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

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

[0001] The present invention relates to a hydrocarbon terminal group-containing compound, and more particularly to a hydrocarbon terminal group-containing compound, particularly an alkyl terminal group-containing compound, that forms a coating film that is excellent in water repellency, slipperiness, dirt-wiping properties, and abrasion resistance; a surface treatment agent containing the compound; and an article that has been surface-treated with the surface treatment agent.

[0002] In recent years, the use of touch panels in displays, such as smartphones and in-vehicle displays, has accelerated. However, touch panels have exposed screens, which are often directly touched by fingers or cheeks, making them susceptible to sebum and other contaminants. Therefore, there is an increasing demand for technologies that make display surfaces less susceptible to fingerprints and easier to clean, thereby improving appearance and visibility. The development of materials that can meet these demands is highly desirable. Because touch panel displays are particularly susceptible to fingerprints, the surface of these displays is particularly susceptible to fingerprints, making it desirable to provide a water- and oil-repellent layer. However, while conventional water- and oil-repellent layers offer high water- and oil-repellent properties and excellent wipeability, they lack sufficient abrasion resistance.

[0003] In general, fluoropolyether group-containing compounds have very low surface free energy and therefore have water and oil repellency, chemical resistance, lubricity, release properties, antifouling properties, etc. Utilizing these properties, they are widely used industrially as water and oil repellent and antifouling agents for paper and textiles, lubricants for magnetic recording media, oil repellents for precision instruments, release agents, cosmetics, protective films, etc. However, these properties also mean that they are non-sticky and non-adhesive to other substrates, and even if they can be applied to the surface of a substrate, it has been difficult to adhere the coating to it.

[0004] 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 one molecule. The hydrolyzable silyl group undergoes a self-condensation reaction in the presence of moisture in the air to form a coating. The hydrolyzable silyl group chemically and physically bonds with the surface of glass, metal, or the like, resulting in a durable, strong coating.

[0005] Thus, compositions have been disclosed that use fluoropolyether group-containing polymers in which hydrolyzable silyl groups have been introduced into fluoropolyether group-containing compounds, which can form coatings that easily adhere to substrate surfaces and have water and oil repellency, chemical resistance, lubricity, releasability, antifouling properties, and the like on the substrate surfaces (Patent Documents 1 to 6: JP-T-2008-534696A, JP-T-2008-537557A, JP-A-2012-072272A, JP-A-2012-157856A, JP-A-2013-136833A, and JP-A-2015-199906A).

[0006] However, fluorine-based compounds are difficult to decompose in nature and tend to accumulate in the natural environment, so there is a growing demand for the development of surface protection agents for non-fluorine-based materials.

[0007] Therefore, WO 2019 / 82583 (Patent Document 7) proposes a surface treatment agent that does not use a fluorine group. However, the abrasion resistance of the surface treatment agent is not sufficient to withstand harsh usage environments.

[0008] Japanese Patent Publication No. 2008-534696 Japanese Patent Publication No. 2008-537557 Japanese Patent Application Laid-Open No. 2012-072272 Japanese Patent Application Laid-Open No. 2012-157856 Japanese Patent Application Laid-Open No. 2013-136833 Japanese Patent Application Laid-Open No. 2015-199906 International Publication No. 2019 / 82583

[0009] The present invention has been made in view of the above circumstances, and aims to provide a non-fluorine-based (i.e., no fluorine atoms in the molecule) hydrocarbon terminal group-containing compound capable of forming a cured coating film that is excellent in water repellency, slipperiness, dirt wipeability, and abrasion resistance; a substantially non-fluorine-based surface treatment agent containing the compound; and an article that has been surface-treated with the surface treatment agent.

[0010] As a result of intensive research to achieve the above object, the present inventors have found 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 material, intermolecular interactions and molecular chain mobility are improved, and a surface treatment agent containing the 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.

[0011] Therefore, the present invention provides the following hydrocarbon terminal group-containing compound, surface treatment agent, and article: [1] A compound represented by the following general formula (1): (wherein 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.) [2] A compound having a hydrocarbon terminal group represented by the following general formula (2): (In the formula, R 1 are independently an alkyl group or a phenyl group having 1 to 4 carbon atoms, X is independently a hydroxyl group or a hydrolyzable group, and n is an integer of 1 to 3.) or a group represented by the following general formula (3): (wherein n" is a number from 0 to 3, and n' is (3-n") / 2). [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 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. [6] In the formula (1), Y is independently a divalent group selected from the following general formula (4): (In the formula, R 2 R is independently a monovalent hydrocarbon group having 1 to 10 carbon atoms, which may be linear, branched, or cyclic, or a combination thereof. 3 are independently divalent cyclic hydrocarbon groups having 3 to 10 carbon atoms, each optionally having a substituent. a is an integer from 0 to 30, b is an integer from 0 to 15, c is an integer from 0 to 10, and d is an integer from 0 to 6, and the sum of a, b, c, and d is an integer such that the 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. [7] The hydrocarbon terminal group-containing compound according to any one of [1] to [5], wherein in formula (1), k is 1 and R is a group represented by the following general formula (5): (In the formula, R 4is a methyl group, a cyclic alkyl group, or a phenyl group. 3 are independently optionally substituted divalent cyclic hydrocarbon groups having 3 to 10 carbon atoms. y is an integer of 0 or greater, 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 k is 2 or 3 in formula (1). [8] The hydrocarbon terminal group-containing compound according to any one of [1] to [7], wherein k is 2 or 3 in 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].

[0012] An article that has been surface-treated with a surface treatment agent containing the hydrocarbon terminal group-containing compound of the present invention has excellent water repellency, slipperiness, dirt wiping properties, and abrasion resistance.

[0013] [Hydrocarbon Terminal Group-Containing Compound] The hydrocarbon terminal group-containing compound of the present invention is represented by the following general formula (1). (In the formula, R is a monovalent hydrocarbon group having 1 to 60 carbon atoms, 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.)

[0014] The hydrocarbon terminal group-containing compound of the present invention is characterized in that it has a monovalent hydrocarbon group (hydrocarbon terminal group, R in formula (1)) at a molecular chain terminal, 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 has a reactive group (substrate-adhering group, A in formula (1)) that exhibits substrate adhesion at the other molecular chain terminal, and the linking group connecting the hydrocarbon terminal group and the substrate-adhering group is a divalent linking group (-(Z-Y)k- in formula (1)) that contains a divalent linking functional group (Z in formula (1)) that contains at least one atom selected from oxygen, nitrogen, sulfur, and silicon atoms. 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 chain is determined by the linking functional group, and the hydrocarbon chains on the surface of the cured coating tend to be oriented in one direction due to intermolecular interactions between the hydrocarbon chains and between the linking functional groups. Therefore, the cured coating of the surface treatment agent containing the compound has excellent water repellency, slip resistance, dirt wipeability, and abrasion resistance.

[0015] 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.)

[0016] As R, the following are more preferred. (In the formula, R 4 is a methyl group, a cyclic alkyl group, or a phenyl group. 3 are independently optionally substituted divalent cyclic hydrocarbon groups having 3 to 10 carbon atoms. 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.

[0017] 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.

[0018] In the above formula (5), R 3 R are independently divalent cyclic hydrocarbon groups having 3 to 10 carbon atoms, which may have a substituent. 3 Examples of the divalent cyclic hydrocarbon group represented by the formula (I) include the following: (In the formula, R 6 is an alkyl group having 1 to 4 carbon atoms, such as a methyl group or an ethyl group.

[0019] In the above formula (1), Z is a linking group that, together with Y, links the hydrocarbon chain (R in formula (1)) at the molecular chain terminal to the reactive group (A in formula (1)), and is a divalent linking functional group that independently contains at least one atom selected from an oxygen atom, a nitrogen atom, a sulfur atom, and a silicon atom, and is a characteristic component of the present invention. The divalent linking functional group containing at least one selected from oxygen, nitrogen, sulfur, and silicon atoms is preferably an ether group, 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 (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, with ether groups, thioether groups, carbamate groups, and urea groups being particularly preferred.

[0020] 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, R 5are 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.

[0021] Here, R 5 are 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, which may be linear, branched, cyclic, or a combination thereof, 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. 5 is preferably a hydrogen atom, a methyl group, or a phenyl group.

[0022] 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, R 2 R is independently a monovalent hydrocarbon group having 1 to 10 carbon atoms, which may be linear, branched, or cyclic, or a combination thereof. 3 are independently optionally substituted divalent cyclic hydrocarbon groups having 3 to 10 carbon atoms. a is an integer from 0 to 30, b is an integer from 0 to 15, c is an integer from 0 to 10, and d is an integer from 0 to 6, and the sum of a, b, c, and d is an integer such that the 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.

[0023] In the above formula (4), R 2R are independently a monovalent hydrocarbon group having 1 to 10 carbon atoms, which may be linear, branched, or cyclic, or a combination thereof. 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. 2 As the aryl group, those represented by the following formula are preferred. (In the formula, g is an integer of 0 to 4.)

[0024] In the above formula (4), R 3 are independently divalent cyclic hydrocarbon groups having 3 to 10 carbon atoms, each of which may have a substituent, and R 3 The examples are the same as those exemplified above.

[0025] In the above formula (4), a is an integer of 0 to 30, preferably an integer of 0 to 20, b is an integer of 0 to 15, preferably an integer of 0 to 5, c is an integer of 0 to 10, preferably an integer of 0 to 5, d is an integer of 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. Furthermore, the repeating units shown in parentheses with a, b, c, and d may be bonded randomly.

[0026] 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.)

[0027] In the above formula (1), A is a monovalent reactive group, preferably a functional group that has adhesion (bonding) reactivity to the surface of a substrate made of various materials, such as paper, cloth, metal and its oxides, glass, plastic (resin), ceramic, quartz, etc., which is the target of surface treatment. Examples of the monovalent reactive group include a monovalent group selected from a carbon-carbon double bond-containing group (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)), a carbon-carbon triple bond-containing group, a cyclic ether group, a hydroxyl group-containing group (excluding those consisting only of hydroxyl groups), a thiol group, an amino group, an azide group, a nitrogen-containing heterocyclic group, a phosphate-containing group, a hydroxyl group-containing silyl group (silanol group), and a hydrolyzable silyl group.

[0028] Examples of A include carbon-carbon double bond-containing groups such as cinnamic acid group, sorbic acid group, acryloyl group, methacryloyl group, acryloyloxy group, methacryloyloxy group, acrylamide group, methacrylamide group, and vinyl ether group; carbon-carbon triple bond-containing groups such as alkynyl groups having 2 to 20 carbon atoms, such as ethynyl group, propargyl group, 2-methyl-2-propynyl group, 3-butynyl group, 4-pentynyl group, and 5-hexynyl group, and propargyloxy group, 2-methyl-2-propynyloxy group, 3-butynyloxy group, 4-pentynyloxy group, and 5-hexynyloxy group. Examples of the alkynyloxy group include alkynyl 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. Among these, hydroxyl group-containing silyl groups (silanol groups) and hydrolyzable silyl groups are preferred.

[0029] The hydroxyl group-containing silyl group and the hydrolyzable silyl group are those represented by the following general formula (2): (In the formula, R 1 are independently an alkyl group or a phenyl group having 1 to 4 carbon atoms, X is independently a hydroxyl group or a hydrolyzable group, and n is an integer of 1 to 3.) or a group represented by the following general formula (3): (wherein n″ is a number of 0 to 3, and n′ is (3−n″) / 2) is preferred.

[0030] In the above formula (2), R 1 are independently an alkyl group having 1 to 4 carbon atoms such as a methyl group, an ethyl group, a propyl group, a butyl group, or a phenyl group, with a methyl group being preferred.

