Compound, surface treatment agent, article, and method for producing article

Abstract

Provided are: a compound which is capable of forming a surface layer that has excellent water resistance and excellent perspiration resistance; a surface treatment agent; an article which has a surface layer that is formed of the compound; and a method for producing the article.　This compound is represented by X-L1-Q1-(L2-T1)n. In the formula, X is a monovalent organosiloxane group; L1 is a straight-chain alkylene group having 23 or more carbon atoms, which may have -C(=O)O- or the like; Q1 is *-CRQ1(-**)2 or the like; RQ1 is a hydrogen atom or an alkyl group which may have O-; * denotes a bonding position to L1; ** denotes a bonding position to L2; L2 is a hydrocarbon group which may have -O-, or the like; T1 is a group having a reactive silyl group; in cases where Q1 is *-CRQ1(-**)2, n is 2; the plurality of L2 may be the same or different; and the plurality of T1 may be the same or different.

Description

Compound, surface treatment agent, article, and method for manufacturing an article

[0001] The present invention relates to a compound, a surface treatment agent, an article, and a method for manufacturing an article.

[0002] In various fields such as electric and electronic materials, semiconductor materials, optical materials, building materials, and automotive parts, a method of forming a surface layer on the surface of a member (substrate) is known for the purpose of suppressing the adhesion of dirt to the member to be used. For example, Patent Document 1 discloses a method of forming a surface layer on the surface of a substrate using a surface treatment agent containing a silane compound represented by the following formula.

[0003]

[0004] International Publication No. 2024 / 034669

[0005] In recent years, the required performance of the surface layer has been increasing, and depending on its use, a surface layer excellent in water resistance and sweat resistance is required. When the present inventors evaluated the surface layer formed using the above compound described in Patent Document 1, they found that the water resistance and sweat resistance of the surface layer were insufficient and there was room for improvement.

[0006] The present invention has been made in view of the above problems, and an object thereof is to provide a compound capable of forming a surface layer excellent in water resistance and sweat resistance, a surface treatment agent, an article having a surface layer formed from the compound, and a method for manufacturing the article.

[0007] As a result of intensive studies on the above problems, the present inventors have found that the above problems can be solved by the following configuration. [1] A compound represented by the following formula (1). X-L １ -Q １ -(L ２ -T １ ) ｎ (1) However, X is a monovalent organosiloxane group, L １ is a linear alkylene group having 23 or more carbon atoms which may have -C(=O)O-, -C(=O)-, -O-, or a phenylene group, Q １ is *-CR Ｑ１ (-**) ２ *, -C(-**)３ , *-N(-**) ２ *-SiR Ｑ１ (-**) ２ , *-Si(-**) ３ , or a (1+n) valency ring structure, R Ｑ１ is a hydrogen atom or an alkyl group which may have -O-, and * is L １ This indicates the bonding position with L. ２ This indicates the bonding position with L ２ T is a hydrocarbon group which may have a single bond or an -O- bond. １ Q is a group having a reactive silyl group. １ *-CR Ｑ１ (-**) ２ , *-N(-**) ２ , or *-SiR Ｑ１ (-**) ２ If this is the case, then n is 2, and Q １ *-C(-**) ３ , or *-Si(-**) ３ If that is the case, then n is 3, and Q １ If the ring structure has (1+n) valencies, then n is an integer greater than or equal to 2, and there are multiple L ２ They may be the same or different, and there may be multiple T １ They may be the same or different. [2] The compound according to [1] in which the number of silicon atoms contained in X in formula (1) is greater than the number of n in formula (1). [3] The compound according to [1] or [2] in which n in formula (1) is 2. [4] T in formula (1) １ However, a compound represented by the following formula (2), as described in any of [1] to [3]. -SiR ａ１ ｚ１ R ａ１１ ３－ｚ１ (2) However, R ａ１ R is a hydrolyzable group, a group having a hydrolyzable group, or a hydroxyl group. ａ１１ is a hydrocarbon group, z1 is an integer from 1 to 3, and R ａ１ , or R ａ１１ If there are multiple Rａ１ , or R ａ１１ These may be the same or different. [5] A surface treatment agent comprising the compound described in any of [1] to [4]. [6] The surface treatment agent according to [5], further comprising a liquid medium. [7] The surface treatment agent according to [5] or [6], which is an antifouling coating agent or a waterproof coating agent. [8] An article having a surface layer formed using the compound described in any of [1] to [4] on the surface of a substrate. [9] The article according to [8], which is an optical component.

[10] The article according to [8] or [9], which has the above surface layer on the surface of a component constituting the surface touched by a finger on a touch panel.

[11] A method for manufacturing an article, comprising forming a surface layer by a dry coating method using the surface treatment agent described in any of [5] to [7].

[12] A method for manufacturing an article, comprising forming a surface layer by a wet coating method using the surface treatment agent described in any of [5] to [7].

[0008] According to the present invention, it is possible to provide a compound capable of forming a surface layer with excellent water resistance and sweat resistance, a surface treatment agent, an article having a surface layer formed from the compound, and a method for manufacturing the article.

[0009] This is a schematic cross-sectional view showing an example of an article of the present invention.

[0010] The meanings of terms used in this invention are as follows: "Reactive silyl group" is a general term for hydrolyzable silyl groups and silanol groups (Si-OH), and "hydrolyzable silyl group" means a group that can form a silanol group through hydrolysis. "Organic group" means a hydrocarbon group that may have substituents and may have heteroatoms or other bonds in its carbon chain. "Hydrogen group" means an aliphatic hydrocarbon group (linear alkylene group, branched alkylene group, cycloalkylene group, etc.), an aromatic hydrocarbon group (phenylene group, etc.), or a group consisting of a combination thereof. "Surface layer" means a layer formed on the surface of a substrate. The "~" indicating a numerical range means that the values ​​described before and after it are included as the lower and upper limits, respectively. In numerical ranges described stepwise in this disclosure, the upper or lower limit described in one numerical range may be replaced with the upper or lower limit of another numerical range described stepwise. Also, in numerical ranges described in this disclosure, the upper or lower limit of that numerical range may be replaced with the values ​​shown in the examples. In this disclosure, each component may contain multiple types of the corresponding substance. When multiple types of the substance corresponding to each component are present in the composition, the content or amount of each component means the total content or amount of the multiple types of substances present in the composition, unless otherwise specified. The bonding order in each divalent group is not limited unless otherwise specified. In this specification, when a compound or group is represented by a specific formula (X), the compound or group represented by formula (X) may be written as compound (X) or compound X, and group (X) or group X, respectively. When the same symbols are present in a single chemical formula, the same symbols may represent the same structure or different structures within a defined range. In this specification, "Me" may represent a methyl group and "Et" may represent an ethyl group.

[0011] [Compound 1] The compound of the present invention is represented by the following formula (1).

[0012] X-L １ - Q １ - (L ２ -T １ )ｎ (1)

[0013] In formula (1), X is a monovalent organosiloxane group, and L １ Q is a linear alkylene group having 23 or more carbon atoms, which may have -C(=O)O-, -C(=O)-, -O-, or a phenylene group. １ *-CR Ｑ１ (-**) ２ , *-C(-**) ３ , *-N(-**) ２ *-SiR Ｑ１ (-**) ２ , *-Si(-**) ３ , or a (1+n) valency ring structure, R Ｑ１ is a hydrogen atom or an alkyl group which may have -O-, and * is L １ This indicates the bonding position with L. ２ This indicates the bonding position with L ２ T is a hydrocarbon group which may have a single bond or an -O- bond. １ Q is a group having a reactive silyl group. １ *-CR Ｑ１ (-**) ２ , *-N(-**) ２ , or *-SiR Ｑ１ (-**) ２ If this is the case, then n is 2, and Q １ *-C(-**) ３ , or *-Si(-**) ３ If that is the case, then n is 3, and Q １ If the ring structure has (1+n) valencies, then n is an integer greater than or equal to 2, and there are multiple L ２ They may be the same or different, and there may be multiple T １ They may be the same or different.

[0014] Compound 1 can form a surface layer with excellent water resistance and sweat resistance. The details of the reason for this are still unknown, but it is believed that the long-chain alkylene group (L in formula (1)) may have a specific group. １ It is presumed that having this feature will suppress the deterioration of the surface layer when it comes into contact with water or sweat for a long period of time.

[0015] X is a monovalent organosiloxane group. From the viewpoint of more excellent effects of the present invention, the group represented by the following formula (X1) is preferable as the monovalent organosiloxane group. [R Ｘ１ -Q Ｘ１ -(Si(R Ｘ２ )) ２ -O) ｐ１ ｑ１ -Si(R Ｘ２ )) ｑ２ -* (X1)

[0016] In the formula (X1), R Ｘ１ are each independently (R Ｘ１１ )) ３ Si-, a monovalent cyclic polysiloxane residue, or a monovalent cage-shaped polysiloxane residue, and R Ｘ１１ are each independently a hydrocarbon group or a trialkylsilyloxy group, Q Ｘ１ are each independently an oxygen atom or an alkylene group. When p1 is 0, Q Ｘ１ is an oxygen atom, R Ｘ２ are each independently a hydrocarbon group, p1 are each independently a number from 0 to 100, q1 is an integer from 1 to 3, q2 is an integer from 0 to 2, and q1 + q2 is 3.

