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

Abstract

The present disclosure addresses the problem of providing: a composition that can form a surface layer which has excellent water repellency; a surface treatment agent; an article; and a method for producing the article.　A composition according to the present disclosure comprises: a specific compound which is selected from the group consisting of compounds represented by formula (1-1) and compounds represented by formula (1-2); and silica particles.　Formula (1-1): Aa1-La1-Qa1-(Ta1)ma1 Formula (1-2): (Ta1)ma1-Qa1-La2-Qa1-(Ta1)ma1

Description

Composition, surface treatment agent, article, and method for manufacturing article

[0001] This disclosure relates to compositions, surface treatment agents, articles, and methods for manufacturing articles.

[0002] In recent years, technologies that make optical articles less prone to fingerprints and easier to clean have become widespread in eyeglass lenses, wearable devices, and touch panel displays to improve their appearance and visibility. One specific method for applying these technologies to improve the appearance, visibility, and other performance aspects of these devices is to form a surface layer on the surface of the article using a surface treatment agent. The use of materials with such surface layers is expected to contribute to achieving Goal 12 of the United Nations' Sustainable Development Goals (SDGs), "Responsible Consumption and Production," as it leads to a longer product lifecycle and, consequently, a reduction in waste.

[0003] For example, Patent Document 1 describes a composition containing a specific silane compound having a divalent linear organopolysiloxane group.

[0004] International Publication No. 2023 / 017830

[0005] Further improvement in water repellency is required for surface layers formed on the surface of articles. As a result of the inventor's investigation with reference to the technology described in Patent Document 1, it was found that there is room for further improvement in the water repellency of surface layers formed using the composition described in Patent Document 1.

[0006] This disclosure has been made in view of these circumstances and aims to provide a composition that can form a surface layer with excellent water repellency. Furthermore, this disclosure aims to provide a surface treatment agent, an article, and a method for manufacturing the article.

[0007] This disclosure includes the following embodiments: [1] A composition comprising a specific compound selected from the group consisting of a compound represented by formula (1-1) described later and a compound represented by formula (1-2) described later, and silica particles. [2] The composition according to [1], wherein the average particle diameter of the silica particles is 12 nm or less. [3] The composition according to [1] or [2], wherein the average particle diameter of the silica particles is 1 μm or more. [4] The specific compound comprises a compound represented by formula (1-1), wherein A in formula (1-1) ａ１ However, the composition is one of the following: the group represented by formula (A1) described later, the group represented by formula (A2) described later, or the group represented by formula (A3) described later. [5] The above specific compound includes the compound represented by formula (1-1), wherein L in formula (1-1) ａ１ However, the composition according to any one of [1] to [4], which includes a group represented by formula (LD) described later. [6] T in formulas (1-1) and (1-2) ａ１The composition according to any one of [1] to [5], wherein the group is represented by formula (TA) described later. [7] The composition according to any one of [1] to [6], wherein the mass ratio of the content of the specific compound to the content of the silica particles is 1 / 3 to 10 / 3. [8] The composition according to any one of [1] to [7], further comprising an acid component. [9] A surface treatment agent comprising the composition according to any one of [1] to [8].

[10] The surface treatment agent according to [9], further comprising a liquid medium.

[11] The surface treatment agent according to [9], which is an antifouling coating agent or a waterproof coating agent.

[12] The surface treatment agent according to

[10] , which is an antifouling coating agent or a waterproof coating agent.

[13] An article having a surface layer formed using the surface treatment agent according to any one of [9] to

[12] on the surface of a substrate.

[14] The article according to

[13] , which is an optical component.

[15] The article according to

[13] or

[14] , wherein the surface layer is located on the surface of a component that constitutes the surface of a touch panel that is touched by a finger.

[16] A method for manufacturing an article, wherein a surface layer is formed by a dry coating method using the surface treatment agent described in [9] or

[11] .

[17] A method for manufacturing an article, wherein a surface layer is formed by a dry coating method using the surface treatment agent described in

[10] or

[12] .

[18] A method for manufacturing an article, wherein a surface layer is formed by a wet coating method using the surface treatment agent described in

[10] or

[12] .

[0008] This disclosure provides a composition capable of forming a surface layer with excellent water repellency. Furthermore, this disclosure provides a surface treatment agent, an article, and a method for manufacturing the article.

[0009] This is a schematic cross-sectional view showing an example of an article according to this embodiment.

[0010] The embodiments for carrying out the embodiments of this disclosure will be described in detail below. However, the embodiments of this disclosure are not limited to the embodiments described below. In the embodiments described below, the components (including elemental steps, etc.) are not essential unless otherwise specified. The same applies to numerical values ​​and their ranges, and do not limit the embodiments of this disclosure.

[0011] In this disclosure, the term "process" includes not only processes that are independent of other processes, but also processes that cannot be clearly distinguished from other processes, provided that the purpose of the process is achieved. In this disclosure, numerical ranges indicated using "~" include the numbers before and after "~" as the minimum and maximum values, respectively. In numerical ranges described in stages in this disclosure, the upper or lower limit of one numerical range may be replaced with the upper or lower limit of another numerical range described in stages. 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. If 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. In this disclosure, "surface layer" means a layer formed on the surface of a substrate using a surface treatment agent. In this disclosure, when a compound or group is represented by a specific formula (X), the compound or group represented by formula (X) may be referred to as compound (X) or compound X, and as group (X) or group X, respectively. In this disclosure, "Me" may mean a methyl group, and "Et" may mean an ethyl group. In this disclosure, when there are multiple identical symbols in a single chemical formula, such identical symbols may represent the same structure or may represent different structures within a defined range.