[0031] 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.

[0032] In the above formula (2), n is an integer of 1 to 3, preferably 3.

[0033] In the above formula (3), n" is a number from 0 to 3 (0 or a positive number of 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 preferably 1.5.

[0034] 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): (In the formula, R 3 , R 4 , y, h, the sum of y and h is the same as above.)

[0035] Examples of the structure of the hydrocarbon terminal group-containing compound represented by the above formula (1) include the following structures: By changing the combination of R, Z, Y, A, and k in the above formula (1), several types of hydrocarbon terminal group-containing compounds can be obtained.

[0036] (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.)

[0037] [Method for Preparing a Hydrocarbon Terminal Group-Containing Compound] 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 having an alkenyl group at its terminal and a compound having a SiH group and a hydrolyzable silyl group are mixed, 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 hydrolyzable silyl group at its terminal). When a compound having a SiH group and a hydrolyzable silyl group in which the hydrolyzable group is a halogen group is used, the compound can then be produced by converting the substituent (halogen atom) on the silyl group to another hydrolyzable group.

[0038] Here, examples of hydrocarbon terminal group-containing compounds having an alkenyl group at the terminal include compounds represented by the following formula (1A). (wherein R, Z, Y, and k are the same as above. Y 1 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.

[0039] In the above formula (1A), Y 1 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, and examples thereof include those having the terminal groups shown below. (In the formula, R 7 may independently be a hydrogen atom, or a linear, branched, cyclic, or combination thereof; 1 It is a monovalent hydrocarbon group having a total carbon number of 30 or less in the structure.

[0040] Y 1 As the above, the following are 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.)

[0041] Examples of the compound represented by formula (1A) include the compounds shown below. (wherein x, y, a1, a', and g are each independently the same as above, and the sum of a' and g is the Y 1 is an integer having a total carbon number of 2 to 30.)

[0042] Examples of methods for preparing a compound represented by formula (1A) (a hydrocarbon terminal group-containing compound having an alkenyl group at its terminal) include the following methods: [Preparation method (1) of a compound represented by formula (1A)] A hydrocarbon terminal group-containing compound having a hydroxyl group at its terminal and a base are mixed, and a compound having a leaving group and an alkenyl group at its terminal is added to carry out a nucleophilic substitution reaction, thereby producing a compound represented by formula (1A) (a hydrocarbon terminal group-containing compound having an alkenyl group at its terminal).

[0043] 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.)

[0044] 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.)

[0045] In the compound represented by formula (1a-1), when m is 1 or 2, examples of the preparation method include a method in which a compound having a hydroxyl group and a functional group other than a hydroxyl group is reacted with a hydrocarbon terminal group-containing compound having a functional group through the reaction between the other functional groups 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 is reacted with the functional groups between the functional groups to obtain a hydrocarbon terminal group-containing compound into which a protected hydroxyl group has been introduced, and then the group that protected the hydroxyl group is deprotected to obtain the target compound; and other methods in which the target compound is obtained by reduction of a carbonyl compound, hydroboration reaction, etc.

[0046] 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). (Wherein Z, Y, Y 1 is the same as above. L is a halogen atom such as fluorine, chlorine, bromine, or iodine, or a leaving group such as mesylate or trilate. q is 0 or 1, and the sum of m and q is 0 or 1.

[0047] 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:

[0048] In the method (1) for preparing 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, particularly 1 to 2 mol, per mol of hydroxyl groups in the hydrocarbon terminal group-containing compound having a terminal hydroxyl group.

[0049] In the method (1) for preparing 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, potassium tert-butoxide, etc. The amount of the 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 a terminal hydroxyl group.

[0050] 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, and more preferably 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.

[0051] In the preparation method (1) of the compound represented by formula (1A), a catalyst can be added that converts the leaving group and 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 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 mol of hydroxyl groups in the hydrocarbon terminal group-containing compound having a terminal hydroxyl group.

[0052] In the method (1) for preparing the compound represented by formula (1A), the reaction conditions are preferably a temperature of 20 to 100°C, particularly 25 to 60°C, for 0.5 to 72 hours, particularly 1 to 36 hours.

[0053] Further examples of the method for preparing the compound represented by formula (1A) (a hydrocarbon terminal group-containing compound having an alkenyl group at its terminal) include the following methods: [Method (2) for preparing the 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 mixing a hydrocarbon terminal group-containing compound having an isocyanate group at its terminal with a compound having a hydroxyl group and an alkenyl group at its terminal, and reacting them in the presence of a catalyst.

[0054] Here, the hydrocarbon terminal group-containing compound having an isocyanate group at the end is not particularly limited, but examples thereof include octyl isocyanate and octadecyl isocyanate.

[0055] 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, Y 1 is the same as above. q is 0 or 1.)

[0056] 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.)

[0057] In the method (2) for preparing the compound represented by formula (1A), the amount of the compound having a terminal hydroxyl group and an alkenyl group is preferably 1 to 3 mol, particularly 1 to 1.5 mol, per mol of isocyanate groups in the hydrocarbon terminal group-containing compound having an isocyanate group at the terminal.

[0058] 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, and particularly preferably 0.1 to 20 parts by mass, per 100 parts by mass of the hydrocarbon terminal group-containing compound having an isocyanate group at its terminal.

[0059] In the preparation method (2) of the compound represented by formula (1A), a solvent can be used during the reaction. Examples of the solvent include the same solvents as those 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 mass, particularly 50 to 200 parts by mass, per 100 parts by mass of the hydrocarbon terminal group-containing compound having an isocyanate group at the terminal.

[0060] In the method (2) for preparing the compound represented by formula (1A), the reaction conditions are preferably a temperature of 20 to 100°C, particularly 23 to 60°C, for 0.5 to 72 hours, particularly 1 to 36 hours.

[0061] Further examples of the method for preparing the compound represented by formula (1A) (a hydrocarbon terminal group-containing compound having an alkenyl group at its terminal) include the following methods: [Method (3) for preparing the 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 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.

[0062] Here, examples of hydrocarbon terminal group-containing compounds having an NH group at the terminal include compounds represented by the following formula (1a-6): (In the formula, R, R 5 , Z, Y, and m are the same as above.)

[0063] Examples of the compound represented by formula (1a-6) include the compounds shown below. (wherein x is the same as above).

[0064] 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 , q is the same as above, and the sum of m and q is 0 or 1.

[0065] Examples of the compound represented by formula (1a-7) include the compounds shown below. (In the formula, a' is independently the same as above.)

[0066] In the method (3) for preparing the compound represented by formula (1A), the amount of the compound having a terminal carboxy group and an alkenyl group to be used is preferably 1 to 5 mol, particularly 1 to 1.5 mol, per 1 mol of the hydrocarbon terminal group-containing compound having a terminal NH group.

[0067] 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, 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide, etc. The amount of the condensing agent used is preferably 1 to 3 mol, particularly 1 to 1.5 mol, per mol of the hydrocarbon terminal group-containing compound having an NH group at the terminal.

[0068] 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 1 mol of the hydrocarbon terminal group-containing compound having an NH group at the terminal.

[0069] 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, and 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 terminal.

[0070] In the method (3) for preparing the compound represented by formula (1A), the reaction conditions are preferably a temperature of 20 to 100°C, particularly 20 to 50°C, for 0.5 to 72 hours, particularly 1 to 24 hours.

[0071] Further examples of the method for preparing the compound represented by formula (1A) (a hydrocarbon terminal group-containing compound having an alkenyl group at its terminal) include the following methods. [Preparation method (4) of the 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 prepared by carrying out the oxazole synthesis described in reference document [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 document [X] Synlett 2009(3): 500-504.

[0072] 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.)

[0073] Examples of the compound represented by formula (1a-9) include the compounds shown below. (wherein x is the same as above).

[0074] 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). (Wherein Z, Y, Y 1 is the same as above. L is a halogen atom such as fluorine, chlorine, bromine, or iodine, or a leaving group such as mesylate or trilate. q is 0 or 1, and the sum of m and q is 0 or 1.

[0075] 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:

[0076] In the method (4) for preparing 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, particularly 1 to 1.5 mol, per 1 mol of the hydrocarbon terminal group-containing compound having an aldehyde group at its terminal.

[0077] 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 the 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.

[0078] 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 are 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, and more preferably 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 terminal.

[0079] 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, for 0.5 to 72 hours, particularly 6 to 24 hours.

[0080] Further examples of the method for preparing the compound represented by formula (1A) (a hydrocarbon terminal group-containing compound having an alkenyl group at its terminal) include the following methods: [Method (5) for preparing the 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 mixing a hydrocarbon terminal group-containing compound having an azide group at its terminal with a compound having an alkynyl group and an alkenyl group at its terminal, and reacting them in the presence of a catalyst.

[0081] 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.)

[0082] Examples of the compound represented by formula (1a-12) include the compounds shown below. (wherein x is the same as above).

[0083] 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, Y 1 is the same as above. q is 0 or 1, and the sum of m and q is 0 or 1.

[0084] Examples of the compound represented by formula (1a-13) include the compounds shown below. (wherein x is the same as above).

[0085] In the method (5) for preparing the compound represented by formula (1A), the amount of the compound having a terminal alkynyl group and an alkenyl group is preferably 1 to 5 mol, particularly 1 to 1.2 mol, per 1 mol of the hydrocarbon terminal group-containing compound having an azide group at its terminal.

[0086] 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), pentamethylcyclopentadienylbis(triphenylphosphine)ruthenium(II) chloride, etc. The amount of catalyst used is preferably 0.001 to 10 mol, particularly 0.1 to 1 mol, per mol of the compound containing a hydrocarbon terminal group having an azide group at its terminal.

[0087] 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 0.2 to 2 mol, per mol of the hydrocarbon terminal group-containing compound having an azide group at its terminal.

[0088] 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 above alcohols in any ratio. The amount of the solvent used is preferably 0 to 3,000 parts by mass, and more preferably 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 terminal.

[0089] In the method (5) for preparing the compound represented by formula (1A), the reaction conditions are preferably a temperature of 20 to 100°C, particularly 23 to 60°C, for 0.5 to 72 hours, particularly 6 to 24 hours.

[0090] In Preparation Method 1, examples of the compound having a SiH group and a hydrolyzable silyl group include trimethoxysilane, triethoxysilane, triacetoxysilane, and trichlorosilane.

[0091] 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, particularly 5 to 10 mol, per 1 mol of alkenyl group in the hydrocarbon terminal group-containing compound having an alkenyl group at the terminal.

[0092] In Preparation Method 1, examples of the hydrosilylation catalyst include platinum black, chloroplatinic acid, alcohol-modified chloroplatinic acid, complexes of chloroplatinic acid with olefins, aldehydes, vinylsiloxanes, acetylene alcohols, and the like, 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 catalyst used is preferably an amount equivalent to 0.001 to 1,000 ppm, more preferably 0.01 to 100 ppm, of transition metal (by mass) relative to the mass of the compound containing a hydrocarbon terminal group having an alkenyl group at its terminal.

[0093] 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 cocatalysts are used, the amount used is preferably an amount that provides 10 to 1,000,000 ppm, and more preferably 100 to 10,000 ppm, calculated by mass, relative to the mass of the hydrocarbon terminal group-containing compound having an alkenyl group at the terminal.

[0094] 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, and more preferably 50 to 200 parts by mass, per 100 parts by mass of the hydrocarbon terminal group-containing compound having an alkenyl group at the terminal.

[0095] In Preparation Method 1, the reaction conditions for the hydrocarbon terminal group-containing compound having an alkenyl group at the terminal with 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.

[0096] 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, and 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 a halogenated silyl group-containing compound.

[0097] In Preparation Method 1, the reaction conditions for converting a substituent (halogen atom) on a 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.