[0017] In (R Ｘ１ )) Ｘ１１ Si- of R ３ , R Ｘ１１ is a hydrocarbon group or a trialkylsilyloxy group. As the hydrocarbon group in R Ｘ１１ , an alkyl group or an aryl group is preferable, and an alkyl group is more preferable. The number of carbon atoms of the alkyl group is preferably 1 to 10, more preferably 1 to 8, and still more preferably 1 to 4. The same applies to the alkyl group in the trialkylsilyloxy group. When the number of carbon atoms of the alkyl group is 3 or more, the alkyl group having 3 or more carbon atoms may be linear, branched, or have a ring structure, but is preferably linear. The trialkylsilyloxy group of R Ｘ１１ is (R Ｘ１２ )) ３ ​Examples of groups represented by SiO- include R Ｘ１２ Each of these is independently a hydrocarbon group. Ｘ１２ The hydrocarbon group is R Ｘ１１ Similar examples include R. Ｘ１１ Specific examples include methyl group, ethyl group, n-propyl group, n-butyl group, and tert-butyl group, with methyl group or ethyl group being preferred, and methyl group being more preferred.

[0018] Multiple R Ｘ１１ They may be the same or they may be different from each other, but from the viewpoint of ease of manufacture, it is preferable that they be the same.

[0019] (R Ｘ１１ ) ３ Examples of groups represented by Si- include methyldiethylsilyl group, methylethylpropylsilyl group, methylethylbutylsilyl group, methyldipropylsilyl group, methylpropylbutylsilyl group, methyldibutylsilyl group, dimethylethylsilyl group, dimethylpropylsilyl group, dimethylbutylsilyl group, trimethylsilyl group, triethylsilyl group, tri-n-propylsilyl group, tri-isopropylsilyl group, and trialkylsilyloxy groups having these groups. From the viewpoint of superior liquid repellency of the surface layer, (R Ｘ１１ ) ３ The three R's in Si- Ｘ１１ Preferably, all of them are alkyl groups having 1 to 4 carbon atoms, more preferably methyl groups or ethyl groups, and even more preferably methyl groups.

[0020] R Ｘ１ The monovalent cyclic organopolysiloxane residue in is preferably a group represented by the following formula (A1).

[0021] However, R ８ Each of these is independently a hydrocarbon group, a hydrocarbon group with a substituent, or a trialkylsilyloxy group, and t1 is an integer from 1 to 4.

[0022] R ８In the hydrocarbon group, alkyl groups or aryl groups are preferred, with alkyl groups being more preferred. The number of carbon atoms in the alkyl group is preferably 1 to 10, more preferably 1 to 8, and even more preferably 1 to 4. The same applies to the alkyl group in the trialkylsilyloxy group. The three alkyl groups contained in the trialkylsilyloxy group may be the same or different from each other. When the alkyl group has 3 or more carbon atoms, the alkyl group with 3 or more carbon atoms may be linear, branched, or have a cyclic structure, but it is preferable that it be linear. Examples of substituents in the hydrocarbon group having substituents include halogen atoms, hydroxyl groups, alkoxy groups, trialkylsilyloxy groups, trialkylsilyl groups, amino groups, nitro groups, cyano groups, sulfonyl groups, trifluoromethyl groups, etc. ８ The trialkylsilyloxy group is R Ｘ１１ Similar examples include R. ８ Specific examples include methyl group, ethyl group, n-propyl group, n-butyl group, tert-butyl group, isobutyl group, and heptyl group, with methyl group or ethyl group being preferred, and methyl group being more preferred.

[0023] Multiple R ８ They may be identical or different from each other, but from the standpoint of ease of manufacture, it is preferable that they be identical.

[0024] Specific examples of monovalent cyclic organopolysiloxane residues include the following groups, where * indicates the binding site.

[0025]

[0026]

[0027] The monovalent cage-like organopolysiloxane residue is preferably a group represented by the following formula (A2).

[0028] However, R ９ Each of these is independently a hydrocarbon group, a substituted hydrocarbon group, or a trialkylsilyloxy group. * indicates the bond position.

[0029] R９ In the hydrocarbon group, alkyl groups or aryl groups are preferred, with alkyl groups being more preferred. The number of carbon atoms in the alkyl group is preferably 1 to 10, more preferably 1 to 8, and even more preferably 1 to 4. The same applies to alkyl groups in the trialkylsilyloxy group. When the number of carbon atoms in the alkyl group is 3 or more, the alkyl group with 3 or more carbon atoms may be linear, branched, or have a cyclic structure, but it is preferable that it be linear. Examples of substituents in the hydrocarbon group having substituents include halogen atoms, hydroxyl groups, alkoxy groups, trialkylsilyloxy groups, trialkylsilyl groups, amino groups, nitro groups, cyano groups, sulfonyl groups, trifluoromethyl groups, etc. ９ The trialkylsilyloxy group is R Ｘ１１ Similar examples include R. ９ Specific examples include methyl group, ethyl group, n-propyl group, n-butyl group, and tert-butyl group, with methyl group or ethyl group being preferred, and methyl group being more preferred.

[0030] Multiple R ９ They may be the same or they may be different from each other, but from the viewpoint of ease of manufacture, it is preferable that they be the same.

[0031] The following are specific examples of monovalent cage-like organopolysiloxane residues. * indicates the binding site.

[0032]

[0033] R Ｘ１ (R Ｘ１１ ) ３ Si- is preferred, (CH ３ ) ３ Si- is preferred.

[0034] Q in equation (X1) Ｘ１ is an oxygen atom or an alkylene group. However, if p1 is 0, Q Ｘ１ It is an oxygen atom. Q Ｘ１The number of carbon atoms in the alkylene group is preferably 1 to 30, more preferably 1 to 12, and even more preferably 1 to 6. When the alkylene group has 3 or more carbon atoms, the alkyl group with 3 or more carbon atoms may be linear, branched, or have a cyclic structure, but it is preferably linear. Specific examples of alkylene groups include methylene, ethylene, propylene, butylene, and hexylene groups. Q Ｘ１ From the standpoint of superior liquid repellency, an oxygen atom or a linear alkylene group having 1 to 6 carbon atoms is preferred, an oxygen atom, a methylene group, or an ethylene group is more preferred, and an oxygen atom is even more preferred.

[0035] Equation (X1) - (Si(R Ｘ２ ) ２ -O) ｐ１ represents a linear organopolysiloxane, and p1 is a number from 0 to 100. Also, in formula (X1), -(Si(R Ｘ２ ) ２ -O) ｐ１ , and Si(R Ｘ２ ) ｑ２ - in R Ｘ２ Each of these is independently a hydrocarbon group.

[0036] R Ｘ２ The hydrocarbon group in is preferably an alkyl group or an aryl group. The alkyl group preferably has 1 to 10 carbon atoms, more preferably 1 to 8, and even more preferably 1 to 4 carbon atoms. When the alkyl group has 3 or more carbon atoms, the alkyl group with 3 or more carbon atoms may be linear, branched, or have a cyclic structure, but it is preferable that it be linear or branched. Specific examples of alkyl groups include methyl, ethyl, n-propyl, n-butyl, and tert-butyl groups. Specific examples of aryl groups include phenyl and naphthyl groups. Ｘ２ From the standpoint of superior liquid repellency, methyl groups, ethyl groups, tert-butyl groups, or phenyl groups are preferred, methyl groups or ethyl groups are more preferred, and methyl groups are even more preferred.

[0037] Multiple R Ｘ２They may be identical or different from each other, but from the viewpoint of ease of manufacture, it is preferable that they be identical.

[0038] p1 is a number from 0 to 100. From the viewpoint of superior wear resistance, p1 is preferably a number from 0 to 50, more preferably a number from 0 to 20, and particularly preferably a number from 0 to 8. In formula (X1), "(Si(R Ｘ２ ) ２ The number of repeating units p1, represented as "-O"), is an average value calculated from data obtained by measuring compounds having the structure p1 using nuclear magnetic resonance (NMR).

[0039] q1 is an integer between 1 and 3, q2 is an integer between 0 and 2, and q1 + q2 is 3. More specifically, when q1 is 1, q2 is 2, when q1 is 2, q2 is 1, and when q1 is 3, q2 is 0. When q1 is 2 or 3, multiple [R] in equation (X1) Ｘ１ - Q Ｘ１ - (Si(R Ｘ２ ) ２ -O) ｐ１ The structures shown in [ ] may be identical or different from each other, but from the viewpoint of ease of manufacture, it is preferable that they be identical.

[0040] The group X1 is preferably the group represented by the following formula: R Ｘ１ -O-(Si(R Ｘ２ ) ２ -O) ｐ１ -Si(R Ｘ２ ) ２ -* (X1-1) [R Ｘ１ -O-(Si(R Ｘ２ ) ２ -O) ｐ１ ] ２ -SiR Ｘ２ - * (X1-2) The definitions of each symbol in these formulas are the same as those of each symbol in formula (X1) described above, and the preferred embodiments are also the same.

[0041] The number of silicon atoms in X in formula (1) is preferably greater than the number of n in formula (1). This ensures sufficient film density and improves the water resistance and sweat resistance of the surface layer.