[0012] [Composition] The composition of the present disclosure (hereinafter also referred to as "the composition") comprises a specific compound selected from the group consisting of a compound represented by formula (1-1) described later and a compound represented by formula (1-2) described later, and silica particles.

[0013] When this composition is used as a surface treatment agent, a surface layer with excellent water repellency can be formed. The reason for this is not entirely clear, but it is presumed that the silica particles are arranged in the in-plane direction in the surface layer formed using this composition, creating a fine uneven structure, which is why a surface layer with excellent water repellency is formed. The components contained in this composition will be described in detail below, component by component.

[0014] <Specific Compound> The specific compound is a compound selected from the group consisting of a compound represented by the following formula (1-1) and a compound represented by the following formula (1-2). A ａ１ -L ａ１ -Q ａ１ -(T ａ１ ) ｍａ１ (1-1) (T ａ１ ) ｍａ１ -Q ａ１ -L ａ２ -Q ａ１ -(T ａ１ ) ｍａ１ (1-2) Provided that A ａ１ is an alkyl group, or a group that contains one or more selected from Si, Ge and Sn and does not have a reactive silyl group; L ａ１ is a chain group; L ａ２ is a chain group; Q ａ１ is a single bond or a (ma1+1)-valent group; T ａ１ is a group containing a reactive silyl group; and ma1 is an integer of 1 or more.

[0015] A ａ１ The alkyl group for A may be any of a linear alkyl group, a branched alkyl group, and a cyclic alkyl group. From the viewpoint of improving liquid repellency, a linear alkyl group or a branched alkyl group is preferred. The number of carbon atoms in the alkyl group is preferably 1 to 10, more preferably 1 to 6, and still more preferably 1 to 4. Specific examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, and a tert-butyl group. From the viewpoint of further improving liquid repellency, a methyl group, an ethyl group, or a tert-butyl group is preferred, and a methyl group is more preferred.

[0016] A ａ１ Examples of the group that contains one or more selected from Si, Ge and Sn and does not have a reactive silyl group for A include groups represented by the following formulas (A1) to (A3). R ａ２１ ３ M-(Q ａ１１ ) ｚａ１ -(R ａＳｉ ) ｚａ２- (A1)

[0017] However, R ａ２１ Each of these independently comprises a hydrocarbon group, or R ｂ２１ ３ M-R ｂ２２ - and R ｂ２１ Each of these independently comprises a hydrocarbon group, or R ｃ２１ ３ M-R ｃ２２ - and R ｃ２１ Each of these independently comprises a hydrocarbon group, or R ｄ２１ ３ M-R ｄ２２ - and R ｄ２１ Each of these independently comprises a hydrocarbon group, or R ｅ２１ ３ M-R ｅ２２ - and R ｅ２１ Each of these is independently a hydrocarbon group, and R ｂ２２ , R ｃ２２ , R ｄ２２ , R ｅ２２ Each is independently an oxygen atom or an alkylene group having 1 to 6 carbon atoms, R ａ２４ Each of these independently comprises a hydrocarbon group or R ｂ２１ ３ M-R ｂ２２ - and ta11 is an integer from 1 to 5, R ａ２５ Each of these independently comprises a hydrocarbon group or R ｂ２１ ３ M-R ｂ２２ - and M is independently Si, Ge, or Sn, Q ａ１１ is -O-, -C(=O)-, or an alkylene group having 1 to 6 carbon atoms, za1 is 0 or 1, za2 is 0 or 1, R ａＳｉ This is a group represented by the following formula (RSi): -(SiR ａ４１ ２ O) ｓａ４１ -SiR ａ４１ ２ - (RSi) R ａ４１ Each of these is independently a hydrocarbon group, and sa41 is a number greater than or equal to 0.

[0018] Rａ２１ , R ｂ２１ , R ｃ２１ , R ｄ２１ , R ｅ２１ , R ａ２４ , R ａ２５ and R ａ４１ The hydrocarbon group in this material can be an aliphatic hydrocarbon group or an aromatic hydrocarbon group, with an aliphatic hydrocarbon group being preferred and an alkyl group being more preferred. The alkyl group may be a linear alkyl group, a branched alkyl group, or a cyclic alkyl group. From the viewpoint of improving liquid repellency, a linear alkyl group or a branched alkyl group is preferred. The number of carbon atoms in the hydrocarbon group is preferably 1 to 10, more preferably 1 to 6, and even more preferably 1 to 4. Specific examples of hydrocarbon groups include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, and a tert-butyl group, with a methyl group or an ethyl group being preferred, and a methyl group being more preferred, from the viewpoint of further improving liquid repellency.