[0098] Other methods for preparing the hydrocarbon terminal group-containing compound represented by general formula (1) of the present invention include the following: [Preparation Method 2] A hydrocarbon terminal group-containing compound having a terminal SiH group is mixed with a compound having a reactive group such as an alkenyl group and a hydrolyzable silyl group, 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).

[0099] 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. Z １ 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.

[0100] In the above formula (1B), Z １ 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.)

[0101] 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.)

[0102] Furthermore, among compounds having a reactive group such as an alkenyl group and a hydrolyzable silyl group, examples of the compound having an alkenyl group and a hydrolyzable silyl group include vinyltrimethoxysilane, allyltrimethoxysilane, octenyltrimethoxysilane, etc. Furthermore, examples of the compound having a reactive group other than an alkenyl group and a hydrolyzable silyl group include allyl glycidyl ether, etc.

[0103] In Preparation Method 2, the amount of the compound having a reactive group such as an alkenyl group or a hydrolyzable silyl group used is preferably 1 to 5 mol, particularly 1 to 3 mol, per 1 mol of SiH groups in the hydrocarbon terminal group-containing compound having SiH groups at the terminals.

[0104] In Preparation Method 2, the hydrosilylation catalyst can be exemplified by the same hydrosilylation catalysts as those in Preparation Method 1. 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 catalyst used is preferably an amount equivalent to 0.001 to 1,000 ppm, more preferably 0.01 to 100 ppm, of transition metal (by mass) relative to the mass of the hydrocarbon terminal group-containing compound having a terminal SiH group.

[0105] In Preparation Method 2, a co-catalyst that activates the hydrosilylation reaction can be used. Examples of co-catalysts that activate the hydrosilylation reaction include acetic acid, formic acid, and propionic acid. The amount of the co-catalyst 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.

[0106] In Preparation Method 2, a solvent can be used during 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, and 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.

[0107] 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.

[0108] Other methods for preparing the hydrocarbon terminal group-containing compound represented by general formula (1) of the present invention include the following: [Preparation Method 3] A hydrocarbon terminal group-containing compound having an alkenyl group at its terminal is mixed with trichlorosilane, reacted in the presence of a hydrosilylation reaction catalyst, and then the resulting compound is reacted with ammonia gas to produce a hydrocarbon terminal group-containing compound represented by formula (1) (particularly a compound having an amino group-containing silyl group at its terminal and / or a polysilazane compound that is a polymer thereof).

[0109] Here, the reaction product of the 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.

[0110] In Preparation Method 3, the amount of ammonia gas used is preferably 1 to 300 cc / min, and particularly preferably 30 to 200 cc / min.

[0111] In Preparation Method 3, a solvent can be used when reacting ammonia gas with the reaction product of trichlorosilane and a hydrocarbon terminal group-containing compound having an alkenyl group at its terminal. Examples of the solvent include the same solvents as those used in Preparation Method 1. The amount of solvent used is preferably 0 to 1,000 parts by mass, and more preferably 50 to 300 parts by mass, per 100 parts by mass of the hydrocarbon terminal group-containing compound having an alkenyl group at its terminal.

[0112] In Preparation Method 3, the reaction conditions for the reaction of ammonia gas with a reactant of a hydrocarbon terminal group-containing compound having an alkenyl group at its terminal and trichlorosilane are preferably room temperature (23±15°C, the same applies hereinafter), particularly a temperature of 20 to 30°C, for 2 to 36 hours, particularly 4 to 12 hours.

[0113] Other methods for preparing the hydrocarbon terminal group-containing compound represented by general formula (1) of the present invention include the following. [Preparation Method 4] A hydrocarbon terminal group-containing compound having a terminal hydroxyl group is mixed with a compound having an isocyanate group and a reactive group (e.g., a hydrolyzable silyl group or a (meth)acryloyloxy group), and the mixture is 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.

[0114] 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.)

[0115] 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.)

[0116] Examples of methods for preparing a compound represented by formula (1C) (a hydrocarbon terminal group-containing compound having a terminal hydroxyl group) include the following methods: [Preparation method (1) of 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.

[0117] Here, the hydrocarbon terminal group-containing compound having an isocyanate group at the end is not particularly limited, but examples thereof include octyl isocyanate and octadecyl isocyanate.

[0118] 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). (In the formula, Z, Y, R 5 is the same as above, and p is an integer of 0 to 2.

[0119] 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.)

[0120] In the method (1) for preparing the compound represented by formula (1C), the amount of the compound having an NH group and a hydroxyl group at its terminals is preferably 1 to 3 mol, particularly 1 to 1.5 mol, per mol of isocyanate groups in the hydrocarbon terminal group-containing compound having an isocyanate group at its terminal.

[0121] In the preparation method (1) of the compound represented by formula (1C), a solvent can be used during 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, and more preferably 500 to 2,000 parts by mass, per 100 parts by mass of the hydrocarbon terminal group-containing compound having an isocyanate group at its terminal.

[0122] In the method (1) for preparing the compound represented by formula (1C), the reaction conditions are preferably a temperature of 20 to 100°C, particularly 23 to 60°C, for 0.5 to 72 hours, particularly 1 to 36 hours.

[0123] 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: [Preparation method (2) of the compound represented by formula (1C)] The compound represented by formula (1C) (a hydrocarbon terminal group-containing compound having a terminal hydroxyl group) can be prepared by mixing a hydrocarbon terminal group-containing compound having an alkenyl group at its terminal with a borane compound, hydroborating the resulting mixture, and then oxidizing the mixture with hydrogen peroxide and a base.

[0124] 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). (Wherein R, Z, Y, Y 1, m is 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.

[0125] 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.)

[0126] 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.)

[0127] The compound represented by formula (1c-4) can be prepared by the same method as the preparation method (1) or (2) of the compound represented by formula (1A).

[0128] 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, 9-borabicyclo[3.3.1]nonane, etc. 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.

[0129] In the method (2) for preparing the compound represented by formula (1C), the amount of hydrogen peroxide used is preferably 1 to 20 mol, particularly 10 to 15 mol, per mol of the hydrocarbon terminal group-containing compound having an alkenyl group at the terminal.

[0130] In the method (2) for preparing 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, potassium carbonate, etc. The amount of the 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.

[0131] 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, and more preferably 100 to 200 parts by mass, per 100 parts by mass of the hydrocarbon terminal group-containing compound having an alkenyl group at the terminal.

[0132] In the method (2) for preparing the compound represented by formula (1C), the reaction conditions are preferably a temperature of 20 to 100°C, particularly 23 to 50°C, for 0.5 to 72 hours, particularly 1 to 9 hours.

[0133] In addition, in Preparation Method 4, examples of the compound having an isocyanate group and a reactive group include 3-isocyanatopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, and 1,1-(bisacryloyloxymethyl)ethyl isocyanate.

[0134] In Preparation Method 4, the amount of the compound having an isocyanate group and a reactive group 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 a terminal hydroxyl group.

[0135] 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 catalyst used is preferably 0.01 to 100 parts by mass, and 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.

[0136] A solvent can be used during the reaction in Preparation Method 4. 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, and more preferably 50 to 200 parts by mass, per 100 parts by mass of the hydrocarbon terminal group-containing compound having a terminal hydroxyl group.

[0137] 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.

[0138] Other methods for preparing the hydrocarbon terminal group-containing compound represented by general formula (1) of the present invention include the following: [Preparation Method 5] A hydrocarbon terminal group-containing compound having a terminal hydroxyl group is mixed with phosphorus oxychloride to cause a reaction, and then water is added to cause a reaction to occur, thereby producing 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).

[0139] Here, examples of hydrocarbon terminal group-containing compounds having a hydroxyl group at the terminal 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.)

[0140] In Preparation Method 5, the amount of phosphorus oxychloride used is preferably 1 to 4 mol, particularly 1 to 2 mol, per mol of hydroxyl groups in the hydrocarbon terminal group-containing compound having terminal hydroxyl groups.

[0141] 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 solvent used is preferably 0 to 1,000 parts by mass, and more preferably 50 to 500 parts by mass, per 100 parts by mass of the hydrocarbon terminal group-containing compound having a terminal hydroxyl group.

[0142] 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.

[0143] In Preparation Method 5, the amount of water used is preferably 50 to 1,000 parts by mass, and particularly preferably 100 to 500 parts by mass, per 100 parts by mass of the compound containing a hydrocarbon terminal group having a terminal hydroxyl group.

[0144] In Preparation Method 5, the reaction conditions for the reaction of water with the reaction product of a hydrocarbon terminal group-containing compound having a terminal hydroxyl group and 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.

[0145] Other methods for preparing the hydrocarbon terminal group-containing compound represented by general formula (1) of the present invention include the following: [Preparation Method 6] A hydrocarbon terminal group-containing compound having an NH group at its terminal is mixed with a compound having an isocyanate group and a reactive group (e.g., a hydrolyzable silyl group, a (meth)acryloyloxy group, etc.) and reacted 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 its terminal via a urea bond).

[0146] Here, examples of hydrocarbon terminal group-containing compounds having an NH group at the terminal include compounds represented by the following formula (1D). (In the formula, R, R 5 , Z, Y, and m are the same as above.)

[0147] Examples of the compound represented by formula (1D) include the compounds shown below. (wherein x and a1 are the same as above.)

[0148] Examples of methods for preparing a compound represented by formula (1D) (a hydrocarbon terminal group-containing compound having an NH group at its terminal) include the following methods: [Preparation method (1) of a compound represented by formula (1D)] A compound represented by formula (1D) (a hydrocarbon terminal group-containing compound having an NH group at its terminal) can be produced by mixing a hydrocarbon terminal group-containing compound having an NH group protected at its terminal with a tert-butoxycarbonyl protecting group with an acid.

[0149] 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). (In the formula, R, R 5 , Z, Y, m are the same as above, ｔ Bu is a tert-butyl group.

[0150] Here, examples of the compound represented by formula (1d-1) include those shown below. (wherein x and a1 are the same as above, ｔ Bu is a tert-butyl group.

[0151] In the preparation method (1) of the compound represented by formula (1D), the acid is not particularly limited, but examples of organic acids include trifluoroacetic acid, trimethylsilyl triflate, etc., and examples of other acids include hydrochloric acid, sulfuric acid, etc. The amount of the acid used is preferably 1 to 100 mol, particularly 1 to 10 mol, per mol of the 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.

[0152] 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, and more preferably 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.

[0153] In the method (1) for preparing the compound represented by formula (1D), the reaction conditions are preferably a temperature of 20 to 100°C, particularly 25 to 65°C, for 0.5 to 72 hours, particularly 1 to 24 hours.

[0154] Further examples of the method for preparing the compound represented by formula (1D) (a hydrocarbon terminal group-containing compound having an NH group at its terminal) include the following methods: [Preparation method (2) of the compound represented by formula (1D)] The compound represented by formula (1D) (a hydrocarbon terminal group-containing compound having an NH group at its terminal) can be prepared by reducing a hydrocarbon terminal group-containing compound having an amide group at its terminal with a base.

[0155] Here, examples of hydrocarbon terminal group-containing compounds having an amide group at the terminal include compounds represented by the following formula (1d-2). (In the formula, R, R 5 , Z, Y, Y 1 , m is the same as above.)

[0156] Here, examples of the compound represented by formula (1d-2) include those shown below. (wherein x and a' are the same as above.)

[0157] In the method (2) for preparing the compound represented by formula (1D), the base is not particularly limited, but examples include lithium aluminum hydride, sodium bis(2-methoxyethoxy)aluminum hydride, etc. The amount of the base used is preferably 1 to 10 mol, particularly 2 to 5 mol, per mol of amide groups in the hydrocarbon terminal group-containing compound having an amide group at the terminal.