[0042] L １ This is a linear alkylene group having 23 or more carbon atoms, which may have -C(=O)O-, -C(=O)-, -O-, or a phenylene group. １ The number of carbon atoms in the alkylene group is 23 or more, and more preferably 25 or more, and more preferably 29 or more, from the viewpoint of achieving superior effects of the present invention. １ In the alkylene group, the number of carbon atoms is preferably 60 or less, and more preferably 40 or less, from the viewpoint of ease of synthesis. １ If the compound has -C(=O)O-, -C(=O)-, -O-, or a phenylene group, each group may be located between carbon atoms or at the terminal. １ The X-side end is preferably a carbon atom. Also, Q １ is *-Si(-**) ３ In the case of L １ Q １ The end portion is preferably a carbon atom. １ If it contains a -C(=O)O-, -C(=O)-, or phenylene group, the number of carbon atoms in these groups is as described above for L １ The number of carbon atoms in the alkylene group is not included in the calculation.

[0043] Among them, L １ From the viewpoint of achieving superior effects of the present invention, it is preferable that the group does not have -C(=O)O-, -C(=O)-, -O-, or a phenylene group, that is, a linear alkylene group having 23 or more carbon atoms.

[0044] Q １ *-CR Ｑ１ (-**) ２ , *-C(-**) ３ , *-N(-**) ２ *-SiR Ｑ１ (-**) ２ , *-Si(-**) ３ , or a (1+n) valency ring structure. * is L １ This indicates the bonding position with L. ２ This indicates the connection point with [the other element].

[0045] R Ｑ１R is a hydrogen atom or an alkyl group which may have an -O- group. The -O- group is preferably located between carbon atoms. Ｑ１ The number of carbon atoms in the alkyl group is preferably 1 to 10, more preferably 1 to 5, and even more preferably 1 to 3. When the alkyl group has 3 or more carbon atoms, the alkyl group with 3 or more carbon atoms may be linear, branched, or have a ring structure.

[0046] As for the (1+n) valent ring structure, from the standpoint of ease of synthesis and superior abrasion resistance, light resistance, and chemical resistance of the surface layer, one selected from the group consisting of a 3- to 8-membered aliphatic ring, a 6-membered aromatic ring, a 5- to 6-membered heterocycle, and a fused ring consisting of two or more of these rings is preferred, and the ring structure shown in the following formula is more preferred. The ring structure may have substituents such as halogen atoms, alkyl groups (which may contain an etheric oxygen atom between carbon atoms), cycloalkyl groups, alkenyl groups, allyl groups, alkoxy groups, and oxo groups (=O).

[0047]

[0048] Among them, Q １ *-CR is preferred because it offers superior effects compared to the present invention. Ｑ１ (-**) ２ , or *-C(-**) ３ Preferably, *-CR Ｑ１ (-**) ２ This is preferable.

[0049] L ２ L is a hydrocarbon group which may have a single bond or an -O-. Examples of hydrocarbon groups include aliphatic hydrocarbon groups (which may be saturated or unsaturated, and which may be linear, branched, or cyclic), aromatic hydrocarbon groups, and groups which are combinations thereof. From the standpoint of excellent wear resistance of the surface layer, aliphatic hydrocarbon groups are preferred, saturated aliphatic hydrocarbon groups are more preferred, and alkylene groups are even more preferred. ２ They may be the same or different from each other. ２The number of carbon atoms in the hydrocarbon group is preferably 1 to 20, more preferably 1 to 15, and even more preferably 1 to 11. When the number of carbon atoms in the hydrocarbon group is 3 or more, the hydrocarbon group with 3 or more carbon atoms may be linear, branched, or have a ring structure. In a hydrocarbon group having -O-, Q １ , or T １ The bonding atom may be -O-, and there may be -O- between the carbon atoms. It is preferable that the -O- is located between the carbon atoms.

[0050] L ２ It is preferable that the group is represented by the following formula (H1): *-(O) ａ４ - (L ｇ１１ O) ａ５ -L ｇ１２ -** (H1) However, L ｇ１１ L is an alkylene group having 1 to 12 carbon atoms. ｇ１１ If there are multiple L ｇ１１ L may be the same or different from each other. ｇ１２ is an alkylene group having 1 to 12 carbon atoms, a4 is 0 or 1, a5 is a non-negative integer, and * is Q １ It is a bonding term that connects to T １ It is a bonding hand that connects to [something].

[0051] When a4 is 0, the atom with a bond* is a carbon atom, and when a4 is 1, the atom with a bond* is an oxygen atom. In compound 1, a4 may be either 0 or 1, and can be appropriately selected from the viewpoint of ease of synthesis, etc. a5 is L ｇ１１ The number of repetitions of O is preferably 0 to 6, more preferably 0 to 3, and even more preferably 0 to 1, from the standpoint of excellent wear resistance of the surface layer. ｇ１１ The number of carbon atoms in the alkylene group is 1 to 12, preferably 1 to 6, and more preferably 1 to 3. When the alkylene group has 3 or more carbon atoms, the alkylene group with 3 or more carbon atoms may be linear or branched. Furthermore, it is preferable that the alkylene group is linear. ｇ１２The alkylene group has 1 to 12 carbon atoms. If the alkylene group has 3 or more carbon atoms, the alkylene group with 3 or more carbon atoms may be linear or branched. It is preferable that the alkylene group is linear.

[0052] T １ It is a group that has a reactive silyl group. There are multiple T １ These may be the same or different. The group having a reactive silyl group is preferably the group represented by the following formula (2) from the viewpoint of superior effects of the present invention.

[0053] -SiR ａ１ ｚ１ R ａ１１ ３－ｚ１ (2)

[0054] In formula (2), R ａ１ R is a hydrolyzable group, a group having a hydrolyzable group, or a hydroxyl group. ａ１１ is a hydrocarbon group, z1 is an integer from 1 to 3, and R ａ１ , or R ａ１１ If there are multiple R ａ１ , or R ａ１１ These may be the same or different.

[0055] R ａ１ If it is a hydroxyl group, it forms a silanol (Si-OH) group together with the Si atom. Also, hydrolyzable groups are groups that become hydroxyl groups through hydrolysis. The silanol group further reacts intermolecularly to form a Si-O-Si bond. In addition, the silanol group undergoes a dehydration condensation reaction with the hydroxyl group on the surface of the substrate (substrate-OH) to form a chemical bond (substrate-O-Si). Compound 1 is T １ Having one or more of these features provides excellent abrasion resistance after the surface layer is formed.

[0056] R ａ１Examples of hydrolyzable groups include alkoxy groups, aryloxy groups, halogen atoms, acyl groups, acyloxy groups, amino groups, and isocyanate groups (-NCO). As alkoxy groups, alkoxy groups having 1 to 4 carbon atoms are preferred. As acyl groups, acyl groups having 1 to 6 carbon atoms are preferred. As acyloxy groups, acyloxy groups having 1 to 6 carbon atoms are preferred.

[0057] R ａ１ The hydrolyzable group can be any of the hydrolyzable groups exemplified above. The hydrolyzable group is -O-L Ａ -L Ｂ This is preferable. L Ａ L is an alkylene group, Ｂ This is a hydrolyzable group. The number of carbon atoms in the alkylene group is preferably 1 to 10. Ｂ The hydrolyzable group represented by the above R ａ１ This is synonymous with the hydrolyzable group in the above, and the preferred embodiment is also the same. A specific example of a group having a hydrolyzable group is -O-CH, which is also one of the alkylene oxide-modified alkoxy groups. ２ CH ２ - OCH ３ Examples include the following. Thus, the group having a hydrolyzable group may be an alkylene oxide-modified alkoxy group. The alkylene oxide-modified alkoxy group is -(O-R ４１ ) ｎ１１ -L Ｃ A group represented by R is preferred. Here, R ４１ L is an alkylene group having 1 to 10 carbon atoms. Ｃ R is an alkoxy group having 1 to 6 carbon atoms, and n11 is an integer from 1 to 6. Among them, R ４１ The alkylene group has 1 to 6 carbon atoms, and n11 is preferably 1.

[0058] R ａ１ From the standpoint of ease of synthesis, alkoxy groups having 1 to 4 carbon atoms, and the aforementioned -O-L Ａ -L Ｂ Alternatively, halogen atoms are preferred. ａ１In this compound, the alkoxy group is preferably a C1-C4 alkoxy group because it provides excellent storage stability for compound 1 and suppresses outgassing during the reaction. An ethoxy group is more preferable from the viewpoint of long-term storage stability, and a methoxy group is more preferable from the viewpoint of shortening the hydrolysis reaction time. Furthermore, a chlorine atom is preferred as the halogen atom.

[0059] R ａ１１ This is a hydrocarbon group. Examples of hydrocarbon groups include alkyl groups, cycloalkyl groups, alkenyl groups, and allyl groups, and alkyl groups are preferred from the viewpoint of ease of synthesis. Furthermore, from the viewpoint of ease of synthesis, the number of carbon atoms in the hydrocarbon group is preferably 1 to 6, more preferably 1 to 3, and even more preferably 1 to 2.

[0060] In base 2, R ａ１ The number z1 can be 1 to 3, and from the viewpoint of excellent adhesion to the substrate, 2 or 3 is preferred, and 3 is more preferred. A specific example of group 2 is -Si(OCH ３ ) ３ ,-SiCH ３ (OCH ３ ) ２ , -Si((CH ３ ) ２ (OCH ３ ), -Si(OCH ２ CH ３ ) ３ , -Si(OCH ２ CH ２ OCH ３ ) ３ , -SiCl ３ , -Si(OCOCH ３ ) ３ , -Si(NCO) ３ ,-Si(N(CH ３ ) ２ ) ３ -Si(OH) ３ One example is -Si(OCH) due to its ease of handling during manufacturing. ３ ) ３ It is preferable.