[0019] R ｂ２２ , R ｃ２２ , R ｄ２２ , R ｅ２２ and Q ａ１１ In this formula, linear alkylene groups with 1 to 6 carbon atoms are preferred. Specific examples of alkylene groups with 1 to 6 carbon atoms include methylene, ethylene, propylene, butylene, pentylene, and hexylene groups.

[0020] ta11 is MR ａ２４ ２ The number of repetitions of O is an integer from 1 to 5, preferably an integer from 1 to 3. M is Si, Ge, or Sn, preferably Si. sa41 is SiR ａ４１ ２ The number of repetitions of O is zero or greater, preferably 1 or greater, more preferably 1 to 600, even more preferably 2 to 500, and particularly preferably 8 to 50.

[0021] From equation (A1), (Q ａ１１ ) ｚａ１ - (R ａＳｉ ) ｚａ２ The following are specific examples of substructures excluding Q. However, * indicates Q ａ１１ , R ａＳｉor L ａ１ is the bonding position to

[0022]

[0023] From formula (A2), (Q ａ１１ ) ｚａ１ -(R ａＳｉ ) ｚａ２ Specific examples of the partial structure excluding are as shown below. However, * represents the bonding position to Q ａ１１ , R ａＳｉ or L ａ１

[0024]

[0025] From formula (A3), (Q ａ１１ ) ｚａ１ -(R ａＳｉ ) ｚａ２ Specific examples of the partial structure excluding are as shown below. However, * represents the bonding position to Q ａ１１ , R ａＳｉ or L ａ１

[0026]

[0027] As A ａ１ , a group represented by the above formula (A1), a group represented by the above formula (A2), or a group represented by the above formula (A3) in which each M is independently Si is preferred, and it is more preferred that the group represented by each formula is the above-mentioned preferred embodiment

[0028] L ａ１ and L ａ２ Examples of the chain group in include one or a combination of two or more selected from groups represented by the following formulas (LA) to (LE). -(SiR ａ１１ ２ O) ｓａ１ -SiR ａ１１ ２ - (LA) -(SiR ａ１１ ２ -R ａ１２ ) ｓａ２ -SiR ａ１１ ２ - (LB) -(SiR ａ１１ ２ ​​-R ａ１２ O) ｓａ３ -SiR ａ１１ ２ - (LC) - (CR ａ１３ ２ ) ｓａ４ - (LD) - (SiR ａ１１ ２ O) ｓａ５ - (LE) However, R ａ１１ Each of these is independently a monovalent hydrocarbon group or organopolysiloxane residue which may have an ether bond between carbon atoms, and R ａ１２ Each of these is independently a divalent hydrocarbon group which may have an ether bond between carbon atoms, and R ａ１３ Each of these is independently a hydrogen atom or a monovalent hydrocarbon group which may have an ether bond between carbon atoms, sa1, sa2, sa3, and sa5 are each independently a number from 1 to 200, and sa4 is an integer from 1 to 200.

[0029] R ａ１１ Among these, hydrocarbon groups are preferred, and alkyl groups are more preferred. The alkyl group may be a linear alkyl group, a branched alkyl group, or a cyclic alkyl group. From the viewpoint of improving liquid repellency, linear alkyl groups or branched alkyl groups are preferred. The number of carbon atoms in the hydrocarbon group is preferably 1 to 10, more preferably 1 to 6, and even more preferably 1 to 4. Specific examples of hydrocarbon groups include methyl groups, ethyl groups, n-propyl groups, n-butyl groups, and tert-butyl groups. From the viewpoint of further improving liquid repellency, methyl groups or ethyl groups are preferred, and methyl groups are more preferred. ａ１２ Among these, divalent hydrocarbon groups are preferred, and alkylene groups are more preferred. The alkylene group may be a linear alkylene group, a branched alkylene group, or a cyclic alkylene group. From the viewpoint of improving liquid repellency, linear alkylene groups or branched alkylene groups are preferred. The number of carbon atoms in the hydrocarbon group is preferably 1 to 10, more preferably 1 to 6, and even more preferably 1 to 4. ａ１３ R is preferably a hydrogen atom or a monovalent hydrocarbon group, and as a monovalent hydrocarbon group, ａ１１The structure mentioned above is preferred. ａ１３ Hydrogen atoms are more preferred. Sa1, Sa2, Sa3, and Sa5 are each independently preferably 1 to 150, more preferably 1 to 100, and even more preferably 1 to 20. Sa4 is preferably 11 to 150, more preferably 21 to 100, and even more preferably 29 to 36.

[0030] L ａ１ The group is preferably represented by the following formulas (L1a) to (L1b): -Ak １ - (L1a) -Ak １ -R Ｓｉ -Ak １ - (L1b) However, Ak １ R is a group represented by the above formula (LD), Ｓｉ is a group represented by the above formula (LA) or a group represented by the above formula (LB). Among them, L ａ１ As such, the group represented by the above formula (LD) is more preferred, and R in formula (LD) ａ１３ Furthermore, if sa4 is the above-described preferred embodiment, it is even more preferable.

[0031] L ａ２ The group is preferably represented by the following formulas (L2a) to (L2c). -R Ｓｉ - (L2a) -Ak １ -R Ｓｉ -Ak １ - (L2b) -R Ｓｉ -Ak １ -R Ｓｉ - (L2c) However, Ak １ R is a group represented by the above formula (LD), Ｓｉ This is a group represented by the above formula (LA) or a group represented by the above formula (LB).