[0158] 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, and dichloromethane and 1,2-dichloroethane. The amount of the solvent used is preferably 100 to 10,000 parts by mass, and more preferably 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 terminal.

[0159] 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, for 0.5 to 72 hours, particularly 1 to 24 hours.

[0160] In addition, in Preparation Method 6, examples of the compound having an isocyanate group and a reactive group include 3-isocyanatopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, 2-(acryloyloxy)ethyl isocyanate, and 2-isocyanatoethyl methacrylate.

[0161] In Preparation Method 6, the amount of the compound having an isocyanate group and a reactive group used is preferably 1 to 3 mol, particularly 1 to 1.5 mol, per mol of the hydrocarbon terminal group-containing compound having an NH group at the terminal.

[0162] In Preparation Method 6, a solvent can be used during 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 its terminal.

[0163] 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.

[0164] Other methods for preparing the hydrocarbon terminal group-containing compound represented by general formula (1) of the present invention include the following: [Preparation Method 7] A hydrocarbon terminal group-containing compound having an alkenyl group at its terminal and a silane compound having a thiol group at its terminal, or a hydrocarbon terminal group-containing compound having a thiol group at its terminal and a silane compound having an alkenyl group at its terminal, are mixed together and reacted in the presence of a polymerization initiator to produce the hydrocarbon terminal group-containing compound represented by formula (1).

[0165] 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). (Wherein R, Z, Y, Y 1 , m is 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.

[0166] 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.)

[0167] 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.)

[0168] The compound represented by formula (1E-2) can be prepared by the same method as the preparation method (1) or (2) of the compound represented by formula (1A).

[0169] 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.)

[0170] Examples of the compound represented by formula (1F) include the compounds shown below. (wherein a1 is the same as above.)

[0171] 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.)

[0172] Examples of the compound represented by formula (1G) include the compounds shown below. (wherein x is the same as above).

[0173] Here, examples of preparation methods for compounds represented by formula (1G) when 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 via the other functional groups 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 that protected the thiol group is deprotected to obtain the target compound.

[0174] 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). (In the formula, Y 1 , Z, Y, A, and p are the same as above.)

[0175] Examples of the compound represented by formula (1H) include the compounds shown below. (wherein a' is the same as above.)

[0176] In Preparation Method 7, the amount of the silane compound having a terminal thiol group 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.

[0177] 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 0.1 to 1.5 mol, per mol of alkenyl groups in the hydrocarbon terminal group-containing compound having an alkenyl group at its terminal or thiol groups in the hydrocarbon terminal group-containing compound having a thiol group at its terminal.

[0178] In Preparation Method 7, a solvent can be used during the reaction. Examples of the solvent include the same solvents as those used in Preparation Method 1. The amount of solvent used is preferably 0 to 1,000 parts by mass, and more preferably 50 to 800 parts by mass, per 100 parts by mass of the hydrocarbon terminal group-containing compound having an alkenyl group at its terminal or the hydrocarbon terminal group-containing compound having a thiol group at its terminal.

[0179] 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.

[0180] Other methods for preparing the hydrocarbon terminal group-containing compound represented by general formula (1) of the present invention include the following: [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.

[0181] 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.)

[0182] Examples of the compound represented by formula (1I) include the compounds shown below. (wherein x is the same as above).

[0183] 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.)

[0184] Examples of the compound represented by formula (1J) include the compounds shown below. (In the formula, a1 is independently the same as above.)

[0185] In Preparation Method 8, the amount of the silane compound having an amino 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 an acid halide at its terminal.

[0186] 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, and more preferably 1 to 1.5 mol, per mol of the hydrocarbon terminal group-containing compound having an acid halide at the terminal.

[0187] In Preparation Method 8, a solvent can be used during 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, and more preferably 50 to 400 parts by mass, per 100 parts by mass of the compound not having a terminal silyl group.

[0188] 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.

[0189] [Surface Treatment Agent] The present invention further provides a substantially fluorine-free surface treatment agent containing, as a main component, a non-fluorine-based (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 also contain a partial (hydrolyzed) condensate obtained by partial hydrolysis and condensation of the hydrolyzable silyl group by a known method.

[0190] If necessary, the surface treatment agent may contain a hydrolysis condensation catalyst, such as an organotin compound (dibutyltin dimethoxide, dibutyltin dilaurate, etc.), an organotitanium compound (tetra n-butyl titanate, tetra n-propyl titanate, etc.), an organozirconium 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 condensation catalyst is added, the amount added is a catalytic amount, and is typically 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).

[0191] The surface treatment agent may contain a suitable solvent. Such a solvent is preferably a non-fluorinated solvent, and examples thereof include hydrocarbon solvents (petroleum benzine, toluene, xylene, hexane, cyclohexane, methylcyclohexane, ethylcyclohexane, heptane, octane (n-octane, isooctane, etc.), nonane (n-nonane, isononane, etc.)), ketone solvents (acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, etc.), ether solvents (tetrahydrofuran (THF), dipropyl ether, dibutyl ether, methylcyclopentyl ether, methyl t-butyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, propylene glycol dimethyl ether, etc.), alcohol solvents (propylene glycol monomethyl ether, butanol, isopropanol, etc.), and ester solvents (ethyl acetate, propyl acetate, butyl acetate, pentyl acetate, propylene glycol monomethyl ether acetate). Among these, toluene, hexane, heptane, isooctane, isononane, cyclopentanone, dipropyl ether, dibutyl ether, 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, and the like.

[0192] Two or more of the above solvents may be mixed, and it is preferable that the hydrocarbon terminal group-containing compound (and its partial (hydrolyzed) condensate) be dissolved uniformly. 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 treatment method, and may be any amount that is easy to weigh. In the case of direct coating, the amount is preferably 0.01 to 100 parts by mass, and more preferably 0.05 to 30 parts by mass, per 100 parts by mass of the solvent and the hydrocarbon terminal group-containing compound (and its partial (hydrolyzed) condensate). In the case of vapor deposition treatment, the amount is preferably 1 to 100 parts by mass, and more preferably 3 to 50 parts by mass, per 100 parts by mass of the solvent and the hydrocarbon terminal group-containing compound (and its partial (hydrolyzed) condensate). In either case, the amount of 100 parts by mass refers to the case where the coating is carried out directly without using a solvent.

[0193] 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 used 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.), the curing temperature 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, the curing temperature is preferably in the range of 20 to 200°C for 1 to 24 hours. Curing may also be performed under humidified conditions. For example, when using a hydrocarbon terminal group-containing compound having a hydrolyzable silyl group, spray coating can be performed by diluting the compound in an organic solvent containing water in advance and hydrolyzing the compound, i.e., generating Si—OH, before spray coating, thereby achieving rapid curing after coating.

[0194] The thickness of the cured coating is determined appropriately depending on the type of substrate, but is usually 0.1 to 100 nm, particularly 1 to 20 nm. The thickness can be measured by, for example, spectral reflectance measurement, X-ray reflectance measurement, spectroscopic ellipsometry measurement, X-ray fluorescence measurement, etc.

[0195] 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. SiO-treated glass and film are particularly preferred.

[0196] The surface treatment agent of the present invention can form a cured coating film that has high levels of water repellency, slipperiness, dirt wiping properties and abrasion resistance.

[0197] [Articles] Examples of articles to be treated with the surface treatment agent of the present invention include car navigation systems, mobile phones, smartphones, digital cameras, digital video cameras, PDAs, portable audio players, car audio, 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, anti-reflection films, and other optical articles and electronic components. 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.

[0198] 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 for 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 for 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 release agent or paint additive for molds, a resin modifier, a flowability modifier or dispersibility modifier for inorganic fillers, or a lubricity improver for tapes, films, etc.

[0199] The present invention will be described in more detail below with reference to synthesis examples, examples, and comparative examples. However, the present invention is not limited to the following examples. In the following examples, the molar amount of a compound is expressed as the molar amount of the compound relative to the measured mass of the target compound. 1The film thickness was measured by spectroscopic ellipsometry using a spectroscopic ellipsometer. The room temperature was 23°C.

[0200] Synthesis Example 1 A reaction vessel was charged with a compound represented by the following formula (A): 5.00 g (1.76 × 10 -2 mol), 10.0 g of tetrahydrofuran, and 3.62 g (1.76 × 10 -2 The resulting mixture was 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.

[0201] The resulting compound is 1 H-NMR confirmed that the compound had a structure represented by the following formula (B):

[0202] Synthesis Example 2: 5.00 g (1.86 x 10) of octadecylamine was placed in a reaction vessel. -2 mol), 10.00 g of tetrahydrofuran, and 3.81 g (1.86 × 10 -2 The resulting mixture was 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.

[0203] The resulting compound is 1 H-NMR confirmed that the compound had a structure represented by the following formula (C):

[0204] Synthesis Example 3 5.00 g (1.85 × 10) of 1-octadecanol was placed in a reaction vessel. -2 mol), tetrahydrofuran 10.00 g, 3-isocyanatopropyltrimethoxysilane 3.79 g (1.85 × 10 -2 mol), and tetrakis(2-ethylhexyl) orthotitanate 1.03 × 10 -2 g (1.82 x 10 -5 The resulting mixture was 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 a product.

[0205] The resulting compound is 1 H-NMR confirmed that the compound had a structure represented by the following formula (D):

[0206] Synthesis Example 4 A reaction vessel was charged with a compound represented by the following formula (E): 5.00 g (1.65 × 10 -2 mol), tetrahydrofuran 20.00 g, 3-aminopropyltrimethoxysilane 3.55 g (1.98 × 10 -2 mol), and 2.50 g (2.48 × 10 -2 mol) 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.

[0207] The resulting compound is 1 H-NMR confirmed that the compound had a structure represented by the following formula (F):

[0208] Synthesis Example 5: 5.00 g (1.98 × 10 -2 mol), toluene 40.00 g, 3-thiolpropyltrimethoxysilane 4.28 g (2.18 × 10 -2 mol), and 2,2'-azobis(isobutyrate) dimethyl 4.56 × 10 -1 g (1.98 x 10 -3 The resulting mixture was 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 a product.

[0209] The resulting compound is 1 H-NMR confirmed that the compound had a structure represented by the following formula (G):

[0210] Synthesis Example 6 A reaction vessel was charged with a compound represented by the following formula (H): 5.00 g (1.69 × 10 -2 mol), toluene 5.00 g, trimethoxysilane 10.30 g (8.43 × 10 -2 mol), chloroplatinic acid / vinylsiloxane complex toluene solution 2.60 × 10 -3g (8.05 x 10 as Pt alone) -9 mol) and acetic acid 3.15 x 10 -3 g (5.25 x 10 -5 The resulting mixture was 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 a product.

[0211] The resulting compound is 1 H-NMR confirmed that the compound had a structure represented by the following formula (I):

[0212] Synthesis Example 7-1: 5.00 g (1.69 × 10) of octadecyl isocyanate was placed in a reaction vessel. -2 mol), tetrahydrofuran 10.00 g, allyl alcohol 1.18 g (2.03 × 10 -2 mol), and tetrakis(2-ethylhexyl) orthotitanate 1.03 × 10 -2 g (1.82 x 10 -5 The resulting mixture was mixed with the above-mentioned components (mol) 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 a product.

[0213] The resulting compound is 1 H-NMR confirmed that the compound had a structure represented by the following formula (J):

[0214] Synthesis Example 7-2 A reaction vessel was charged with a compound represented by the following formula (J): 5.00 g (1.41 × 10) of a compound represented by the formula -2 mol), toluene 5.00 g, trimethoxysilane 8.65 g (7.08 × 10 -2 mol), chloroplatinic acid / vinylsiloxane complex toluene solution 2.60 × 10 -3 g (8.05 x 10 as Pt alone) -9 mol) and acetic acid 3.15 x 10 -3 g (5.25 x 10 -5 The resulting mixture was 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 a product.

