatment agents of the Examples, a cured coating film having high levels of water repellency, slipperiness, dirt wipeability, and abrasion resistance could be obtained by spray coating, which is an example of wet coating.

[Example 29]
The compound obtained in Synthesis Example 1 was dissolved in toluene to a concentration of 20% by mass to prepare a surface treatment agent.

[Example 30]
The compound obtained in Synthesis Example 2 was dissolved in dibutyl ether to a concentration of 20% by mass to prepare a surface treatment agent.

[Example 31]
The compound obtained in Synthesis Example 3 was dissolved in butyl acetate to a concentration of 10% by mass to prepare a surface treatment agent.

[Example 32]
The compound obtained in Synthesis Example 4 was dissolved in isooctane to a concentration of 10% by mass to prepare a surface treatment agent.

[Example 33]
The compound obtained in Synthesis Example 5 was dissolved in a 50/50 mixed solution of hexane/isooctane to a concentration of 30% by mass to prepare a surface treatment agent.

[Example 34]
The compound obtained in Synthesis Example 6 was dissolved in dibutyl ether to a concentration of 50% by mass to prepare a surface treatment agent.

[Example 35]
The compound obtained in Synthesis Example 7-2 was dissolved in butyl acetate to a concentration of 20% by mass to prepare a surface treatment agent.

[Example 36]
The compound obtained in Synthesis Example 8-2 was dissolved in dibutyl ether to a concentration of 10% by mass to prepare a surface treatment agent.

[Example 37]
The compound obtained in Synthesis Example 9 was dissolved in isooctane to a concentration of 10% by mass to prepare a surface treatment agent.

[Example 38]
The compound obtained in Synthesis Example 10 was dissolved in isooctane to a concentration of 10% by mass to prepare a surface treatment agent.

[Example 39]
The compound obtained in Synthesis Example 11 was dissolved in dibutyl ether to a concentration of 20% by mass to prepare a surface treatment agent.

[Example 40]
The compound obtained in Synthesis Example 12 was dissolved in isononane to a concentration of 20% by mass to prepare a surface treatment agent.

[Example 41]
The compound obtained in Synthesis Example 13-2 was dissolved in butyl acetate to a concentration of 20% by mass to prepare a surface treatment agent.

[Example 42]
The compound obtained in Synthesis Example 14-3 was dissolved in dibutyl ether to a concentration of 20% by mass to prepare a surface treatment agent.

[Example 43]
The compound obtained in Synthesis Example 15-2 was dissolved in dibutyl ether to a concentration of 20% by mass to prepare a surface treatment agent.

[Example 44]
The compound obtained in Synthesis Example 16-2 was dissolved in butyl acetate to a concentration of 20% by mass to prepare a surface treatment agent.

[Example 45]
The compound obtained in Synthesis Example 17-2 was dissolved in hexane to a concentration of 10% by mass to prepare a surface treatment agent.

[Example 46]
The compound obtained in Synthesis Example 19-4 was dissolved in dibutyl ether to a concentration of 20% by mass to prepare a surface treatment agent.

[Example 47]
The compound obtained in Synthesis Example 21-3 was dissolved in dibutyl ether to a concentration of 30% by mass to prepare a surface treatment agent.

[Example 48]
The compound obtained in Synthesis Example 22-2 was dissolved in toluene to a concentration of 20% by mass to prepare a surface treatment agent.

[Example 49]
The compound obtained in Synthesis Example 23-2 was dissolved in dibutyl ether to a concentration of 20% by mass to prepare a surface treatment agent.

[Example 50]
The compound obtained in Synthesis Example 25-2 was dissolved in isooctane to a concentration of 10% by mass to prepare a surface treatment agent.

[Example 51]
The compound obtained in Synthesis Example 28-2 was dissolved in dibutyl ether to a concentration of 20% by mass to prepare a surface treatment agent.

[Example 52]
The compound obtained in Synthesis Example 29 was dissolved in toluene to a concentration of 20% by mass to prepare a surface treatment agent.

[Example 53]
The compound obtained in Synthesis Example 32-2 was dissolved in dibutyl ether to a concentration of 20% by mass to prepare a surface treatment agent.

[Example 54]
The compound obtained in Synthesis Example 38 was dissolved in dibutyl ether to a concentration of 20% by mass to prepare a surface treatment agent.

[Example 55]
The compound obtained in Synthesis Example 39 was dissolved in dibutyl ether to a concentration of 20% by mass to prepare a surface treatment agent.