[0061] Q １ *-CR Ｑ１ (-**) ２ , *-N(-**) ２, or *-SiR Ｑ１ (-**) ２ If that is the case, -(L ２ -T １ The value of n, which represents the number of ( ), is 2. Q １ *-C(-**) ３ , or *-Si(-**) ３ If that is the case, then n is 3. Q １ If the ring structure has (1+n) valencies, then n is an integer of 2 or more, preferably 2 to 5, and more preferably 2 to 3.

[0062] n is preferably 2 or 3, and more preferably 2, from the viewpoint of achieving superior effects of the present invention.

[0063] A specific example of compound 1 is the compound represented by the following formula, where n1 is an integer between 0 and 100.

[0064]

[0065] <Physical Properties of Compound 1> The molecular weight of Compound 1 is preferably 500 to 20,000, more preferably 600 to 10,000, and even more preferably 700 to 5,000. If the molecular weight of Compound 1 is above the lower limit of the above range, the wear resistance of the surface layer is better. If the molecular weight of Compound 1 is below the upper limit of the above range, the viscosity is easier to adjust within an appropriate range, and the solubility is improved, resulting in excellent handling during film formation.

[0066] [Surface Treatment Agent] The surface treatment agent of the present invention (hereinafter referred to as "this surface treatment agent") contains compound 1 described above. This surface treatment agent is suitable for applications where it is required that the water-repellent and oil-repellent properties of the surface layer not deteriorate even when repeatedly rubbed with fingers (abrasion resistance), and that fingerprints adhering to the surface layer can be easily removed by wiping (fingerprint removal properties) be maintained for a long period of time, such as components that make up the surface that is touched by fingers on a touch panel, eyeglass lenses, and displays of wearable devices. Furthermore, because this surface treatment agent has excellent slip resistance, it is also suitable for use on glass-coated casings of portable devices such as smartphones and tablet terminals. This surface treatment agent is also suitable for use as an anti-fouling coating agent or a waterproof coating agent.

[0067] This surface treatment agent may further contain a liquid medium. In the following description, this surface treatment agent containing a liquid medium may be referred to as a coating solution. The coating solution may be a liquid, a solution, or a dispersion. The coating solution may contain compound 1 and may contain impurities such as by-products generated in the manufacturing process of compound 1. The concentration of compound 1 in the coating solution is preferably 0.001 to 40% by mass, more preferably 0.01 to 20% by mass, even more preferably 0.1 to 10% by mass, and particularly preferably 0.1 to 1% by mass.

[0068] As the liquid medium, an organic solvent is preferred. The organic solvent may be a fluorine-containing organic solvent, a non-fluorine-containing organic solvent, or a mixture of both. Specific examples of fluorine-containing organic solvents include fluorinated alkanes, fluorinated aromatic compounds, fluoroalkyl ethers, fluorinated alkylamines, fluoroalcohols, and hydrofluoroolefins (HFOs). As fluorinated alkanes, compounds having 4 to 8 carbon atoms are preferred. Specific examples of commercially available products include C ６ F １３ H (AGC Corporation, Asahi Clean® AC-2000), C ６ F １３ C ２ H ５ (Manufactured by AGC Corporation, Asahi Clean® AC-6000), C２ F ５ CHFCHFCF ３ (Chemours Bartrell® XF) is one example. Specific examples of fluorinated aromatic compounds include hexafluorobenzene, trifluoromethylbenzene, perfluorotoluene, and bis(trifluoromethyl)benzene. As for fluoroalkyl ethers, compounds with 4 to 12 carbon atoms are preferred. A specific example of a commercially available product is CF ３ CH ２ OCF ２ CF ２ H (manufactured by AGC Corporation, Asahi Clean® AE-3000), C ４ F ９ OCH ３ (Manufactured by 3M, Novec® 7100), C ４ F ９ OC ２ H ５ (Manufactured by 3M, Novec® 7200), C ２ F ５ CF(OCH) ３ ) C ３ F ７ (Novec® 7300, manufactured by 3M) is one example. Specific examples of fluorinated alkylamines include perfluorotripropylamine and perfluorotributylamine. Specific examples of fluoroalcohols include 2,2,3,3-tetrafluoropropanol, 2,2,2-trifluoroethanol, and hexafluoroisopropanol. Specific examples of HFOs include 1-chloro-2,3,3-trifluoro-1-propene (HCFO-1233yd) (Amorea® AS-300, manufactured by AGC). As non-fluorinated organic solvents, compounds consisting only of hydrogen atoms and carbon atoms, and compounds consisting only of hydrogen atoms, carbon atoms, and oxygen atoms are preferred, and examples include hydrocarbon organic solvents, alcohol organic solvents, ketone organic solvents, ether organic solvents, ester organic solvents, and glycol organic solvents.

[0069] Specific examples of hydrocarbon organic solvents include pentane, hexane, heptane, octane, hexadecane, isohexane, isooctane, isononane, cycloheptane, cyclohexane, bicyclohexane, benzene, toluene, ethylbenzene, o-xylene, m-xylene, p-xylene, o-diethylbenzene, m-diethylbenzene, p-diethylbenzene, n-butylbenzene, sec-butylbenzene, and tert-butylbenzene.

[0070] Specific examples of alcoholic organic solvents include methanol, ethanol, 1-propanol, isopropyl alcohol, n-butanol, diacetone alcohol, isobutanol, sec-butanol, tert-butanol, pentanol, 3-methyl-1,3-butanediol, 1,3-butanediol, 1,3-butylene glycol, octanediol, 2,4-diethylpentanediol, butylethylpropanediol, 2-methyl-1,3-propanediol, 4-hydroxy-4-methyl-2-pentanone, 2-ethyl-1-hexanol, 3,5,5-trimethyl-1-hexanol, isodecanol, isotridecanol, 3-methoxy-3-methyl-1-butanol, 2-methoxybutanol, 3-methoxybutanol, cyclohexanol, furfuryl alcohol, tetrahydrofurfuryl alcohol, benzyl alcohol, and methylcyclohexanol.

[0071] Specific examples of ketone organic solvents include acetone, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, cyclohexanone, 2-heptanone, 4-heptanone, 3,5,5-trimethyl-2-cyclohexen-1-one, and 3,3,5-trimethylcyclohexanone and isophorone.

[0072] Specific examples of ether-based organic solvents include diethyl ether, cyclopentyl methyl ether, tetrahydrofuran, and 1,4-dioxane.

[0073] Specific examples of ester-based organic solvents include methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, isobutyl acetate, tert-butyl acetate, amyl acetate, isoamyl acetate, ethyl 3-ethoxypropionate, ethyl lactate, ethylene glycol monobutyl ether acetate, diethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, dipropylene glycol methyl ether acetate, 3-methoxy-3-methylbutyl acetate, 3-methoxybutyl acetate, propylene glycol monomethyl acetate, propylene glycol dimethyl acetate, and ethylene glycol monoethyl ether acetate. Examples include tate, ethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, cyclohexanol acetate, propylene glycol diacetate, propylene glycol monomethyl ether propionate, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether acetate, propylene glycol monopropyl ether acetate, 1,3-butylene glycol diacetate, 1,4-butanediol diacetate, 1,6-hexanediol diacetate, γ-butyrolactone, triacetin, and 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate.

[0074] Specific examples of glycol-based organic solvents include ethylene glycol, ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, triethylene glycol monobutyl ether, tetraethylene glycol monobutyl ether, ethylene glycol monohexyl ether, diethylene glycol monohexyl ether, ethylene glycol mono-2-ethylhexyl ether, diethylene glycol mono-2-ethylhexyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, propylene glycol monopropyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monoethyl ether, ethylene glycol monotert-butyl ether, ethylene glycol monopropyl ether, ethylene glycol monomethyl ether, diethylene glycol monoisopropyl ether, and diethylene glycol monobutyl ether. Examples include propylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monobutyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monomethyl ether, tripropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, propylene glycol monophenyl ether, 1,3-butylene glycol, diethylene glycol monoethyl ether, tripropylene glycol methyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, dipropylene glycol dimethyl ether, diethylene glycol dibutyl ether, tetraethylene glycol dimethyl ether, triethylene glycol dimethyl ether, and polyethylene glycol dimethyl ether.

[0075] Other organic solvents include chlorinated organic solvents, nitrogen-containing compounds, sulfur-containing compounds, and siloxane compounds.

[0076] Specific examples of chlorinated organic solvents include dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane, chlorobenzene, o-chlorotoluene, m-chlorotoluene, p-chlorotoluene, m-dichlorobenzene, and 1,2,3-trichloropropane.

[0077] Specific examples of nitrogen-containing compounds include nitrobenzene, acetonitrile, benzonitrile, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, and 1,3-dimethyl-2-imidazolidinone.

[0078] Specific examples of sulfur-containing compounds include carbon disulfide and dimethyl sulfoxide.

[0079] Specific examples of siloxane compounds include hexamethyldisiloxane, octamethyltrisiloxane, and decamethyltetrasiloxane.