[0215] The resulting compound is 1H-NMR confirmed that the compound had a structure represented by the following formula (K):

[0216] Synthesis Example 8-1: 10.00 g (3.71 × 10) of 1-octadecylamine was placed in a reaction vessel. -2 mol), 200.00 g of 1,2-dichloroethane, 3.83 g (4.45 × 10 -2 mol), 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride 9.95 g (5.19 × 10 -2 mol), and 4-dimethylaminopyridine 9.10 × 10 -1 g (7.42 x 10 -3 The resulting mixture (mol) was mixed 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 layers were washed with purified water and saturated brine, and dried over magnesium sulfate. After that, the mixture was treated with activated carbon, and the solvent and unreacted materials were distilled off under reduced pressure to obtain 5.27 g of product.

[0217] The resulting compound is 1 H-NMR confirmed that the compound had a structure represented by the following formula (L):

[0218] Synthesis Example 8-2 A reaction vessel was charged with a compound represented by the following formula (L): 5.00 g (1.48 × 10 -2 mol), toluene 5.00 g, trimethoxysilane 9.04 g (7.40 × 10 -2 mol), chloroplatinic acid / vinylsiloxane complex toluene solution 2.60 × 10 -3 g (8.05 x 10 as Pt alone) -9 mol), and formamide 3.30 × 10 -3 g (7.33 x 10 -5 The resulting mixture was 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 a product.

[0219] The resulting compound is 1 H-NMR confirmed that the compound had a structure represented by the following formula (M):

[0220] Synthesis Example 9 5.00 g (1.98 × 10) of 1-octadecene was placed in a reaction vessel. -2 mol), toluene 38.50 g, 1,4-bis(dimethylsilyl)benzene 38.50 g (1.98 × 10 -1 mol), chloroplatinic acid / vinylsiloxane complex toluene solution 2.60 × 10 -3 g (8.05 x 10 as Pt alone) -9 mol), and formamide 3.30 × 10 -3 g (7.33 x 10 -5 The resulting mixture was aged at 80° C. for 1 hour. Thereafter, the solvent and unreacted materials were distilled off under reduced pressure to obtain 6.11 g of a product.

[0221] The resulting compound is 1 H-NMR confirmed that the compound had a structure represented by the following formula (N):

[0222] In a reaction vessel, the following formula (N) 5.00 g (1.12 × 10 -2 mol), toluene 5.00 g, allyltrimethoxysilane 1.82 g (1.12 × 10 -2 mol), chloroplatinic acid / vinylsiloxane complex toluene solution 2.60 × 10 -3 g (8.05 x 10 as Pt alone) -9 mol), and acetic acid 3.15 × 10 -3 g (5.25 x 10 -5 The resulting mixture was 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.

[0223] The resulting compound is 1 H-NMR confirmed that the compound had a structure represented by the following formula (O):

[0224] Synthesis Example 10: 5.00 g (1.98 × 10 -2 mol), toluene 38.50 g, tetramethyldisiloxane 26.60 g (1.98 × 10 -1mol), chloroplatinic acid / vinylsiloxane complex toluene solution 2.60 × 10 -3 g (8.05 x 10 as Pt alone) -9 mol), and formamide 3.30 × 10 -3 g (7.33 x 10 -5 The resulting mixture was aged for 2 hours at 80° C. Thereafter, the solvent and unreacted materials were distilled off under reduced pressure to obtain 6.33 g of a product.

[0225] The resulting compound is 1 H-NMR confirmed that the compound had a structure represented by the following formula (P):

[0226] A reaction vessel was charged with the following formula (P): 5.00 g (1.29 × 10 -2 mol), toluene 5.00 g, allyltrimethoxysilane 2.09 g (1.29 × 10 -2 mol), chloroplatinic acid / vinylsiloxane complex toluene solution 2.60 × 10 -3 g (8.05 x 10 as Pt alone) -9 mol), and acetic acid 3.15 × 10 -3 g (5.25 x 10 -5 The resulting mixture was 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.

[0227] The resulting compound is 1 H-NMR confirmed that the compound had a structure represented by the following formula (Q):

[0228] Synthesis Example 11 5.00 g (1.98 × 10) of 1-octadecene was placed in a reaction vessel. -2 mol), toluene 38.50 g, bis(dimethylsilyl)octane 45.65 g (1.98 × 10 -1 mol), chloroplatinic acid / vinylsiloxane complex toluene solution 2.60 × 10 -3 g (8.05 x 10 as Pt alone) -9 mol), and formamide 3.30 × 10 -3 g (7.33 x 10 -5The resulting mixture was aged for 24 hours at 80° C. Thereafter, the solvent and unreacted materials were distilled off under reduced pressure to obtain 9.56 g of a product.

[0229] The resulting compound is 1 H-NMR confirmed that the compound had a structure represented by the following formula (R):

[0230] In a reaction vessel, the following formula (R) 5.00 g (1.04 × 10 -2 mol), toluene 5.00 g, allyltrimethoxysilane 1.68 g (1.04 × 10 -2 mol), chloroplatinic acid / vinylsiloxane complex toluene solution 2.60 × 10 -3 g (8.05 x 10 as Pt alone) -9 mol), and acetic acid 3.15 × 10 -3 g (5.25 x 10 -5 The resulting mixture was 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.

[0231] The resulting compound is 1 H-NMR confirmed that the compound had a structure represented by the following formula (S):

[0232] Synthesis Example 12 A reaction vessel was charged with a compound represented by the following formula (T): 10.00 g (2.88 × 10 -2 mol) and 50.00 g of toluene were mixed and stirred at 0° C. To the mixture was added 12.50 g of a toluene solution of sodium bis(2-methoxyethoxy)aluminum hydride (4.32×10 as elemental aluminum). -2 mol) was added dropwise and aged at 0°C for 1 hour. 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 powdered with activated carbon and Kyoward 500, and the solvent and unreacted materials were distilled off under reduced pressure to obtain 8.94 g of product.

[0233] The resulting compound is 1H-NMR confirmed that the compound had a structure represented by the following formula (U):

[0234] A reaction vessel was charged with the following formula (U): 5.00 g (1.60 × 10 -2 mol), toluene 5.00 g, allyltrimethoxysilane 2.86 g (1.76 × 10 -2 mol), chloroplatinic acid / vinylsiloxane complex toluene solution 2.60 × 10 -3 g (8.05 x 10 as Pt alone) -9 mol), and acetic acid 3.15 × 10 -3 g (5.25 x 10 -5 The resulting mixture was 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.

[0235] The resulting compound is 1 H-NMR confirmed that the compound had a structure represented by the following formula (V):

[0236] Synthesis Example 13-1: 5.00 g (1.69 × 10) of octadecyl isocyanate was placed in a reaction vessel. -2 mol), tetrahydrofuran 10.00 g, ethylene glycol monoallyl ether 1.81 g (1.78 × 10 -2 mol), and tetrakis(2-ethylhexyl) orthotitanate 1.03 × 10 -2 g (1.82 x 10 -5 The mixture was mixed with the above components (mol) and aged at room temperature for 24 hours. The solvent and unreacted materials were removed by distillation under reduced pressure, and then the mixture was treated with activated carbon, and the solvent was removed by distillation under reduced pressure to obtain 5.30 g of a product.

[0237] The resulting compound is 1 H-NMR confirmed that the compound had a structure represented by the following formula (W):

[0238] Synthesis Example 13-2 A reaction vessel was charged with a compound represented by the following formula (W): 5.00 g (1.26 × 10 -2 mol), toluene 5.00 g, trimethoxysilane 7.68 g (6.29 × 10-2 mol), chloroplatinic acid / vinylsiloxane complex toluene solution 2.60 × 10 -3 g (8.05 x 10 as Pt alone) -9 mol), and formamide 3.30 × 10 -3 g (7.33 x 10 -5 The resulting mixture was 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 a product.

[0239] The resulting compound is 1 H-NMR confirmed that the compound had a structure represented by the following formula (X):

[0240] Synthesis Example 14-1: 5.00 g (1.69 × 10) of octadecyl isocyanate was placed in a reaction vessel. -2 mol), 100.00 g of tetrahydrofuran, and 1.09 g (1.78 × 10 -2 The resulting mixture was 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.

[0241] The resulting compound is 1 H-NMR confirmed that the compound had a structure represented by the following formula (Y):

[0242] Synthesis Example 14-2 A reaction vessel was charged with a compound represented by the following formula (Y): 5.00 g (1.40 × 10 -2 mol), tetrahydrofuran 75.00 g, tetrabutylammonium iodide 4.65 × 10 -1 g (1.26 x 10 -3 mol), and 1.56 g (1.39 × 10 -2 mol) and aged at 50°C for 1 hour. -2mol) was added dropwise and the mixture was aged at 50°C for 24 hours. 10.00 g of 2 M hydrochloric acid was added to the resulting solution, and the aqueous layer was extracted three times with toluene. The combined organic layers were washed with pure water and saturated 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 to obtain 3.43 g of product.

[0243] The resulting compound is 1 H-NMR confirmed that the compound had a structure represented by the following formula (Z):

[0244] Synthesis Example 14-3 A reaction vessel was charged with a compound represented by the following formula (Z): 5.00 g (1.26 × 10 -2 mol), toluene 5.00 g, trimethoxysilane 7.69 g (6.29 × 10 -2 mol), chloroplatinic acid / vinylsiloxane complex toluene solution 2.60 × 10 -3 g (8.05 x 10 as Pt alone) -9 mol), and formamide 3.30 × 10 -3 g (7.33 x 10 -5 The resulting mixture was 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 a product.

[0245] The resulting compound is 1 H-NMR confirmed that the compound had a structure represented by the following formula (AA):

[0246] Synthesis Example 15-1: 5.00 g (1.85 × 10) of octadecyl alcohol was placed in a reaction vessel. -2 mol), tetrahydrofuran 50.00 g, tetrabutylammonium iodide 6.80 × 10 -1 g (1.85 x 10 -3 mol), and 2.28 g (2.03 × 10 -2 mol) and aged at 50°C for 1 hour. -2mol) 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 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 to obtain 5.51 g of product.

[0247] The resulting compound is 1 H-NMR confirmed that the compound had a structure represented by the following formula (AB):

[0248] Synthesis Example 15-2 A reaction vessel was charged with a compound represented by the following formula (AB): 5.00 g (1.61 × 10) of a compound represented by the formula -2 mol), toluene 5.00 g, trimethoxysilane 9.84 g (8.05 × 10 -2 mol), chloroplatinic acid / vinylsiloxane complex toluene solution 2.60 × 10 -3 g (8.05 x 10 as Pt alone) -9 mol), and formamide 3.30 × 10 -3 g (7.33 x 10 -5 The resulting mixture was 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.

[0249] The resulting compound is 1 H-NMR confirmed that the compound had a structure represented by the following formula (AC):

[0250] Synthesis Example 16-1: 5.00 g (1.53 × 10) of behenyl alcohol was placed in a reaction vessel. -2 mol), tetrahydrofuran 50.00 g, tetrabutylammonium iodide 5.65 × 10 -1 g (1.53 x 10 -3 mol), and 2.23 g (1.99 × 10 -2 mol) and aged at 50°C for 1 hour. -2mol) was added dropwise and the mixture was aged at 50°C for 24 hours. 10.00 g of 2 M hydrochloric acid was added to the resulting solution, and the aqueous layer was extracted three times with toluene. The combined organic layers were washed with pure water and saturated 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 to obtain 5.79 g of product.