[0032] Q ａ１ In this, the (ma1+1) valence base is preferably the base represented by the following formula (QA). * ａ２ -Q ａ４ -R ａ３ -Q ａ５ (-R ａ４ - * ａ３ )ｍａ１ (QA) However, Q ａ４ R is a single bond or a divalent group. ａ３ Q is a hydrocarbon group which may have a single bond or an ether bond between carbon atoms. ａ５ R is a single bond or a (ma1+1) valence group. ａ４ is a hydrocarbon group which may have a single bond or an ether bond between carbon atoms, ma1 is an integer of 1 or more, * ａ２ is, L ａ１ or L ａ２ This is the bonding position with * ａ３ is, T ａ１ This is the connection point.

[0033] Q ａ４ These are single bonds, -O-, -S-, -C(=O)NR ａ５ -, -NR ａ５ C(=O)-, -C(=O)-, -C(=O)O-, -OC(=O)-, -NR ａ５ C(=O)NR ａ５ -, -C(=O)S-, -SC(=O)-, -S(=O) ２ NR ａ５ -, -NR ａ５ S (=O) ２ -, -S (=O) ２ O-, -OS (=O) ２ - or a phenylene group is preferred. However, R ａ５ is a hydrogen atom or a hydrocarbon group.

[0034] Q ａ５ is a single bond, CR ａ６ ｍａ２ , NR ａ７ ｍａ３ , SiR ａ８ ｍａ４ A (ma1+1) valent ring structure, a (ma1+1) valent organopolysiloxane residue, or a (ma1+1) valent hydrocarbon residue is preferred. However, R ａ６ R is a hydrogen atom, a hydroxyl group, or a hydrocarbon group which may have an ether bond between carbon atoms. ａ７ and R ａ８m is a hydrogen atom, or a hydrocarbon group which may have an ether bond between carbon atoms, ma2 is an integer from 0 to 2 and the sum of ma1 and ma2 is 3, ma3 is 0 or 1 and the sum of ma1 and ma3 is 2, and ma4 is an integer from 0 to 2 and the sum of ma1 and ma4 is 3.

[0035] T ａ１ Examples of groups containing a reactive silyl group represented by the following formula (TA) include the group represented by the following formula. * ａ１ -[Si(R ａ１ ) ２ -Q ａ３ ] ｒａ１ -Si(R ａ１ ) ３ (TA) However, R ａ１ Each of these is independently a hydrolyzable group, a group having a hydrolyzable group, a hydroxyl group, or a hydrocarbon group, R ａ１ At least one of them is a hydrolyzable group, a group having a hydrolyzable group, or a hydroxyl group, Q ａ３ is an oxygen atom, or -CR ａ２ ２ - and R ａ２ is a hydrogen atom or hydrocarbon group, ra1 is an integer from 0 to 3, * ａ１ Q ａ１ This is the connection point.

[0036] A hydrolyzable group is a group that becomes a hydroxyl group through hydrolysis. Si-R ａ１ If the group represented is a silyl group having a hydrolyzable group, it undergoes a hydrolysis reaction to become a silanol group represented as Si-OH. The silanol groups further react with each other to form Si-O-Si bonds. In addition, silanol groups can undergo a dehydration condensation reaction with silanol groups derived from oxides present on the surface of the substrate to form Si-O-Si bonds.

[0037] R ａ１ Examples of hydrolyzable groups in this context include alkoxy groups, aryloxy groups, halogen atoms, acyl groups, acyloxy groups, amino groups, and -O-N=CR groups. ｒ ２and isocyanate groups (-NCO) are examples. The alkoxy group is preferably an alkoxy group having 1 to 4 carbon atoms. The aryloxy group is preferably an aryloxy group having 3 to 10 carbon atoms. However, the aryl group of the aryloxy group includes heteroaryl groups. The halogen atom is preferably a chlorine atom. The acyl group is preferably an acyl group having 1 to 6 carbon atoms. The acyloxy group is preferably an acyloxy group having 1 to 6 carbon atoms. R ｒ Each of these is independently an alkyl group having 1 to 10 carbon atoms.

[0038] R ａ１ Groups having hydrolyzable groups include groups in which the hydrolyzable group is bonded to a linking group. Examples of linking groups include alkylene groups, -O- groups, and combinations thereof. Examples of groups having hydrolyzable groups include alkoxyalkyleneoxy groups. Preferably, an alkoxyalkyleneoxy group is a group in which an alkoxy group having 1 to 4 carbon atoms is bonded to a carbon atom of an alkyleneoxy group having 1 to 10 carbon atoms. Specific examples of alkoxyalkyleneoxy groups include 2-methoxyethoxy groups. Among these, R ａ１ From the viewpoint of ease of compound production, an alkoxy group having 1 to 4 carbon atoms or a halogen atom is preferred. ａ１ Because it exhibits less outgassing during application and superior storage stability of the compound, an alkoxy group having 1 to 4 carbon atoms is preferred, and an ethoxy group or a methoxy group is more preferred. Specific examples of hydrolyzable groups include -O-Si(OCH) ３ ) ３ ien-CH ２ -Si(OCH) ３ ) ３ , -C(CH ３ ) ２ -Si(OCH) ３ ) ３ , -O-Si(OCH ２ CH ３ ) ３ ien-CH ２ -Si(OCH) ２ CH ３ ) ３ , -C(CH ３ ) ２ -Si(OCH) ２ CH３ ) ３ These are some examples.