[0080] The coating liquid preferably contains 60 to 99.999% by mass of the liquid medium, more preferably 80 to 99.99% by mass, even more preferably 90 to 99.9% by mass, and particularly preferably 99 to 99.9% by mass.

[0081] The surface treatment agent may contain other components besides compound 1 and the liquid medium, to the extent that they do not impair the effects of the disclosure. Examples of other components include known additives such as acid catalysts and basic catalysts that promote the hydrolysis and condensation reaction of hydrolyzable silyl groups. The content of other components in the surface treatment agent is preferably 10% by mass or less, and more preferably 1% by mass or less.

[0082] The total concentration of compound 1 and other components in the coating solution (hereinafter referred to as "solid content concentration") is preferably 0.001 to 40% by mass, more preferably 0.01 to 20% by mass, even more preferably 0.01 to 10% by mass, and particularly preferably 0.01 to 1% by mass. The solid content concentration of the coating solution is calculated from the mass of the coating solution before heating and the mass after heating in a convection dryer at 120°C for 4 hours.

[0083] [Article] The article of the present invention (hereinafter referred to as "the Article") has a surface layer formed from compound 1 or the surface treatment agent on the surface of a substrate. An example of the Article will be described with reference to the drawings. Figure 1 is a schematic cross-sectional view showing a first article, which is an example of the Article. The first article is an article 20 having a substrate 12, a base layer 14, and a surface layer 22 in that order, wherein the base layer 14 contains an oxide containing silicon, and the surface layer 22 contains a condensate of compound 1.

[0084] The material and shape of the base material 12 may be appropriately selected according to the intended use of the article 20. Examples of materials for the base material 12 include glass, resin, sapphire, metal, ceramic, stone, and composite materials thereof. The glass may be chemically strengthened. Examples of base materials 12 that require water-repellent and oil-repellent properties include base materials for touch panels, base materials for displays, and base materials that constitute the housing of electronic devices. The base materials for touch panels and display substrates are translucent. "Translucent" means that the normal incidence visible light transmittance in accordance with JIS R3106:1998 (ISO 9050:1990) is 25% or more. Glass or transparent resin is preferred as the material for the base material for touch panels.

[0085] The substrate 12 may have surface treatments such as corona discharge treatment, plasma treatment, or plasma graft polymerization treatment applied to the surface on which the underlayer 14 is provided. Surface treatment further improves the adhesion between the substrate 12 and the underlayer 14, and as a result, the abrasion resistance of the surface layer 22 is further improved. As for the surface treatment, corona discharge treatment or plasma treatment is preferred because it further improves the abrasion resistance of the surface layer 22.

[0086] The base layer 14 is a layer containing an oxide that includes at least silicon, and may also contain other elements. By including silanol groups on the surface of the base layer 14, the reactive silyl groups of compound 1 undergo dehydration condensation, forming Si-O-Si bonds between them and the base layer 14, resulting in a surface layer 22 with superior abrasion resistance.

[0087] The silicon dioxide content in the base layer 14 is preferably 65% ​​by mass or more, more preferably 80% by mass or more, even more preferably 85% by mass or more, and particularly preferably 90% by mass or more. If the silicon dioxide content is above the lower limit of the above range, sufficient Si-O-Si bonds are formed in the base layer 14, and the mechanical properties of the base layer 14 are sufficiently ensured. The silicon dioxide content is the remainder obtained by subtracting the total content of other elements (or the sum of the amounts converted to oxides in the case of oxides) from the mass of the base layer 14.

[0088] From the standpoint of providing excellent durability of the surface layer 22, it is preferable that the oxide in the base layer 14 further contains one or more elements selected from alkali metal elements, alkaline earth metal elements, platinum group elements, boron, aluminum, phosphorus, titanium, zirconium, iron, nickel, chromium, molybdenum, and tungsten. Including these elements strengthens the bond between the base layer 14 and compound 1, improving abrasion resistance.

[0089] When the base layer 14 contains one or more elements selected from iron, nickel, and chromium, the total content of these elements is preferably 10 to 1,100 ppm by mass, more preferably 50 to 1,100 ppm by mass, even more preferably 50 to 500 ppm by mass, and particularly preferably 50 to 250 ppm by mass, relative to silicon oxide. When the base layer 14 contains one or more elements selected from aluminum and zirconium, the total content of these elements is preferably 10 to 2,500 ppm by mass, more preferably 15 to 2,000 ppm by mass, and even more preferably 20 to 1,000 ppm by mass. When the base layer 14 contains alkali metal elements, the total content of these elements is preferably 0.05 to 15% by mass, more preferably 0.1 to 13% by mass, and even more preferably 1.0 to 10% by mass. Examples of alkali metal elements include lithium, sodium, potassium, rubidium, and cesium. When the base layer 14 contains platinum group elements, the total content of these elements is preferably 0.02 to 800 ppm by mass, more preferably 0.04 to 600 ppm by mass, and even more preferably 0.7 to 200 ppm by mass. Examples of platinum group elements include platinum, rhodium, ruthenium, palladium, osmium, and iridium. When the base layer 14 contains one or more elements selected from boron and phosphorus, the total content of these elements is preferably 0.003 to 9, more preferably 0.003 to 2, and even more preferably 0.003 to 0.5, as a ratio of the molar concentration of the total of boron and phosphorus to the molar concentration of silicon, from the viewpoint of excellent abrasion resistance of the surface layer 22. When the base layer 14 contains alkaline earth metal elements, the total content of these elements is preferably 0.005 to 5, more preferably 0.005 to 2, and even more preferably 0.007 to 2, as a ratio of the molar concentration of the total alkaline earth metal elements to the molar concentration of silicon, from the viewpoint of excellent abrasion resistance of the surface layer 22. Examples of alkaline earth metal elements include calcium, strontium, barium, and magnesium.

[0090] To improve the adhesion of this surface treatment agent and to improve the water-repellent, oil-repellent, and abrasion-resistant properties of article 20, the base layer 14 is preferably a silicon oxide layer containing alkali metal atoms. In the silicon oxide layer, the average concentration of alkali metal atoms in the region at a depth of 0.1 to 0.3 nm from the surface in contact with the surface layer 22 is 2.0 × 10⁻¹⁶. １９ atoms / cm ３ The above is preferable. On the other hand, in order to sufficiently ensure the mechanical properties of the silicon oxide layer, the average value of the alkali metal atom concentration is 4.0 × 10 ２２ atoms / cm ３ The following is preferable:

[0091] The thickness of the base layer 14 is preferably 1 to 200 nm, and more preferably 2 to 20 nm. If the thickness of the base layer 14 is above the lower limit of the above range, the adhesive improvement effect of the base layer 14 is easily obtained. If the thickness of the base layer 14 is below the upper limit of the above range, the abrasion resistance of the base layer 14 itself will be increased. Methods for measuring the thickness of the base layer 14 include cross-sectional observation of the base layer 14 using an electron microscope (SEM, TEM, etc.), and methods using an optical interferometer, spectroscopic ellipsometer, step meter, etc.

[0092] Specific examples of methods for forming the underlayer 14 include a method of depositing a vapor deposition material having the desired underlayer 14 composition onto the surface of the substrate 12. One example of a vapor deposition method is the vacuum vapor deposition method. The vacuum vapor deposition method involves evaporating the vapor deposition material in a vacuum chamber and depositing it onto the surface of the substrate 12. The temperature during vapor deposition (for example, the temperature of the boat in which the vapor deposition material is placed when using a vacuum vapor deposition apparatus) is preferably 100 to 3,000°C, and more preferably 500 to 3,000°C. The pressure during vapor deposition (for example, the absolute pressure in the chamber in which the vapor deposition material is placed when using a vacuum vapor deposition apparatus) is preferably 1 Pa or less, and more preferably 0.1 Pa or less. When forming the underlayer 14 using a vapor deposition material, one vapor deposition material may be used, or two or more vapor deposition materials containing different elements may be used. Examples of evaporation methods for the vapor deposition material include the resistance heating method, in which the vapor deposition material is melted and evaporated on a resistance heating boat made of high melting point metal, and the electron gun method, in which an electron beam is irradiated onto the vapor deposition material to directly heat the material, melt the surface, and evaporate it. As a method for evaporating the deposition material, the electron gun method is preferred because it allows for localized heating, enabling the evaporation of high-melting-point substances, and because the temperature is low in areas not exposed to the electron beam, eliminating the risk of reaction with the container or contamination by impurities. As the deposition material used in the electron gun method, molten granules or sintered bodies are preferred because they are less likely to scatter even if an airflow is generated.

[0093] The surface layer 22 on the base layer 14 contains a condensate of compound 1. The condensate of compound 1 includes a compound in which hydrolyzable silyl groups in compound 1 undergo hydrolysis to form silanol groups (Si-OH), and these silanol groups undergo intermolecular condensation to form Si-O-Si bonds, and a compound in which silanol groups in compound 1 undergo condensation with silanol groups or Si-OM groups (where M is an alkali metal element) on the surface of the base layer 14 to form Si-O-Si bonds. The surface layer 22 may also contain condensates of compounds other than compound 1 contained in this surface treatment agent. The surface layer 22 may contain compounds having reactive silyl groups in a state in which some or all of the reactive silyl groups of the compound have undergone condensation.