[0251] The resulting compound is 1 H-NMR confirmed that the compound had a structure represented by the following formula (AD):

[0252] Synthesis Example 16-2 A reaction vessel was charged with a compound represented by the following formula (AD): 5.00 g (1.36 × 10 -2 mol), toluene 5.00 g, trimethoxysilane 8.32 g (6.81 × 10 -2 mol), chloroplatinic acid / vinylsiloxane complex toluene solution 2.60 × 10 -3 g (8.05 x 10 as Pt alone) -9 mol), and formamide 3.30 × 10 -3 g (7.33 x 10 -5 The resulting mixture was 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 a product.

[0253] The resulting compound is 1 H-NMR confirmed that the compound had a structure represented by the following formula (AE):

[0254] Synthesis Example 17-1: 5.00 g (1.85 × 10) of octadecyl alcohol was placed in a reaction vessel. -2 mol), tetrahydrofuran 50.00 g, tetrabutylammonium iodide 6.80 × 10 -1 g (1.85 x 10 -3 mol), and 2.28 g (2.03 × 10 -2 mol) and aged at 50°C for 1 hour. -2mol) 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 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 to obtain 5.38 g of product.

[0255] The resulting compound is 1 H-NMR confirmed that the compound had a structure represented by the following formula (AF):

[0256] Synthesis Example 17-2 A reaction vessel was charged with a compound represented by the following formula (AF): 5.00 g (1.54 × 10 -2 mol), toluene 5.00 g, trimethoxysilane 18.81 g (1.54 × 10 -1 mol), chloroplatinic acid / vinylsiloxane complex toluene solution 2.60 × 10 -3 g (8.05 x 10 as Pt alone) -9 mol), and acetic acid 3.15 × 10 -3 g (5.25 x 10 -5 The resulting mixture was 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 a product.

[0257] The resulting compound is 1 H-NMR confirmed that the compound had a structure represented by the following formula (AG):

[0258] Synthesis Example 18-1: 5.00 g (1.14 × 10) of myricyl alcohol was placed in a reaction vessel. -2 mol), tetrahydrofuran 50.00 g, tetrabutylammonium iodide 4.21 × 10 -1 g (1.14 x 10 -3 mol), and 1.92 g (1.71 × 10 -2 mol) and aged at 50°C for 1 hour. -2mol) 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 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 to obtain 4.49 g of product.

[0259] The resulting compound is 1 H-NMR confirmed that the compound had a structure represented by the following formula (AH):

[0260] Synthesis Example 18-2 A reaction vessel was charged with a compound represented by the following formula (AH): 5.00 g (1.01 × 10) of a compound represented by the formula -2 mol), toluene 5.00 g, triethoxysilane 8.33 g (5.07 × 10 -2 mol), and a toluene solution of chloroplatinic acid / vinylsiloxane complex 2.60 × 10 -3 g (8.05 x 10 as Pt alone) -9 The resulting mixture was 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 a product.

[0261] The resulting compound is 1 H-NMR confirmed that the compound had a structure represented by the following formula (AI):

[0262] Synthesis Example 19-1: 5.00 g (4.90 × 10 -2 mol), 10.00 g of 1,2-dichloroethane, and 9.80 g of tosyl chloride (5.14 × 10 -2 mol) was mixed and stirred at 0°C, and 5.20 g (5.14 × 10 -2 mol) 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, and the layers were separated. 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 then distilled off under reduced pressure to obtain 8.84 g of product.

[0263] The resulting compound is1 H-NMR confirmed that the compound had a structure represented by the following formula (AJ):

[0264] 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), 50.00 g of acetone, and 2.54 g (2.93 × 10 -2 mol) were mixed and aged for 24 hours at 25° C. The resulting solution was distilled to give 2.25 g of product.

[0265] The resulting compound is 1 H-NMR confirmed that the compound had a structure represented by the following formula (AK):

[0266] Synthesis Example 19-3: 5.00 g (1.85 × 10) of octadecyl alcohol was placed in a reaction vessel. -2 mol), tetrahydrofuran 50.00 g, tetrabutylammonium iodide 6.80 × 10 -1 g (1.85 x 10 -3 mol), and 2.28 g (2.03 × 10 -2 mol) were mixed and aged at 50°C for 1 hour. 6.11 g (3.70 × 10 -2 mol) 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 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 to obtain 5.25 g of product.

[0267] The resulting compound is 1 H-NMR confirmed that the compound had a structure represented by the following formula (AL):

[0268] Synthesis Example 19-4 A reaction vessel was charged with a compound represented by the following formula (AL): 5.00 g (1.41 × 10) of a compound represented by the formula -2mol), toluene 5.00 g, triethoxysilane 23.16 g (1.41 × 10 -1 mol), chloroplatinic acid / vinylsiloxane complex toluene solution 2.60 × 10 -3 g (8.05 x 10 as Pt alone) -9 mol), and formamide 3.30 × 10 -3 g (7.33 x 10 -5 The resulting mixture was 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 a product.

[0269] The resulting compound is 1 H-NMR confirmed that the compound had a structure represented by the following formula (AM):

[0270] Synthesis Example 20 A reaction vessel was charged with a compound of the following formula (AL) obtained in the same manner as in Synthesis Example 19-3. 5.00 g (1.41 × 10) of a compound represented by the formula -2 mol), toluene 40.00 g, 3-thiolpropyltrimethoxysilane 3.05 g (1.55 × 10 -2 mol), and 2,2'-azobis(isobutyrate) dimethyl 3.25 × 10 -1 g (1.41 x 10 -3 The resulting mixture was aged for 8 hours at 50° C. Thereafter, the solvent and unreacted materials were distilled off under reduced pressure to obtain 5.67 g of a product.

[0271] The resulting compound is 1 H-NMR confirmed that the compound had a structure represented by the following formula (AN):

[0272] Synthesis Example 21-1 In a reaction vessel, 25.00 g (1.55 × 10 -1 mol), 50.00 g of 1,2-dichloroethane, and 31.03 g (1.63 × 10 -1 mol) was mixed and stirred at 0°C, and 16.49 g (1.63 × 10 -1mol) 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, and the layers were separated. 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 then distilled off under reduced pressure to obtain 37.65 g of product.

[0273] The resulting compound is 1 H-NMR confirmed that the compound had a structure represented by the following formula (AO):

[0274] In a reaction vessel, a compound represented by the following formula (AO) 37.00 g (1.17 × 10 -1 mol), 250.00 g of acetone, and 15.28 g (1.76 × 10 -1 mol) were mixed and aged for 24 hours at 25° C. The resulting solution was distilled to give 11.60 g of product.

[0275] The resulting compound is 1 H-NMR confirmed that the compound had a structure represented by the following formula (AP):

[0276] Synthesis Example 21-2: 5.00 g (1.85 × 10) of octadecyl alcohol was placed in a reaction vessel. -2 mol), tetrahydrofuran 50.00 g, tetrabutylammonium iodide 6.80 × 10 -1 g (1.85 x 10 -3 mol), and 2.28 g (2.03 × 10 -2 mol) were mixed and aged at 50°C for 1 hour. 8.29 g (3.70 × 10 -2 mol) 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 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 to obtain 7.65 g of product.

[0277] The resulting compound is 1H-NMR confirmed that the compound had a structure represented by the following formula (AQ):

[0278] In a reaction vessel, a compound represented by the following formula (AQ) 7.00 g (1.69 × 10 -2 mol), 70.00 g of 1,2-dichloroethane, and 19.29 g (1.69 × 10 -1 The resulting mixture was 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.

[0279] The resulting compound is 1 H-NMR confirmed that the compound had a structure represented by the following formula (AR):

[0280] Synthesis Example 21-3 A reaction vessel was charged with a compound represented by the following formula (AR): 5.00 g (1.59 × 10 -2 mol), 10.0 g of tetrahydrofuran, and 3.27 g (1.59 × 10 -2 The resulting mixture was 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.

[0281] The resulting compound is 1 H-NMR confirmed that the compound had a structure represented by the following formula (AS):

[0282] Synthesis Example 22-1: In a reaction vessel, 10.00 g (3.38 × 10 -2 mol), tetrahydrofuran 10.00 g, 2-(tert-butoxycarbonylamino)-1-ethanol 5.72 g (3.55 × 10 -2 mol), and tetrakis(2-ethylhexyl) orthotitanate 1.03 × 10 -2 g (1.82 x 10 -5 The resulting mixture was 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 a product.

[0283] The resulting compound is1 H-NMR confirmed that the compound had a structure represented by the following formula (AT):

[0284] A reaction vessel was charged with the following formula (AT): 10.00 g (2.19 × 10 -2 mol), 50.00 g of 1,2-dichloroethane, and 24.97 g (2.19 × 10 -1 The resulting mixture was 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.

[0285] The resulting compound is 1 H-NMR confirmed that the compound had a structure represented by the following formula (AU):

[0286] Synthesis Example 22-2 A reaction vessel was charged with a compound represented by the following formula (AU): 5.00 g (1.40 × 10 -2 mol), 10.0 g of tetrahydrofuran, and 2.88 g (1.40 × 10 -2 The resulting mixture was 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.

[0287] The resulting compound is 1 H-NMR confirmed that the compound had a structure represented by the following formula (AV):

[0288] Synthesis Example 23-1: 5.00 g (1.69 × 10) of octadecyl isocyanate was placed in a reaction vessel. -2 mol), 10.00 g of tetrahydrofuran, and 2.85 g (1.78 × 10 -2 The resulting mixture was 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.

[0289] The resulting compound is 1 H-NMR confirmed that the compound had a structure represented by the following formula (AW):

[0290] A reaction vessel was charged with a compound represented by the following formula (AW): 7.00 g (1.54 × 10 -2 mol), 70.00 g of 1,2-dichloroethane, and 17.51 ​​g (1.54 × 10 -1 The resulting mixture was 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.

[0291] The resulting compound is 1 H-NMR confirmed that the compound had a structure represented by the following formula (AX):

[0292] Synthesis Example 23-2 A reaction vessel was charged with a compound represented by the following formula (AX): 5.00 g (1.41 × 10) of a compound represented by the formula -2 mol), 50.0 g of tetrahydrofuran, and 2.89 g (1.41 × 10 -2 The resulting mixture was 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.

[0293] The resulting compound is 1 H-NMR confirmed that the compound had a structure represented by the following formula (AY):

[0294] Synthesis Example 24-1 A reaction vessel was charged with a compound represented by the following formula (L) obtained in the same manner as in Synthesis Example 8-1. 5.00 g (1.48 × 10 -2 mol) and 50.00 g of tetrahydrofuran were mixed and stirred at 0° C. 2.96 mL (2.96×10) of a 1 M solution of diisobutylaluminum hydride in n-hexane was added thereto. -2 mol) was added and the mixture was aged at 25°C for 8 hours. While the obtained solution was cooled to 0°C, 20.00 g of pure water and 20.00 g of methanol were added and the layers were 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 to obtain 3.73 g of product.

[0295] The resulting compound is 1 H-NMR confirmed that the compound had a structure represented by the following formula (AZ):

[0296] Synthesis Example 24-2 A reaction vessel was charged with a compound represented by the following formula (AZ): 3.00 g (9.27 × 10 -3 mol), toluene 5.00 g, triethoxysilane 7.62 g (4.64 × 10 -2 mol), and a toluene solution of chloroplatinic acid / vinylsiloxane complex 2.60 × 10 -3 g (8.05 x 10 as Pt alone) -9 The resulting mixture was 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.