[0039] R ａ１ Examples of hydrocarbon groups in this compound include alkyl groups, cycloalkyl groups, alkenyl groups, and allyl groups. From the viewpoint of ease of synthesis, saturated hydrocarbon groups are preferred, and alkyl groups are more preferred. ａ１ 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.

[0040] In order to form a surface layer with superior sweat resistance, it is preferable that ra1 is an integer between 1 and 3. Specific examples of the base (TA) when ra1 is an integer between 1 and 3 include -Si(OCH) ３ ) ２ -O-Si(OCH) ３ ) ３ , -Si(OCH ３ ) ２ -CH ２ -Si(OCH) ３ ) ３ , -Si(OCH ３ ) ２ -C(CH ３ ) ２ -Si(OCH) ３ ) ３ , -Si(OCH ２ CH ３ ) ２ -O-Si(OCH) ３ ) ３ , -Si(OCH ３ ) ２ -O-Si(OCH) ２ CH ３ ) ３ , -Si(OCH ２ CH ３ ) ２ -O-Si(OCH) ２ CH ３ ) ３ , -Si(OCH ２ CH ３ ) ２ -CH ２ -Si(OCH) ３ ) ３ , -Si(OCH ３ ) ２ -CH ２-Si (O) ２ HH ３ ) ３ ,-Si(OCH ２ HH ３ ) ２ -CH ２ -Si (O) ２ HH ３ ) ３ ,-Si(OCH ２ HH ３ ) ２ -C(CH ３ ) ２ -Si (O) ３ ) ３ ,-Si(OCH ３ ) ２ -C(CH ３ ) ２ -Si (O) ２ HH ３ ) ３ ,-Si(OCH ２ HH ３ ) ２ -C(CH ３ ) ２ -Si (O) ２ HH ３ ) ３ ,-Si(OH) ２ -O-Si (O) ３ ,-Si(OH) ２ -O-Si (OCH) ３ ) ３ ,-Si(OCH ３ ) ２ -O-Si (O) ３ ,-Si(OH) ２ -CH ２ -Si (O) ３ ,-Si(OH) ２ -CH ２ -Si (O) ３ ) ３ ,-Si(OCH ３ ) ２ -CH ２ -Si (O) ３ ,-Si(OH) ２ -C(CH ３ ) ２ -Si (O) ３ ,-Si(OH) ２ -C(CH ３ )２ -Si(OCH) ３ ) ３ , -Si(OCH ３ ) ２ -C(CH ３ ) ２ -Si(OH) ３ These are some examples.

[0041] When ra1 is 0, the above group (TA) is the group represented by the following formula (T1). * ａ１ -Si(R ａ１ ) ３ (T1) However, R ａ１ Each of these is independently a hydrolyzable group, a group having a hydrolyzable group, a hydroxyl group, or a hydrocarbon group, R ａ１ At least one of them is a hydrolyzable group, a group having a hydrolyzable group, or a hydroxyl group, * ａ１ Q ａ１ This is the connection point.

[0042] Furthermore, in equations (1-1) and (1-2), ma1 is T ａ１ This represents the number of elements, and can be any integer greater than or equal to 1, preferably between 1 and 3, more preferably between 1 and 2, and even more preferably 1.

[0043] Q ａ１ - (T ａ１ ) ｍａ１ Specific examples include the following. However, α is an integer from 1 to 100, and * is L ａ１ or L ａ２ This is the connection point.

[0044]

[0045]

[0046] The composition preferably contains a compound represented by formula (1-1) as a specific compound, and more preferably contains a compound represented by formula (1-1) in which each group in formula (1-1) is in the preferred form described above.

[0047] Specific examples of the specified compounds are listed below. In the formula, n1 is the average and is 3, 4, 5, 6, 7, 8, 9, 10, 13, or 15.5.

[0048]

[0049]

[0050]

[0051]

[0052] The content of the specific compound is preferably 0.001 to 99% by mass, more preferably 0.01 to 80% by mass, and even more preferably 0.1 to 70% by mass, based on the total amount of the composition. When the composition is used in a wet coating method, the content of the specific compound is preferably 0.01 to 10% by mass, more preferably 0.02 to 5% by mass, even more preferably 0.03 to 3% by mass, particularly preferably 0.05 to 2% by mass, and extremely preferably 0.2 to 2% by mass, based on the total amount of the composition.

[0053] <Silica Particles> Examples of silica particles included in this composition include solid silica particles, porous silica particles, and hollow silica particles. The silica particles may be in powder form or in sol form (colloidal silica) dispersed in a solvent. Examples of solvents for dispersing silica particles in colloidal silica include organic solvents such as alcohol and water. More specifically, examples include isopropanol, methanol, ethylene glycol, ethylene glycol monopropyl ether, propylene glycol monomethyl ether, dimethylacetamide, N-methylpyrrolidone, methyl isobutyl ketone, dimethyl sulfoxide, acetone, and water. The silica particles may contain metals other than silicon atoms. These other metals may form complex oxides with the silicon atoms. The silica particles may also be silica particles that have been surface-treated with surfactants and silane coupling agents.