[0094] The thickness of the surface layer 22 is preferably 1 to 100 nm, and more preferably 1 to 50 nm. If the thickness of the surface layer 22 is above the lower limit of the above range, the effect of the surface layer 22 can be sufficiently obtained. If the thickness of the surface layer 22 is below the upper limit of the above range, the utilization efficiency is high. The thickness of the surface layer 22 is the thickness obtained by an X-ray diffractometer for thin film analysis. The thickness of the surface layer 22 can be calculated from the vibration period of the interference pattern obtained by the X-ray reflectivity method using an X-ray diffractometer for thin film analysis.

[0095] Another example of the article of the present invention is a second article. The second article 20 has a substrate 10 with a base layer and a surface layer 22 in that order, wherein the substrate 10 with the base layer contains a silicon-containing oxide and the surface layer 22 contains a condensate of compound 1.

[0096] In the second article, since the substrate 10 with the underlayer has the same composition as the underlayer 14 in the first article, the surface layer 22 has excellent abrasion resistance even when the surface layer 22 is directly formed on the substrate 10 with the underlayer. The material of the substrate 10 with the underlayer in the second article can be any material having the same composition as the underlayer 14, for example, a glass substrate. Details of the material of the substrate 10 with the underlayer are the same as those of the substrate 12 and the underlayer 14, so the explanation is omitted here. Also, the composition of the surface layer 22 is the same as that of the first article, so the explanation is omitted here.

[0097] Specific examples of articles of the present invention include optical components, touch panels, anti-reflective films, anti-reflective glass, and SiO2 used as parts of the following products. ２ Examples include processed glass, tempered glass, sapphire glass, quartz substrates, and mold metals. Products include: car navigation systems, mobile phones, digital cameras, digital video cameras, personal digital assistants (PDAs), portable audio players, car audio systems, gaming devices, eyeglass lenses, camera lenses, lens filters, sunglasses, medical equipment (endoscopes, etc.), photocopiers, personal computers (PCs), liquid crystal displays, organic EL displays, plasma displays, touch panel displays, protective films, anti-reflective films, anti-reflective glass, nanoimprint templates, molds, etc.

[0098] [Method for Manufacturing Articles] The method for manufacturing articles of the present invention is to form a surface layer using compound 1 or the surface treatment agent by a dry coating method or a wet coating method.

[0099] Compound 1 and this surface treatment agent can be used directly in a dry coating method and are suitable for forming a surface layer with excellent adhesion by the dry coating method. Examples of dry coating methods include vacuum deposition, CVD, and sputtering. Vacuum deposition is preferably used because it suppresses the decomposition of this surface treatment agent and because of the simplicity of the equipment. For vacuum deposition, a pellet-like material in which compound 1, etc., is supported on a porous metal body made of a metal material such as iron or steel may be used. The pellet-like material supported on compound 1, etc., can be manufactured by impregnating a porous metal body with a solution containing compound 1 and drying it to remove the liquid medium.

[0100] This surface treatment agent (coating solution) containing a liquid medium can be suitably used in wet coating methods. Examples of wet coating methods include spin coating, wipe coating, spray coating, squeegee coating, dip coating, die coating, inkjet coating, flow coating, roll coating, casting, Langmuir-Bludget coating, and gravure coating.

[0101] To improve the abrasion resistance of the surface layer, operations to promote the reaction between compound 1 and the substrate may be performed as needed. Such operations include heating, humidification, and light irradiation. For example, heating a substrate with a surface layer formed in a humid atmosphere can promote reactions such as the hydrolysis of hydrolyzable groups, the reaction between hydroxyl groups on the substrate surface and silanol groups, and the formation of siloxane bonds through the condensation reaction of silanol groups. After surface treatment, compounds in the surface layer that are not chemically bonded to other compounds or the substrate may be removed as needed. Specific methods include, for example, pouring a solvent onto the surface layer or wiping it with a cloth soaked in a solvent.

[0102] The present invention will be described in detail below with reference to examples. Of Examples 1 to 6, Examples 1 to 3 and 5 to 6 are examples, and Example 4 is a comparative example. However, the present invention is not limited to these examples.

[0103] [Example 1] <Synthesis of Compound A> 10 g of 18-bromo-1-octadecene was mixed with 10 g of dichloromethane, 6.6 g of 1,1,1,3,3-pentamethyldisiloxane, and a toluene solution of platinum / 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (platinum content: 3% by mass, 50 mg), and the mixture was stirred at 25°C for 24 hours. After removing the low-boiling components under reduced pressure, 12 g of Compound A was obtained by silica gel column chromatography (developing solvent: hexane) on the resulting crude solution. The structure of Compound A was confirmed from the following NMR data.

[0104]

[0105] (NMR data of compound A) 1 H-NMR (400 MHz, CDCl3) δ: 3.41 (t, J = 6.9 Hz, 2H), 1.89 - 1.82 (m, 2H), 1.49 - 1.04 (m, 30H), 0.52 - 0.48 (m, 2H), 0.06 (s, 9H), 0.03 (s, 6H).

[0106] <Synthesis of Compound B> 10 g of 11-bromo-1-undecene was mixed with THF (tetrahydrofuran, 20 g) and magnesium (1.1 g), and the mixture was stirred at 60°C for 2 hours. The reaction mixture was filtered to obtain 30 g of a solution containing compound B. The product was confirmed to have a concentration of 0.8 M by titration using 1,10-phenanthroline.

[0107]

[0108] <Synthesis of Compound C> Compound A (2.0 g) was mixed with THF (20 g), Compound B (0.8 M, 20 mL), and copper(II) chloride (0.10 g), and the mixture was stirred at 60°C for 24 hours. Hydrochloric acid and hexane were added for extraction, and low-boiling point components were removed by distillation under reduced pressure. Then, 1.4 g of Compound C was obtained by column chromatography using 10% silver nitrate silica gel (developing solvent: hexane / dichloromethane). The structure of Compound C was confirmed from the following NMR data.

[0109]

[0110] (NMR data of compound C) 1 H-NMR (400 MHz, CDCl3) δ: 5.81 (ddt, J = 16.9, 10.1, 6.7 Hz, 1H), 5.08 - 4.82 (m, 2H), 2.13 - 1.93 (m, 2H), 1.44 - 1.26 (m, 50H), 0.54 - 0.48 (m, 2H), 0.06 (s, 9H), 0.03 (s, 6H).

[0111] <Synthesis of Compound D> Compound C (1.4 g) was mixed with dried dichloromethane (10 g) and zirconocene chloride hydride (0.57 g) and stirred at 25°C for 30 minutes. Then, N-bromosuccinimide (1.1 g) was added and stirred for another 30 minutes. The reaction was terminated by adding an aqueous solution of sodium thiosulfate. After extraction with hexane and removal of low-boiling components under reduced pressure, 1.0 g of compound D was obtained by silica gel column chromatography (eluent: hexane) on the resulting crude solution. The structure of compound D was confirmed from the following NMR data.

[0112]

[0113] (NMR data of compound D) 1 H-NMR (400 MHz, CDCl3) δ: 3.41 (t, J = 6.9 Hz, 2H), 1.89 - 1.82 (m, 2H), 1.45 - 1.20 (m, 52H), 0.52 - 0.48 (m, 2H), 0.06 (s, 9H), 0.03 (s, 6H).

[0114] <Synthesis of Compound E> 10 g of 4-(bromomethyl)-1,6-heptadiene was mixed with 30 g of THF and 1.4 g of magnesium, and the mixture was stirred at 60°C for 2 hours. The reaction mixture was filtered to obtain 30 g of a solution containing compound E. The product was confirmed to have a concentration of 1.1 M by titration using 1,10-phenanthroline.

[0115]

[0116] <Synthesis of Compound F> Compound D (1.0 g) was mixed with THF (5.0 g), Compound E (1.1 M, 2.5 mL), and copper(II) chloride (4.0 mg), and the mixture was stirred at 25°C for 24 hours. The reaction was terminated by adding an aqueous solution of ammonium chloride. After extraction with hexane and removal of low-boiling components under reduced pressure, 350 mg of Compound F was obtained by silica gel column chromatography (eluent: hexane) on the resulting crude solution. The structure of Compound F was confirmed from the following NMR data.

[0117]

[0118] (NMR data of compound F) 1 H-NMR (400 MHz, CDCl3) δ:5.82 - 5.72 (m, 2H), 5.03 - 4.98 (m, 4H), 2.04 - 2.01 (m, 4H), 1.50 - 1.25 (m, 59H), 0.52 - 0.48 (m, 2H), 0.06 (s, 9H), 0.03 (s, 6H).

[0119] <Synthesis of Compound 1A> Compound F (0.10 g) was mixed with dichloromethane (500 mg), a toluene solution of platinum / 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (platinum content: 3% by mass, 3.0 mg), aniline (1.0 mg), and trimethoxysilane (40 mg), and the mixture was stirred at 25°C for 2 hours. By removing the solvent under reduced pressure, 120 mg of compound 1A was obtained. The structure of compound 1A was confirmed from the following NMR data.

[0120]

[0121] (NMR data of compound 1A)1 H-NMR (400 MHz, CDCl3) δ: 3.58 (s, 18H), 1.42 - 1.22 (m, 67H), 0.64 - 0.60 (m, 4H), 0.52 - 0.48 (m, 2H), 0.06 (s, 9H), 0.03 (s, 6H).