[0297] The resulting compound is 1 H-NMR confirmed that the compound had a structure represented by the following formula (BA):

[0298] Synthesis Example 25-1 A reaction vessel was charged with a compound represented by the following formula (AL) obtained in the same manner as in Synthesis Example 19-3. 5.00 g (1.41 × 10) of a compound represented by the formula -2 mol) and 10.00 g of tetrahydrofuran were mixed and stirred at 0°C. 36.7 mL of 9-borabicyclo[3.3.1]nonane / tetrahydrofuran solution (2.24 g (1.83 × 10) of 9-borabicyclo[3.3.1]nonane) was added thereto. -2 mol) was added dropwise, and the mixture was aged at 25° C. for 6 hours. After that, 15 mL of 30% by mass hydrogen peroxide solution and 90 mL (9.43×10) of saturated sodium bicarbonate aqueous solution were added. -2 mol) was added, and the mixture was aged at 25°C for 1 hour. A saturated aqueous solution of sodium thiosulfate was added to the resulting solution to stop 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 substances were distilled off under reduced pressure, and the mixture was washed with toluene to obtain 3.36 g of a product.

[0299] The resulting compound is 1H-NMR confirmed that the compound had a structure represented by the following formula (BB):

[0300] Synthesis Example 25-2 A reaction vessel was charged with a compound represented by the following formula (BB): 3.00 g (8.05 × 10 -3 mol), tetrahydrofuran 6.00 g, 3-isocyanatopropyltrimethoxysilane 1.65 g (8.05 × 10 -3 mol), and tetrakis(2-ethylhexyl) orthotitanate 1.03 × 10 -2 g (1.82 x 10 -5 The resulting mixture was 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.

[0301] The resulting compound is 1 H-NMR confirmed that the compound had a structure represented by the following formula (BC):

[0302] Synthesis Example 26-1: 5.00 g (1.69 × 10) of octadecyl isocyanate was placed in a reaction vessel. -2 mol), tetrahydrofuran 10.00 g, 4-penten-1ol 1.75 g (2.03 × 10 -2 mol), and tetrakis(2-ethylhexyl) orthotitanate 1.03 × 10 -2 g (1.82 x 10 -5 The resulting mixture was mixed with the above-mentioned components (mol) 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 a product.

[0303] The resulting compound is 1 H-NMR confirmed that the compound had a structure represented by the following formula (BD):

[0304] Synthesis Example 26-2 A reaction vessel was charged with a compound represented by the following formula (BD): 5.00 g (1.31 × 10 -2 mol), toluene 5.00 g, trimethoxysilane 8.00 g (6.55 × 10 -2 mol), chloroplatinic acid / vinylsiloxane complex toluene solution 2.60 × 10-3 g (8.05 x 10 as Pt alone) -9 mol) and acetic acid 3.15 x 10 -3 g (5.25 x 10 -5 The resulting mixture was 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 a product.

[0305] The resulting compound is 1 H-NMR confirmed that the compound had a structure represented by the following formula (BE):

[0306] Synthesis Example 27-1: 5.00 g (1.69 × 10) of octadecyl isocyanate was placed in a reaction vessel. -2 mol), tetrahydrofuran 10.00 g, 4-butene-1ol 1.46 g (2.03 × 10 -2 mol), and tetrakis(2-ethylhexyl) orthotitanate 1.03 × 10 -2 g (1.82 x 10 -5 The resulting mixture was mixed with the above-mentioned components (mol) 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 a product.

[0307] The resulting compound is 1 H-NMR confirmed that the compound had a structure represented by the following formula (BF):

[0308] Synthesis Example 27-2 A reaction vessel was charged with a compound represented by the following formula (BF): 5.00 g (1.36 × 10 -2 mol), toluene 5.00 g, trimethoxysilane 8.31 g (6.80 × 10 -2 mol), chloroplatinic acid / vinylsiloxane complex toluene solution 2.60 × 10 -3 g (8.05 x 10 as Pt alone) -9 mol) and acetic acid 3.15 x 10 -3 g (5.25 x 10 -5 The resulting mixture was 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.

[0309] The resulting compound is 1H-NMR confirmed that the compound had a structure represented by the following formula (BG):

[0310] Synthesis Example 28-1: 5.00 g (1.69 × 10) of octadecyl isocyanate was placed in a reaction vessel. -2 mol), tetrahydrofuran 10.00 g, 10-undecen-1-ol 3.46 g (2.03 × 10 -2 mol), and tetrakis(2-ethylhexyl) orthotitanate 1.03 × 10 -2 g (1.82 x 10 -5 mol) were mixed 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.

[0311] The resulting compound is 1 H-NMR confirmed that the compound had a structure represented by the following formula (BH):

[0312] Synthesis Example 28-2 A reaction vessel was charged with a compound represented by the following formula (BH): 2.00 g (4.29 × 10 -3 mol), toluene 2.00 g, trimethoxysilane 5.24 g (4.29 × 10 -2 mol), chloroplatinic acid / vinylsiloxane complex toluene solution 2.60 × 10 -3 g (8.05 x 10 as Pt alone) -9 mol) and acetic acid 3.15 x 10 -3 g (5.25 x 10 -5 The resulting mixture was 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 a product.

[0313] The resulting compound is 1 H-NMR confirmed that the compound had a structure represented by the following formula (BI):

[0314] Synthesis Example 29 A reaction vessel was charged with a compound represented by the following formula (BJ): 5.00 g (1.46 × 10 -2mol), toluene 40.00 g, trimethoxy(7-octen-1-yl)silane 4.07 g (1.75 × 10 -2 mol), and 2,2'-azobis(isobutyrate) dimethyl 4.56 × 10 -1 g (1.98 x 10 -3 The resulting mixture was 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 a product.

[0315] The resulting compound is 1 H-NMR confirmed that the compound had a structure represented by the following formula (BK):

[0316] Synthesis Example 30 A reaction vessel was charged with a compound represented by the following formula (H): 5.00 g (1.69 × 10 -2 mol), toluene 5.00 g, trichlorosilane 6.87 g (5.07 × 10 -2 mol), and a toluene solution of chloroplatinic acid / vinylsiloxane complex 2.60 × 10 -3 g (8.05 x 10 as Pt alone) -9 The resulting mixture (containing 1.5 mol) was mixed with 15.00 g of toluene 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.

[0317] The resulting compound is 1 H-NMR confirmed that the compound had a structure represented by the following formula (BL):

[0318] Synthesis Example 31 A reaction vessel was charged with a compound represented by the following formula (Z) obtained in the same manner as in Synthesis Example 14-2. 1.00 g (2.52 × 10 -3 mol), toluene 1.00 g, trichlorosilane 1.02 g (7.56 × 10 -3 mol), and a toluene solution of chloroplatinic acid / vinylsiloxane complex 7.54 × 10 -3 g (2.33 x 10 as Pt alone)-8 The resulting mixture (containing 1.00 mol) was mixed with 3.00 g of toluene 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 x 10 product. -1 g was obtained.

[0319] The resulting compound is 1 H-NMR confirmed that the compound had a structure represented by the following formula (BM):

[0320] Synthesis Example 32-1: 5.00 g (3.22 × 10 -2 mol), tetrahydrofuran 10.00 g, ethylene glycol monoallyl ether 3.45 g (3.38 × 10 -2 mol), and tetrakis(2-ethylhexyl) orthotitanate 1.03 × 10 -2 g (1.82 x 10 -5 The mixture was mixed with the above components (mol) and aged at room temperature for 24 hours. The solvent and unreacted materials were removed by distillation under reduced pressure, and then the mixture was treated with activated carbon, and the solvent was removed by distillation under reduced pressure to obtain 7.96 g of a product.

[0321] The resulting compound is 1 H-NMR confirmed that the compound had a structure represented by the following formula (BN):

[0322] Synthesis Example 32-2 A reaction vessel was charged with a compound represented by the following formula (BN): 5.00 g (1.94 × 10 -2 mol), toluene 5.00 g, trimethoxysilane 11.87 g (9.71 × 10 -2 mol), chloroplatinic acid / vinylsiloxane complex toluene solution 2.60 × 10 -3 g (8.05 x 10 as Pt alone) -9 mol), and formamide 3.30 × 10 -3 g (7.33 x 10 -5The resulting mixture was 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 a product.

[0323] The resulting compound is 1 H-NMR confirmed that the compound had a structure represented by the following formula (BO):

[0324] Synthesis Example 33 A reaction vessel was charged with a compound represented by the following formula (BP): 53.17 g (1.98 × 10) of a compound represented by the formula -1 mol), 5.00 g (1.98 × 10 -2 mol), toluene 38.50 g, toluene solution of chloroplatinic acid / vinylsiloxane complex 2.60 × 10 -3 g (8.05 x 10 as Pt alone) -9 mol), and formamide 3.30 × 10 -3 g (7.33 x 10 -5 The resulting mixture was aged for 1 hour at 80° C. Thereafter, the solvent and unreacted materials were distilled off under reduced pressure to obtain 9.70 g of a product.

[0325] The resulting compound is 1 H-NMR confirmed that the compound had a structure represented by the following formula (BQ):

[0326] Synthesis Example 33 A reaction vessel was charged with a compound represented by the following formula (BQ): 5.00 g (9.60 × 10 -3 mol), toluene 5.00 g, allyltrimethoxysilane 1.56 g (9.60 × 10 -3 mol), chloroplatinic acid / vinylsiloxane complex toluene solution 2.60 × 10 -3 g (8.05 x 10 as Pt alone) -9 mol), and acetic acid 3.15 × 10 -3 g (5.25 x 10 -5 The resulting mixture was 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 a product.

[0327] The resulting compound is 1H-NMR confirmed that the compound had a structure represented by the following formula (BR):

[0328] Synthesis Example 34-1 A reaction vessel was charged with 3.38 g (2.79 × 10 -2 mol), p-toluenesulfonylmethyl isocyanide 3.63 g (1.86 × 10 -2 mol), 46.5 mL (60.5 g) of 1-butyl-3-methylimidazolium bromide, and 7.72 g (5.59 × 10 -2 mol) and aged at 50°C for 24 hours. -2 mol) was 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 layers were washed with pure water and saturated saline, and dried over magnesium sulfate. Thereafter, the mixture was 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.

[0329] The resulting compound is 1 H-NMR confirmed that the compound had a structure represented by the following formula (BS):

[0330] Synthesis Example 34-2 A reaction vessel was charged with a compound represented by the following formula (BS): 4.00 g (1.11 × 10 -2 mol), toluene 4.00 g, trimethoxysilane 13.52 g (1.11 × 10 -1 mol), chloroplatinic acid / vinylsiloxane complex toluene solution 2.60 × 10 -3 g (8.05 x 10 as Pt alone) -9 mol), and formamide 3.30 × 10 -3 g (7.33 x 10 -5 The resulting mixture was 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.

[0331] The resulting compound is 1 H-NMR confirmed that the compound had a structure represented by the following formula (BT):

[0332] 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), the following formula (BV) 1.34 g (2.03 × 10) of a compound represented by the formula -2 mol) 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) of sodium ascorbate was added thereto. -2 mol), and 4.22 g of copper(II) sulfate pentahydrate (1.69×10 -2 The resulting mixture (mol) was mixed 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 layers were washed with pure water and saturated brine, and dried over magnesium sulfate. Then, activated carbon treatment was performed, and the solvent and unreacted materials were distilled off under reduced pressure. The resulting crude product was washed with methanol, yielding 4.95 g of product.

[0333] The resulting compound is 1 H-NMR confirmed that the compound had a structure represented by the following formula (BW):

[0334] Synthesis Example 35-2 A reaction vessel was charged with a compound represented by the following formula (BW): 4.00 g (1.11 × 10 -2 mol), toluene 4.00 g, trimethoxysilane 13.52 g (1.11 × 10 -1 mol), chloroplatinic acid / vinylsiloxane complex toluene solution 2.60 × 10 -3 g (8.05 x 10 as Pt alone) -9 mol), and formamide 3.30 × 10 -3 g (7.33 x 10 -5 The resulting mixture was 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 a product.