[Example 56]
The compound obtained in Synthesis Example 40-2 was dissolved in dibutyl ether to a concentration of 20% by mass to prepare a surface treatment agent.

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

[Comparative Example 5]
The compound represented by the formula (B') was dissolved in toluene to a concentration of 10% by mass to prepare a surface treatment agent.

[Comparative Example 6]
No surface treatment agents.

Preparation of Surface Treatment Agents and Formation of Cured Coatings Surface treatment agents were prepared as in the above Examples and Comparative Examples. Each surface treatment agent was vacuum-deposited (treatment conditions: pressure: 2.0 × ^10-2 Pa, heating temperature: 700°C) onto glass (Gorilla, manufactured by Corning Incorporated) whose outermost surface had been coated with _SiO2 to a thickness of 10 nm. The coating was 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 coating with a thickness of 3 to 5 nm.

The glass on which the cured coating was formed was evaluated for water repellency, slipperiness, ease of wiping, and abrasion resistance using the methods described below. The same evaluations were carried out for Comparative Example 6, which was a glass without surface treatment, but with a 10 nm thick _SiO2 coating on the outermost surface (Gorilla, manufactured by Corning Incorporated).

Evaluation of Water Repellency The contact angle (water repellency) of the cured coating with water was measured for the glass on which the cured coating was formed using a contact angle meter, Drop Master (manufactured by Kyowa Interface Science Co., Ltd.) (droplet: 2 μl, temperature: 25° C., relative humidity: 40%). A contact angle (water repellency) of 85° or more was rated as good. The results (initial water contact angle) are shown in Table 2.
In the initial stage, both the Example and Comparative Examples showed good water repellency.

Evaluation of Slipperiness The glass having the cured coating formed thereon prepared as described above was evaluated for its slipperiness by measuring the coefficient of dynamic friction against nonwoven fabric using the method described below. The coefficient of dynamic friction of the glass having the cured coating formed thereon against nonwoven fabric was measured in accordance with ASTM D1894 using a surface property measuring instrument Type: 14FW (manufactured by Shinto Scientific Co., Ltd.) under conditions of a load of 100 gf and a tensile speed of 500 mm/min. A slipperiness of 0.25 or less was rated as good. The results (coefficient of dynamic friction) are shown in Table 2.
[Slipperiness evaluation conditions]
Load: 100gf
Stroke: 100mm
Contact area: 1 x 3 cm ²
Nonwoven fabric: BEMCOT (manufactured by Asahi Kasei Corporation)

Evaluation of Dirt Wiping Ability A 2 cm straight line was drawn on the glass surface on which the cured coating prepared above was formed using a Hi-Mackey (manufactured by Zebra), the ink was allowed to dry, and the line was wiped off with tissue paper. The number of times the ink was rubbed until it was wiped off was evaluated according to the following criteria. Dirt wiping ability was rated as good when rated A or B. The results are shown in Table 2.
[Evaluation criteria for dirt wiping ability]
A: Rubbed 4 times or less B: Rubbed 5 times or more C: Ink cannot be wiped off

Evaluation of Abrasion Resistance: The glass on which the cured coating prepared above was formed was rubbed every 500 times using a rubbing tester (manufactured by Shinto Scientific Co., Ltd.) under the following conditions, and the contact angle (water repellency) of the cured coating with water was measured in the same manner as above. The number of times the contact angle became less than 80° was counted and used to evaluate abrasion resistance. The test environmental conditions were 25°C and a relative humidity of 40%. A sample that became less than 80° 2,000 times or more was rated as good. The results (the number of times the water contact angle became less than 80°) are shown in Table 2.
[Steel wool abrasion resistance test conditions]
Steel wool: Bonster #0000
Contact area: ^1cm2
Travel distance (one way): 40 mm
Traveling speed: 4,800mm/min Load: 500gf/1cm ²