[0122] [Example 2] <Synthesis of Compound G> Compound G was obtained using the same procedure as in the synthesis of Compound A, except that 1,1,1,3,3,5,5-heptamethyltrisiloxane (9.9 g) was used instead of 1,1,1,3,3-pentamethyldisiloxane (15 g). The structure of Compound G was confirmed from the following NMR data.

[0123]

[0124] (NMR data of compound G) 1 H-NMR (400 MHz, CDCl3) δ: 3.41 (t, J = 6.9 Hz, 2H), 1.89 - 1.82 (m, 2H), 1.49 - 1.04 (m, 30H), 0.54 - 0.50 (m, 2H), 0.09 (s, 9H), 0.05 (s, 6H), 0.01 (s, 6H).

[0125] <Synthesis of Compound H> Compound H was obtained using the same procedure as in the synthesis of Compound C, except that Compound G (2.3 g) was used instead of Compound A. The structure of Compound H was confirmed from the following NMR data.

[0126]

[0127] (NMR data of compound H) 1 H-NMR (400 MHz, CDCl3) δ: 5.81 (ddt, J = 16.9, 10.1, 6.7 Hz, 1H), 5.08 - 4.82 (m, 2H), 2.13 - 1.93 (m, 2H), 1.44 - 1.26 (m, 50H), 0.54 - 0.50 (m, 2H), 0.09 (s, 9H), 0.05 (s, 6H), 0.01 (s, 6H).

[0128] <Synthesis of Compound J> Compound J was obtained using the same procedure as the synthesis of Compound D, except that Compound H (1.8 g) was used instead of Compound C. The structure of Compound J was confirmed from the following NMR data.

[0129]

[0130] 1 H-NMR (400 MHz, CDCl3) δ: 3.41 (t, J = 6.9 Hz, 2H), 1.89 - 1.82 (m, 2H), 1.45 - 1.20 (m, 52H), 0.54 - 0.50 (m, 2H), 0.09 (s, 9H), 0.05 (s, 6H), 0.01 (s, 6H).

[0131] <Synthesis of Compound K> Compound K was obtained in 620 mg using the same procedure as the synthesis of compound F, except that compound J (1.4 g) was used instead of compound D. The structure of compound K was confirmed from the following NMR data.

[0132]

[0133] (NMR data of compound K) 1 H-NMR (400 MHz, CDCl3) δ:5.82 - 5.72 (m, 2H), 5.03 - 4.98 (m, 4H), 2.04 - 2.01 (m, 4H), 1.50 - 1.25 (m, 59H), 0.54 - 0.50 (m, 2H), 0.09 (s, 9H), 0.05 (s, 6H), 0.01 (s, 6H).

[0134] <Synthesis of Compound 1B> Compound 1B was obtained in 810 mg using the same procedure as the synthesis of Compound 1A, except that Compound K (620 mg) was used instead of Compound F. The structure of Compound 1B was confirmed from the following NMR data.

[0135]

[0136] (NMR data of compound 1B) 1H-NMR (400 MHz, CDCl3) δ: 3.58 (s, 18H), 1.42 - 1.22 (m, 67H), 0.64 - 0.60 (m, 4H), 0.54 - 0.50 (m, 2H), 0.09 (s, 9H), 0.05 (s, 6H), 0.01 (s, 6H).

[0137] [Example 3] <Synthesis of Compound L> Compound L was obtained in 13 g using the same procedure as in the synthesis of Compound A, except that 1,1,1,3,3-pentamethyldisiloxane (9.9 g) was used instead of 1,1,1,3,3-pentamethyldisiloxane (15 g). The structure of Compound L was confirmed from the following NMR data.

[0138]

[0139] (NMR data of compound L) 1 H-NMR (400 MHz, CDCl3) δ: 3.41 (t, J = 6.9 Hz, 2H), 1.88 - 1.82 (m, 2H), 1.48 - 1.04 (m, 30H), 0.46 - 0.42 (m, 2H), 0.08 (s, 18H), -0.01 (s, 3H).

[0140] <Synthesis of Compound M> 10 g of 18-bromo-1-octadecene was mixed with 40 g of THF and 0.9 g of magnesium, and the mixture was stirred at 60°C for 2 hours. The reaction mixture was filtered to obtain 50 g of Compound M. The product was confirmed to be 0.4 M in concentration by titration using 1,10-phenanthroline.

[0141]

[0142] <Synthesis of Compound N> Compound N was obtained using the same procedure as in the synthesis of Compound C, except that Compound L (2.0 g) was used instead of Compound A, and Compound M (0.4 M, 14 mL) was used instead of Compound B. The structure of Compound N was confirmed from the following NMR data.

[0143]

[0144] (NMR data of compound N)1 H-NMR (400 MHz, CDCl3) δ: 5.81 (ddt, J = 16.9, 10.1, 6.7 Hz, 1H), 5.08 - 4.82 (m, 2H), 2.12 - 1.94 (m, 2H), 1.44 - 1.12 (m, 64H), 0.46 - 0.42 (m, 2H), 0.08 (s, 18H), -0.01 (s, 3H).

[0145] <Synthesis of Compound P> Compound P was obtained by following the same procedure as in the synthesis of Compound D, except that Compound N (1.5 g) was used instead of Compound C. The structure of Compound P was confirmed from the following NMR data.

[0146]

[0147] (NMR data of compound P) 1 H-NMR (400 MHz, CDCl3) δ: 3.41 (t, J = 6.9 Hz, 2H), 1.90 - 1.82 (m, 2H), 1.45 - 1.10 (m, 66H), 0.46 - 0.41 (m, 2H), 0.08 (s, 18H), -0.01 (s, 3H).

[0148] <Synthesis of Compound Q> Compound Q was obtained by following the same procedure as in the synthesis of compound F, except that compound P (1.5 g) was used instead of compound D, and 2,2-di-2-propen-1-yl-4-penten-1-ylmagnesium chloride (0.5 M THF solution, 6.9 mL) was used instead of compound E. The structure of compound Q was confirmed from the following NMR data.

[0149]

[0150] (NMR data of compound Q) 1H-NMR (400 MHz, CDCl3) δ: 5.86 - 5.75 (m, 3H), 5,05 - 5.01 (m, 6H), 1.98 (d, J = 7.4 Hz, 6H), 1.45 - 1.15 (m, 72H), 0.46 - 0.40 (m, 2H), 0.08 (s, 18H), -0.01 (s, 3H).

[0151] <Synthesis of Compound 1C> Compound 1C was obtained by following the same procedure as in the synthesis of Compound 1A, except that Compound Q (1.2 g) was used instead of Compound F. The structure of Compound 1C was confirmed from the following NMR data.

[0152]

[0153] (NMR data of compound 1C) 1 H-NMR (400 MHz, CDCl3) δ: 3.56 (s, 27H), 1.45 - 1.12 (m, 84H), 0.57 - 0.53 (m,6H), 0.46 - 0.40 (m, 2H), 0.08 (s, 18H), -0.01 (s, 3H).

[0154] [Example 4] Compound (26) described in International Publication No. 2024 / 034669 was designated as compound H1.

[0155]

[0156] [Example 5] <Synthesis of Compound R> Compound R was obtained by referring to the method described in International Publication No. 2024 / 262627. The average value of n in compound R was 6.

[0157]

[0158] <Synthesis of Compound S> Compound S was obtained in 920 mg using the same procedure as the synthesis of Compound D, except that Compound R (1.0 g) was used instead of Compound C. The average value of n in Compound S was 6. The structure of Compound S was confirmed from the following NMR data.

[0159]

[0160] (NMR data of compound S)1 H-NMR (400 MHz, CDCl3) δ: 3.41 (t, J = 6.9 Hz, 2H), 1.90 - 1.82 (m, 2H), 1.45 - 1.10 (m, 66H), 0.54 - 0.51 (m, 2H), 0.10 - 0.00 (s, 63H).

[0161] <Synthesis of Compound T> Compound T was obtained in 780 mg using the same procedure as the synthesis of compound Q, except that compound S (910 mg) was used instead of compound P. The average value of n in compound T was 6. The structure of compound T was confirmed from the following NMR data.

[0162]

[0163] (NMR data of compound T) 1 H-NMR (400 MHz, CDCl3) δ: 5.86 - 5.75 (m, 3H), 5,05 - 5.01 (m, 6H), 1.98 (d, J = 7.4 Hz, 6H), 1.45 - 1.15 (m, 72H), 0.54 - 0.51 (m, 2H), 0.10 - 0.00 (m, 63H).

[0164] <Synthesis of Compound 1D> Compound 1D was obtained in 980 mg using the same procedure as the synthesis of Compound 1A, except that Compound T (780 mg) was used instead of Compound F. The average value of n in Compound 1D was 6. The structure of Compound 1D was confirmed from the following NMR data.

[0165]

[0166] (NMR data of compound 1D) 1 H-NMR (400 MHz, CDCl3) δ: 3.56 (s, 27H), 1.45 - 1.10 (m, 84H), 0.57 - 0.53 (m,6H), 0.54 - 0.50 (m, 2H), 0.11 - 0.00 (m, 63H).

[0167] [Example 6] <Synthesis of Compound U> Compound U was obtained by referring to the method described in International Publication No. 2024 / 262627. The average value of n in compound U was 6.

[0168]

[0169] <Synthesis of Compound V> Compound V was obtained using the same procedure as the synthesis of Compound C, except that Compound U (2.0 g) was used instead of Compound A. The average value of n in Compound V was 6. The structure of Compound V was confirmed from the following NMR data.