[0335] The resulting compound is 1 H-NMR confirmed that the compound had a structure represented by the following formula (BX):

[0336] Synthesis Example 36 A reaction vessel was charged with a compound represented by the following formula (AX), which was obtained in the same manner as in Synthesis Example 23-2. 5.00 g (1.41 × 10) of a compound represented by the formula -2 mol), tetrahydrofuran 10.00 g, Karenz AOI (2-(acryloyloxy)ethyl isocyanate) 2.08 g (1.47 × 10 -2 The resulting mixture was 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.

[0337] The resulting compound is 1 H-NMR confirmed that the compound had a structure represented by the following formula (BY):

[0338] Synthesis Example 37 A reaction vessel was charged with a compound represented by the following formula (Y) obtained in the same manner as in Synthesis Example 14-1. 5.00 g (1.40 × 10 -2 mol), toluene 25.00 g, phosphorus oxychloride 2.36 g (1.54 × 10 -2 The resulting mixture was mixed with 20.00 g of water 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. The aqueous layer was then removed by separation, and the solvent and unreacted materials were distilled off under reduced pressure to obtain 5.20 g of a product.

[0339] The resulting compound is 1 H-NMR confirmed that the compound had a structure represented by the following formula (BZ):

[0340] Synthesis Example 38 A reaction vessel was charged with a compound represented by the following formula (CA): 5.00 g (1.42 × 10 -2 mol), toluene 5.00 g, trimethoxysilane 8.66 g (7.09 × 10 -2 mol), chloroplatinic acid / vinylsiloxane complex toluene solution 2.60 × 10 -3 g (8.05 x 10 as Pt alone) -9 mol) and acetic acid 3.15 x 10 -3 g (5.25 x 10 -5The resulting mixture was 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 a product.

[0341] The resulting compound is 1 H-NMR confirmed that the compound had a structure represented by the following formula (CB):

[0342] Synthesis Example 39 A reaction vessel was charged with a compound represented by the following formula (BJ): 5.00 g (1.46 × 10 -2 mol), toluene 40.00 g, vinyltrimethoxysilane 2.38 g (1.61 × 10 -2 mol), and 2,2'-azobis(isobutyrate) dimethyl 4.56 × 10 -1 g (1.98 x 10 -3 The resulting mixture was 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 a product.

[0343] The resulting compound is 1 H-NMR confirmed that the compound had a structure represented by the following formula (CC):

[0344] Synthesis Example 40-1: 100.00 g (5.87 × 10 －１ mol), tetrahydrofuran 500.00 g, tetrabutylammonium iodide 21.68 g (5.87 × 10 －２ mol), and 98.86 g (8.81 × 10 －１ mol) and aged at 50°C for 1 hour. －１ mol) 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 layers were washed with pure water and saturated brine 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 to obtain 81.55 g of product.

[0345] The resulting compound is １H-NMR confirmed that the compound had a structure represented by the following formula (DA):

[0346] Synthesis Example 40-2 A reaction vessel was charged with a compound represented by the following formula (DA): 65.00 g (2.09 × 10 －１ mol), toluene 50.00 g, 3-thiolpropyltrimethoxysilane 45.20 g (2.30 × 10 －１ mol), and 4.81 g (2.09 × 10) of dimethyl 2,2'-azobis(isobutyrate). －２ The resulting mixture was 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 a product.

[0347] The resulting compound is １ H-NMR confirmed that the compound had a structure represented by the following formula (DB):

[0348] 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.

[0349] 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.

[0350] 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.

[0351] 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.

[0352] 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.

[0353] 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.

[0354] 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.

[0355] 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.

[0356] 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.

[0357] 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.

[0358] 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.

[0359] 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.

[0360] 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.

[0361] 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.

[0362] 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.

[0363] 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.

[0364] 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.

[0365] 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.

[0366] 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.

[0367] 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.

[0368] 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.

[0369] 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.

[0370] 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.

[0371] 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.

[0372] 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.

[0373] 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.

[0374] 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.

[0375] 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.

[0376] [Comparative Example 1] The following formula (A') A surface treatment agent was prepared by dissolving the compound represented by the following formula in toluene to a concentration of 0.1% by mass.

[0377] [Comparative Example 2] The following formula (B') A surface treatment agent was prepared by dissolving the compound represented by the following formula in toluene to a concentration of 0.1% by mass.

[0378] Comparative Example 3 No surface treatment agent.

[0379] 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 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.

[0380] The glass on which the cured coating was formed was evaluated for water repellency, slipperiness, ease of wiping, and abrasion resistance by the methods described below. Note that the same evaluation was 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.

[0381] 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. Initially, both the Examples and Comparative Examples showed good water repellency.

[0382] 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. [Conditions for evaluating slipperiness] Load: 100 gf Stroke: 100 mm Contact area: 1 x 3 cm 2 Nonwoven fabric: BEMCOT (manufactured by Asahi Kasei Corporation)

[0383] 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), after which the ink was dried and wiped off with tissue paper. The number of times it took to wipe off the ink was evaluated according to the following criteria. Dirt wiping ability rated A or B was evaluated as good. The results are shown in Table 1. [Dirt wiping ability evaluation criteria] A: 4 or fewer rubs B: 5 or more rubs C: Ink could not be wiped off

[0384] 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 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: 1 cm 2 Travel distance (one way): 40 mm Travel speed: 4,800 mm / min Load: 500 gf / 1 cm 2

[0385] The cured coatings of the surface treatment agents of Examples 1 to 28 exhibited water repellency and dirt wipeability due to the presence of a hydrocarbon chain having 1 to 60 carbon atoms at the molecular chain terminal of the compound used, thereby improving the mobility of the molecular chain. Furthermore, the presence of 1 to 3 linking functional groups in the molecular chain of the compound used improved intermolecular interactions and molecular mobility, resulting in good slipperiness 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 slipperiness 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 slipperiness and abrasion resistance. Comparative Example 3 was a glass substrate without a surface treatment agent, but since it was not surface-treated, neither of these characteristics were present, and the effects of the Examples can 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.

[0386]

[0387] 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.

[0388] 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.

[0389] 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.

[0390] 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.

[0391] 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.

[0392] 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.

[0393] 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.

[0394] 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.

[0395] 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.

[0396] 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.

[0397] 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.

[0398] 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.

[0399] 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.

[0400] 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.

[0401] 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.

[0402] 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.

[0403] 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.

[0404] 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.

[0405] 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.

[0406] 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.

[0407] 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.

[0408] 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.

[0409] 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.

[0410] 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.

[0411] 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.

[0412] 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.

[0413] 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.

[0414] 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.

[0415] Comparative Example 4 The compound represented by the above formula (A') was dissolved in dibutyl ether to a concentration of 10% by mass to prepare a surface treatment agent.

[0416] Comparative Example 5 The compound represented by the above formula (B') was dissolved in toluene to a concentration of 10% by mass to prepare a surface treatment agent.

[0417] Comparative Example 6 No surface treatment agent.

[0418] Preparation of Surface Treatment Agents and Formation of Hardened 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 The coating was cured at 80°C and 80% relative humidity for 1 hour, and then at 25°C and 50% relative humidity for 12 hours to form a cured coating having a thickness of 3 to 5 nm.

[0419] The glass on which the cured coating was formed was evaluated for water repellency, slipperiness, dirt wiping ability, and abrasion resistance by the methods described below. Note that the same evaluation was carried out for Comparative Example 6, 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.

[0420] 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. Initially, both the Examples and Comparative Examples showed good water repellency.

[0421] 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. [Conditions for evaluating slipperiness] Load: 100 gf Stroke: 100 mm Contact area: 1 x 3 cm 2 Nonwoven fabric: BEMCOT (manufactured by Asahi Kasei Corporation)

[0422] 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), after which the ink was dried and wiped off with tissue paper. The number of times it took to wipe off the ink was evaluated according to the following criteria. Dirt wiping ability rated A or B was evaluated as good. The results are shown in Table 2. [Dirt wiping ability evaluation criteria] A: 4 or fewer rubs B: 5 or more rubs C: Ink could not be wiped off

[0423] 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 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: 1 cm 2 Travel distance (one way): 40 mm Travel speed: 4,800 mm / min Load: 500 gf / 1 cm 2

[0424] The cured coatings of the surface treatment agents of Examples 29 to 56 exhibited water repellency and dirt wiping properties due to the presence of hydrocarbon chains having 1 to 60 carbon atoms at the molecular chain terminals of the compounds used, thereby improving the mobility of the molecular chains. Furthermore, the presence of 1 to 3 linking functional groups in the molecular chains of the compounds used improved intermolecular interactions and molecular mobility, resulting in good slip properties and abrasion resistance. The cured coatings of the surface treatment agent of Comparative Example 4 exhibited water repellency due to the presence of hydrocarbon chains having 1 to 60 carbon atoms at the molecular chain terminals of the compounds used, but the absence of a linking functional group in the molecular chains of the compounds used resulted in poor slip properties and abrasion resistance. The cured coatings of the surface treatment agent of Comparative Example 5 exhibited high water repellency and dirt wiping properties due to the presence of fluorohydrocarbon chains at the molecular chain terminals of the compounds used, but the absence of a linking functional group in the molecular chains of the compounds used resulted in poor slip properties and abrasion resistance. Comparative Example 6 is a glass substrate that did not use a surface treatment agent, and since it was not surface-treated, none of the properties were present, and the effects of the Examples can be confirmed. As described above, with the surface treatment agents of the Examples, a cured coating that was excellent in water repellency, slipperiness, dirt wiping ability, and abrasion resistance at high levels was obtained even by vapor deposition coating.

[0425]

Claims

1. The following general formula (1) (wherein 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.

2. A in the formula (1) is represented by the following general formula (2): (In the formula, R 1 are independently an alkyl group or a phenyl group having 1 to 4 carbon atoms, X is independently a hydroxyl group or a hydrolyzable group, and n is an integer of 1 to 3.) or a group represented by the following general formula (3):

2. The hydrocarbon terminal group-containing compound according to claim 1, which is a hydroxyl group-containing silyl group or a hydrolyzable silyl group represented by the formula: (wherein n" is a number from 0 to 3, and n' is (3-n") / 2).

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

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

5. The hydrocarbon terminal group-containing compound according to claim 1, wherein in formula (1), Z's independently represent a divalent group selected from the group consisting of 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.

6. In the formula (1), Y independently represents the following general formula (4): (In the formula, R 2 R is independently a monovalent hydrocarbon group having 1 to 10 carbon atoms, which may be linear, branched, or cyclic, or a combination thereof. 3 are independently optionally substituted divalent cyclic hydrocarbon groups having 3 to 10 carbon atoms. a is an integer from 0 to 30, b is an integer from 0 to 15, c is an integer from 0 to 10, and d is an integer from 0 to 6, and the sum of a, b, c, and d is an integer such that the 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.

7. In the formula (1), k is 1 and R is represented by the following general formula (5): (In the formula, R 4 is a methyl group, a cyclic alkyl group, or a phenyl group. 3 are divalent cyclic hydrocarbon groups having 3 to 10 carbon atoms, each of which may independently have a substituent. y is an integer of 0 or greater, 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.

8. The hydrocarbon terminal group-containing compound according to claim 1, wherein k is 2 or 3 in formula (1).

9. A surface treatment agent comprising the hydrocarbon terminal group-containing compound according to any one of claims 1 to 8.

10. An article surface-treated with the surface treatment agent according to claim 9.

Images