[0054] In one embodiment, the average particle diameter of the silica particles may be, for example, 0.1 nm or more, 1 nm or more, or 200 μm or less. In another embodiment, the average particle diameter of the silica particles is preferably 20 nm or less, and more preferably 12 nm or less, in that it can form a surface layer with excellent water repellency. In yet another embodiment, the average particle diameter of the silica particles is preferably 1 μm or more, more preferably 10 μm or more, even more preferably 30 to 100 μm, particularly preferably 45 to 80 μm, and extremely preferably 50 to 75 μm, in that it can form a surface layer with excellent water repellency.

[0055] In this disclosure, the average particle diameter of silica particles refers to the volume-based cumulative 50% diameter (D50), which is the particle diameter at the point where the cumulative volume distribution curve, where the total volume of the particle size distribution determined by volume is set to 100%, reaches 50%. The particle size distribution is determined by the frequency distribution and cumulative volume distribution curve measured with a laser diffraction / scattering particle size distribution analyzer. If the silica particles used in the preparation of this composition are commercially available products, the above average particle diameter may be a catalog value.

[0056] The silica particles mentioned above may be commercially available colloidal silica or powdered silica particles, or silica particles synthesized from raw materials such as alkoxysilanes.

[0057] The silica particles contained in this composition may be of one type or two or more types. The silica particle content may be, for example, 0.01 to 99% by mass of the total amount of the composition, preferably 1 to 99% by mass, more preferably 2 to 60% by mass, and even more preferably 5 to 40% by mass. When this composition is used for wet coating, the silica particle content may be, for example, 0.01 to 10% by mass of the total amount of the composition, preferably 0.01 to 5% by mass, more preferably 0.1 to 4% by mass, even more preferably 0.05 to 3% by mass, and very preferably 0.2 to 2% by mass.

[0058] In this composition, the mass ratio of the content of the specific compound to the content of silica particles may be, for example, 1 / 20 to 20 / 1, and is preferably 1 / 3 to 10 / 3, and more preferably 1 / 2 to 10 / 3, in that it can form a surface layer with excellent water repellency.

[0059] <Acid Components> This composition may contain acid components. It is preferable that this composition contains acid components in that it can promote the hydrolysis and condensation reactions of reactive silyl groups possessed by specific compounds. The acid components may be either inorganic acids or organic acids. Examples of acid components include hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, acetic acid, formic acid, trifluoroacetic acid, and sulfonic acids (e.g., methanesulfonic acid and p-toluenesulfonic acid), with hydrochloric acid, acetic acid, nitric acid, sulfuric acid, or formic acid being preferred.

[0060] If the composition contains an acidic component, the amount of the acidic component may be, for example, 0.1 to 50% by mass, preferably 1 to 40% by mass, and more preferably 1 to 10% by mass, based on the total mass of the composition.

[0061] <Liquid Medium> This composition may further contain a liquid medium. When this composition contains a liquid medium, it may be a solution or a dispersion. This composition containing a liquid medium is useful for coating applications and can be used as a coating liquid.

[0062] 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), C ２F 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.

[0063] Specific examples of hydrocarbon organic solvents include pentane, hexane, heptane, octane, hexadecane, isohexane, isooctane, isononane, cycloheptane, cyclohexane, bicyclohexyl, benzene, toluene, ethylbenzene, o-xylene, m-xylene, p-xylene, o-diethylbenzene, m-diethylbenzene, p-diethylbenzene, n-butylbenzene, sec-butylbenzene, and tert-butylbenzene.

[0064] 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.

[0065] 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.

[0066] Specific examples of ether-based organic solvents include diethyl ether, cyclopentyl methyl ether, tetrahydrofuran, and 1,4-dioxane.

[0067] 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.

[0068] 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.

[0069] Other organic solvents include chlorinated organic solvents, nitrogen-containing compounds, sulfur-containing compounds, and siloxane compounds.

[0070] 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.

[0071] Specific examples of nitrogen-containing compounds include nitrobenzene, acetonitrile, benzonitrile, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, and 1,3-dimethyl-2-imidazolidinone.

[0072] Specific examples of sulfur-containing compounds include carbon disulfide and dimethyl sulfoxide.

[0073] Specific examples of siloxane compounds include hexamethyldisiloxane, octamethyltrisiloxane, and decamethyltetrasiloxane.

[0074] The liquid medium contained in this composition may be one type or two or more types. When this composition contains a liquid medium, the content of the liquid medium is preferably 60 to 99.999% by mass, more preferably 80 to 99.99% by mass, and even more preferably 90 to 99.9% by mass, based on the total amount of the composition. When this composition is used in a wet coating method, the content of the liquid medium is preferably 90 to 99.99% by mass, more preferably 95 to 99.98% by mass, even more preferably 97 to 99.97% by mass, and particularly preferably 98 to 99.95% by mass, based on the total amount of the composition.