[0170]

[0171] (NMR data of compound V) 1 H-NMR (400 MHz, CDCl3) δ: 5.81 (ddt, J = 16.9, 10.1, 6.7 Hz, 1H), 5.08 - 4.82 (m, 2H), 2.13 - 1.93 (m, 2H), 1.44 - 1.26 (m, 50H), 0.54 - 0.50 (m, 2H), 0.10 - 0.03 (m, 51H).

[0172] <Synthesis of Compound W> Compound W was obtained using the same procedure as the synthesis of compound D, except that compound V (1.6 g) was used instead of compound C. The average value of n in compound W was 6. The structure of compound W was confirmed from the following NMR data.

[0173]

[0174] (NMR data of compound W) 1 H-NMR (400 MHz, CDCl3) δ: 3.41 (t, J = 6.9 Hz, 2H), 1.89 - 1.82 (m, 2H), 1.45 - 1.23 (m, 52H), 0.54 - 0.50 (m, 2H), 0.10 - 0.03 (m, 51H).

[0175] <Synthesis of Compound X> Compound X was obtained in 700 mg using the same procedure as the synthesis of compound F, except that compound W (1.5 g) was used instead of compound D. The average value of n in compound X was 6. The structure of compound X was confirmed from the following NMR data.

[0176]

[0177] (NMR data of compound X) 1 H-NMR (400 MHz, CDCl3) δ: 5.82 - 5.72 (m, 2H), 5.03 - 4.98 (m, 4H), 2.04 - 2.01 (m, 4H), 1.50 - 1.22 (m, 59H), 0.54 - 0.50 (m, 2H), 0.10 - 0.03 (m, 51H).

[0178] <Synthesis of Compound 1E> Compound 1E was obtained in 850 mg using the same procedure as the synthesis of Compound 1A, except that Compound X (700 mg) was used instead of Compound F. The average value of n in Compound 1E was 6. The structure of Compound 1E was confirmed from the following NMR data.

[0179]

[0180] (NMR data of compound 1E) 1 H-NMR (400 MHz, CDCl3) δ: 3.58 (s, 18H), 1.42 - 1.22 (m, 67H), 0.64 - 0.60 (m, 4H), 0.54 - 0.50 (m, 2H), 0.11 - 0.03 (m, 51H).

[0181] [Manufacturing of Articles] 30 g of silicon oxide was placed as a deposition source in the copper hearth inside a vacuum deposition apparatus (VTR-350M, manufactured by ULVAC, Inc.). A glass substrate was placed inside the vacuum deposition apparatus, and the inside of the vacuum deposition apparatus was 5 × 10 －３The chamber was evacuated until the pressure was below Pa. The hearth was heated to approximately 2,000°C, and silicon dioxide was vacuum-deposited onto the surface of the substrate to prepare a substrate with a silicon dioxide layer approximately 20 nm thick. The substrate with the silicon dioxide layer was placed on the sample stage of a spray coater (API-90RS, manufactured by Apiros Co., Ltd.) with the silicon dioxide layer facing the surface. Next, 13 g of a heptane solution containing 0.2% by mass of the compound obtained in each example was put into a syringe in the spray coater and spray-coated at an atomization pressure of 130 kPa, a nozzle-to-sample surface distance of 50 mm, and a scanning speed of 300 mm / second (wet coating method). Subsequently, the substrate with the silicon dioxide layer coated on the surface was heat-treated at 140°C for 30 minutes to obtain an evaluation sample (article) in which the substrate, silicon dioxide layer, and surface layer were stacked in this order.

[0182] [Evaluation] The following evaluations were conducted using the obtained items. The results of the evaluation tests are shown in Table 1.

[0183] <Water Resistance> The articles were immersed in water at 20°C for 100 hours. After that, the articles were removed, washed with ethanol, dried, and the water contact angle on the surface layer of the articles was measured. The smaller the decrease in water repellency (water contact angle) after immersion, the smaller the decrease in performance due to water and the better the water resistance. The evaluation criteria are as follows: A: Decrease in water contact angle after immersion is 2° or less. B: Decrease in water contact angle after immersion is greater than 2° and 5° or less. C: Decrease in water contact angle after immersion is greater than 5°. (Method of measuring water contact angle) The contact angle of approximately 2 μL of distilled water placed on the surface of the surface layer was measured using a contact angle measuring device (Kyowa Interface Science Co., Ltd., DM-500). Measurements were taken at five different locations on the surface of the surface layer, and the average value was calculated to be the water contact angle. The 2θ method was used to calculate the contact angle.

[0184] <Sweat Resistance> The articles were immersed in artificial sweat (composition: 2g anhydrous sodium phosphate, 20g sodium chloride, 2g 85% lactate, 5g histidine hydrochloride, 1kg distilled water) at 20°C for 100 hours. After that, the articles were removed, washed with ethanol, dried, and the water contact angle on the surface layer of the articles was measured using the method described above. The smaller the decrease in water repellency (water contact angle) after immersion, the smaller the decrease in performance due to sweat components, and the better the sweat resistance. The evaluation criteria are as follows: A: Decrease in water contact angle after immersion is 3° or less. B: Decrease in water contact angle after immersion is greater than 3° and less than or equal to 10°. C: Decrease in water contact angle after immersion is greater than 10°.

[0185]

[0186] As shown in Table 1, the compounds obtained in Examples 1-3 and 5-6 were confirmed to be able to form a surface layer with excellent water resistance and sweat resistance.

[0187] Articles having a surface layer containing compound 1 are, for example, optical articles, touch panels, anti-reflective films, anti-reflective glass, and SiO2 used as parts of the following products. ２ It is useful as processed glass, tempered glass, sapphire glass, quartz substrates, mold metals, etc. Products: Car navigation systems, mobile phones, digital cameras, digital video cameras, personal digital assistants (PDAs), portable audio players, car audio systems, game consoles, eyeglass lenses, camera lenses, lens filters, sunglasses, medical equipment (endoscopes, etc.), photocopiers, personal computers (PCs), liquid crystal displays, organic EL displays, plasma displays, touch panel displays, protective films, anti-reflective films, anti-reflective glass, nanoimprint templates, molds, etc.

[0188] This application claims priority based on Japanese Patent Application No. 2024-232026, filed on 27 December 2024, and incorporates all of its disclosures herein.

[0189] 10 Substrate with undercoat 12 Substrate 14 Undercoat 20 Article 22 Surface layer

Claims

1. A compound represented by the following formula (1). X-L １ -Q １ -(L ２ -T １ ) ｎ (1) However, X is a monovalent organosiloxane group, L １ is -C(=O)O-, -C(=O)-, -O-, or a linear alkylene group having 23 or more carbon atoms which may have a phenylene group, Q １ is *-CR Ｑ１ (-**) ２ , *-C(-**) ３ , *-N(-**) ２ , *-SiR Ｑ１ (-**) ２ , *-Si(-**) ３ , or a (1 + n)-valent ring structure, R Ｑ１ is a hydrogen atom or an alkyl group which may have -O-, * represents the bonding position with L １ , ** represents the bonding position with L ２ , L ２ is a single bond or a hydrocarbon group which may have -O-, T １ is a group having a reactive silyl group, Q １ is *-CR Ｑ１ (-**) ２ , *-N(-**) ２ , or *-SiR Ｑ１ (-**) ２ when Q is, n is 2, Q １ is *-C(-**) ３ , or *-Si(-**) ３ when Q is, n is 3, Q １ is a (1 + n)-valent ring structure when Q is, n is an integer of 2 or more, and a plurality of L ２ may be the same or different, and a plurality of T １ may be the same or different.

2. The compound according to claim 1, wherein the number of silicon atoms contained in X in formula (1) is greater than the number of n in formula (1).

3. The compound according to claim 1, wherein n in formula (1) is 2.

4. T in formula (1) above １ However, the compound according to claim 1, represented by the following formula (2): -SiR ａ１ ｚ１ R ａ１１ ３－ｚ１ (2) However, R ａ１ R is a hydrolyzable group, a group having a hydrolyzable group, or a hydroxyl group. ａ１１ is a hydrocarbon group, z1 is an integer from 1 to 3, and R ａ１ , or R ａ１１ If there are multiple R ａ１ , or R ａ１１ These may be the same or different.

5. A surface treatment agent comprising the compound described in any one of claims 1 to 4.

6. The surface treatment agent according to claim 5, further comprising a liquid medium.

7. The surface treatment agent according to claim 5, which is an antifouling coating agent or a waterproof coating agent.

8. The surface treatment agent according to claim 6, which is a stain-resistant coating agent or a waterproof coating agent.

9. An article having a surface layer formed using a compound according to any one of claims 1 to 4 on the surface of a substrate.

10. The article according to claim 9, which is an optical component.

11. The article according to claim 9, wherein the surface layer is provided on the surface of a component that constitutes the surface of a touch panel that is touched by a finger.

12. A method for manufacturing an article, comprising forming a surface layer by a dry coating method using the surface treatment agent described in claim 5.

13. A method for manufacturing an article, comprising forming a surface layer by a dry coating method using the surface treatment agent described in claim 6.

14. A method for manufacturing an article, comprising forming a surface layer by a wet coating method using the surface treatment agent described in claim 6.

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