The cured coatings of the surface treatment agents of Examples 29 to 56 exhibited water repellency and dirt wiping properties due to the improved mobility of the molecular chains caused by the hydrocarbon chains having 1 to 60 carbon atoms at the molecular chain terminals of the compounds used. Furthermore, the intermolecular interactions and molecular mobility were improved by the presence of 1 to 3 linking functional groups in the molecular chains of the compounds used, resulting in good slip properties and abrasion resistance.
The cured coating of the surface treatment agent of Comparative Example 4 exhibited water repellency due to the presence of a hydrocarbon chain having 1 to 60 carbon atoms at the molecular chain terminal of the compound used, but the absence of a linking functional group in the molecular chain of the compound used resulted in poor slip properties and abrasion resistance. The cured coating of the surface treatment agent of Comparative Example 5 exhibited high water repellency and dirt wiping properties due to the presence of a fluorohydrocarbon chain at the molecular chain terminal of the compound used, but the absence of a linking functional group in the molecular chain of the compound used resulted in poor slip properties and abrasion resistance. Comparative Example 6 was a glass substrate that did not use a surface treatment agent, but since it was not surface treated, it did not have any of these properties, and the effects of the Examples could be confirmed.
As described above, with the surface treatment agents of the Examples, even when vapor-deposited coating was used, it was possible to obtain cured coatings that exhibited high levels of water repellency, slipperiness, dirt-wiping ability, and abrasion resistance.

Claims (10)

The following general formula (1)
(In the formula, R is a monovalent hydrocarbon group having 1 to 60 carbon atoms, which may be linear, branched, or cyclic, or a combination thereof; Z is independently a divalent linking functional group containing at least one atom selected from oxygen atoms, nitrogen atoms, sulfur atoms, and silicon atoms; Y is independently a divalent hydrocarbon group having 1 to 30 carbon atoms, which may be linear, branched, or cyclic, or a combination thereof; A is a monovalent reactive group; and k is an integer of 1 to 3.)
A hydrocarbon terminal group-containing compound represented by the formula: A in the formula (1) is represented by the following general formula (2):
(In the formula, ^R1 is independently an alkyl group having 1 to 4 carbon atoms or a phenyl group, X is independently a hydroxyl group or a hydrolyzable group, and n is an integer of 1 to 3.)
Or the following general formula (3)
(wherein n″ is a number from 0 to 3, and n′ is (3−n″)/2.)
2. The hydrocarbon terminal group-containing compound according to claim 1, wherein the hydroxyl group-containing silyl group or hydrolyzable silyl group is represented by the formula: The hydrocarbon terminal group-containing compound according to claim 2, wherein in formula (2), 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. The hydrocarbon terminal group-containing compound according to claim 1, wherein in formula (1), R is a monovalent hydrocarbon group having 3 to 32 carbon atoms, which may be linear, branched, or cyclic, or a combination thereof. The hydrocarbon terminal group-containing compound according to claim 1, wherein in formula (1), Z is independently a divalent group selected from an ether group, a carbonyl (ketone) group, an ester group, a carbonate group, a thioether group, a sulfinyl group, a sulfonyl group, a thioester group, a thiocarbonate group, a thiocarbamate group, an amino group, an amide group, a carbamate group, a urea group, a divalent nitrogen-containing heterocyclic group, a diorganosilylene group, and a divalent organopolysiloxane residue that is linear having 2 to 10 silicon atoms or branched or cyclic having 3 to 10 silicon atoms. In the formula (1), Y independently represents the following general formula (4):
(In the formula, ^R2 independently represents a monovalent hydrocarbon group having 1 to 10 carbon atoms, which may be linear, branched, or cyclic, or a combination thereof. ^R3 independently represents a divalent cyclic hydrocarbon group having 3 to 10 carbon atoms, which may have a substituent. a represents an integer of 0 to 30, b represents an integer of 0 to 15, c represents an integer of 0 to 10, and d represents an integer of 0 to 6, and 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. The repeating units shown in parentheses with a, b, c, and d may be bonded randomly.)
2. The hydrocarbon terminal group-containing compound according to claim 1, wherein the hydrocarbon terminal group is a group represented by the formula: In the formula (1), k is 1, and R is represented by the following general formula (5):
(In the formula, ^R4 is a methyl group, a cyclic alkyl group, or a phenyl group. ^R3 is independently a divalent cyclic hydrocarbon group having 3 to 10 carbon atoms, which may 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 formula (5) is 60 or less. The repeating units shown in parentheses with y and h may be bonded randomly.)
2. The hydrocarbon terminal group-containing compound according to claim 1, wherein the hydrocarbon terminal group is a monovalent hydrocarbon group represented by the formula: The hydrocarbon terminal group-containing compound according to claim 1, wherein k in formula (1) is 2 or 3. A surface treatment agent containing the hydrocarbon terminal group-containing compound according to any one of claims 1 to 8. An article whose surface has been treated with the surface treatment agent described in claim 9.