[0075] <Other Components> The composition may further contain other components besides the specific compound, silica particles, acid component, and liquid medium, to the extent that they do not impair the effects of the disclosed herein. Other components include other catalysts other than the acid component (e.g., base catalysts).

[0076] Other catalysts that can be used include any suitable base, transition metals (e.g., Ti, Ni, Sn, Zr, Al, B, etc.), sulfur-containing compounds having lone pairs of electrons in their molecular structure, nitrogen-containing compounds (e.g., sulfoxide compounds, aliphatic amine compounds, aromatic amine compounds, phosphate amide compounds, amide compounds, urea compounds), etc. Examples of base catalysts include ammonia, sodium hydroxide, potassium hydroxide, and organic amines such as triethylamine and diethylamine.

[0077] Other components include metal compounds having hydrolyzable groups. When a composition contains metal compounds having hydrolyzable groups, the slipperiness and antifouling properties of the surface layer formed using the composition can be further improved.

[0078] The content of other components that may be included in the composition is preferably 10% by mass or less, and more preferably 1% by mass or less, based on the total mass of the composition. If the composition contains the above-mentioned metal compound, the content of the above-mentioned metal compound is preferably 0.01 to 30% by mass, more preferably 0.01 to 10% by mass, and even more preferably 0.05 to 5% by mass, based on the total mass of the composition.

[0079] The total content of specific compounds, silica particles, acidic components, and other components (hereinafter also referred to as "solid content concentration") is preferably 0.001 to 40% by mass, more preferably 0.01 to 20% by mass, and even more preferably 0.1 to 10% by mass, based on the total mass of the composition. The solid content concentration of the composition is calculated from the mass before heating and the mass after heating in a convection dryer at 120°C for 4 hours.

[0080] [Surface Treatment Agent] In one embodiment, the surface treatment agent of the present disclosure (hereinafter also referred to as "the surface treatment agent") comprises the composition of the present disclosure. The surface treatment agent may also be the composition of the present disclosure. Preferred embodiments of the surface treatment agent are the same as preferred embodiments of the composition of the present disclosure.

[0081] This surface treatment agent is suitable for applications requiring water repellency, such as forming a surface layer on components that make up the touch surfaces of touch panels, eyeglass lenses, and displays of wearable devices. Furthermore, due to its excellent water repellency, this surface treatment agent 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 or waterproof coating agent.

[0082] [Article] In one embodiment, the article of the present disclosure (hereinafter also referred to as "the Article") has a surface layer formed using the surface treatment agent on the surface of a substrate. Preferably, the Article has a substrate and the above-mentioned surface layer.

[0083] The surface layer may be formed on a part of the surface of the substrate or on the entire surface of the substrate. The surface layer may spread as a film on the surface of the substrate or may be scattered as dots. In the surface layer, the specific compound is contained in a state in which some or all of the reactive silyl groups have undergone hydrolysis and the dehydration condensation reaction of the silanol groups has progressed.

[0084] The thickness of the surface layer can be appropriately adjusted within the range of 1 nm to 200 μm. For example, when the average particle diameter of the silica particles is 20 nm or less, the surface layer thickness is preferably 1 to 100 nm, and more preferably 1 to 50 nm. If the surface layer thickness is 1 nm or more, the effect of the surface layer is easily obtained. If the surface layer thickness is 100 nm or less, the utilization efficiency is high. Also, when the average particle diameter of the silica particles is 1 μm or more, the surface layer thickness is preferably 1 to 200 μm, more preferably 30 to 105 μm, even more preferably 45 to 85 μm, and particularly preferably 50 to 80 μm. The surface layer thickness 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 (product name "ATX-G", manufactured by RIGAKU Corporation).

[0085] The surface layer may be provided directly on the surface of the substrate, or a base layer may be provided between the substrate and the surface layer. From the viewpoint of further improving the water repellency and abrasion resistance of the surface layer, it is preferable that the article includes a substrate, a base layer disposed on the substrate, and a surface layer formed using the surface treatment agent disposed on the base layer.

[0086] An example of this 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 this article. The first article is an article 20 having a base material 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 is a surface layer formed using this surface treatment agent.

[0087] The material and shape of the substrate 12 may be appropriately selected according to the intended use of the article 20. Examples of materials for the substrate 12 include glass, resin, sapphire, metal, ceramic, stone, and composite materials thereof. The glass may be chemically strengthened. Examples of substrates 12 that require water repellency include substrates for touch panels, substrates for displays, substrates that constitute the housing of electronic devices, and eyeglass lenses. Substrates for touch panels and substrates for displays 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 substrate for touch panels.

[0088] 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.

[0089] 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 hydrolyzable silyl groups of the compound undergo dehydration condensation, forming Si-O-Si bonds between it and the base layer 14, resulting in a surface layer 22 with superior abrasion resistance.

[0090] 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.

[0091] From the standpoint of excellent wear resistance 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. The inclusion of these elements strengthens the bond between the base layer 14 and the compound, improving wear resistance.

[0092] To improve the adhesion of this surface treatment agent and to improve the water repellency and abrasion resistance 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 ensure sufficient mechanical properties of the underlying layer, the average value of the alkali metal atom concentration should be 4.0 × 10 ２２ atoms / cm ３ The following is preferable:

[0093] The base layer may be a single layer or multiple layers. The base layer may have irregularities on its surface. 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 effect of improving adhesion by the base layer 14 is likely to be sufficiently 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.

[0094] 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.

[0095] Another example of this article is a second article. The second article is an article 20 having 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 is a surface layer formed using this surface treatment agent.

[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 this article include optical components (for example, optical components used as part of the products listed below), touch panels, anti-reflective films, anti-reflective glass, and SiO2. 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, 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.

[0098] [Method for Manufacturing Articles] One method for manufacturing articles is to use this surface treatment agent to form a surface layer on the surface of a substrate, thereby manufacturing an article having a substrate and a surface layer. Methods for forming the surface layer include dry coating and wet coating.

[0099] This surface treatment agent can be used directly in dry coating methods and is suitable for forming a surface layer with excellent adhesion by dry coating. 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 may be used in which a specific compound and silica particles, etc., are supported using this composition on a porous metal body made of a metal material such as iron or steel. The pellet-like material on which the above compound, etc., is supported can be manufactured by impregnating the porous metal body with this composition containing a liquid medium and drying 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 specific compounds contained in this composition and the substrate may be performed as needed. Such operations include heating, humidification, and light irradiation. For example, heating a substrate on which a surface layer has been formed in a humid atmosphere can promote reactions such as the hydrolysis of hydrolyzable groups, the reaction between hydroxyl groups on the surface of the substrate and silanol groups, and the formation of siloxane bonds through the condensation reaction of silanol groups. After the formation of the surface layer, compounds in the surface layer that are not chemically bonded to other compounds or the substrate may be removed as needed. Methods of removal 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 more detail below using examples, but the present invention is not limited to these examples. Examples 1 to 15 are examples, and Examples 16 to 18 are comparative examples.

[0103] [Synthesis Example 1: Synthesis of Compound 1-A] (Synthesis of Compound 1-A-1) 65 g of hexamethylcyclotrisiloxane was mixed with 101 g of THF (tetrahydrofuran) and stirred at 25°C until dissolved. The reaction mixture was then cooled to -30°C, and 100 mL of methyllithium (3.1 M in diethoxymethane) was added and the mixture was stirred at -30°C for 2 hours. Next, 100 g of chlorodimethylsilane was added and the mixture was stirred at -30°C for 1 hour, then the temperature was raised to 25°C and stirred for another hour. After removing the low-boiling components by distillation, hexane and water were added for extraction, and then the mixture was purified by distillation to obtain 65 g of Compound 1-A-1.

[0104]

[0105] 1 H NMR (400 MHz, CDCl3) δ 4.71 (p, J = 2.8 Hz, 1H), 0.50 - -0.23 (m, 27H).

[0106] (Synthesis of Compound 1-A-2) Compound 1-A-1 (1.0 g) was mixed with dichloromethane (20 g) and 18-bromo-1-octadecene (1.0 g) and stirred at 25°C until homogeneous. Next, a toluene solution of platinum / 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (platinum content: 3% by mass, 4.1 mg) was added and stirred at 25°C for 2 hours. After removing the low-boiling components under reduced pressure, 1.5 g of compound 1-A-2 was obtained by flash column chromatography using silica gel (developing solvent: decane / dichloromethane).

[0107]

[0108] 1 H NMR (400 MHz, CDCl3) δ 3.41 (t, J = 6.9 Hz, 2H), 1.94 - 1.78 (m, 2H), 1.52 - 1.10 (m, 30H), 0.53 (t, J = 7.7 Hz, 2H), 0.39 - -0.24 (m, 27H).

[0109] (Synthesis of Compound 1-A-3) 11-bromo-1-undecene (2.0 g) was mixed with THF (20 g) and magnesium (1.1 g) and stirred at 60°C for 2 hours. After removing the magnesium residue by filtration of the reaction mixture, the reaction mixture was cooled to 0°C, and compound 1-A-2 (1.5 g) and tetrachlorocopper(II) dilithium solution (0.1 M in THF, 0.05 g) were added and stirred at 0°C for 24 hours. After extraction with hydrochloric acid and decane, low-boiling point components were removed by vacuum distillation, and 1.1 g of compound 1-A-3 was obtained by flash column chromatography using silica gel (developing solvent: decane).

[0110]

[0111] 1 H NMR (400 MHz, CDCl3) δ 6.00 - 5.67 (m, 1H), 5.15 - 4.67 (m, 2H), 2.19 - 1.86 (m, 2H), 1.55 - 1.08 (m, 50H), 0.53 (dd, J = 10.0, 5.3 Hz, 2H), 0.39 - -0.24 (m, 27H).

[0112] (Synthesis of Compound 1-A) Compound 1-A-3 (1.1 g) was dissolved in decane (10 g). Then, a toluene solution of platinum / 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (platinum content: 3% by mass, 4.1 mg), aniline (2.6 mg), and trimethoxysilane (0.60 g) were added, and the mixture was stirred at 50°C for 2 hours. By removing the solvent under reduced pressure, 1.3 g of compound 1-A was obtained.

[0113]

[0114] 1 H NMR (400 MHz, CDCl3) δ 3.48 (s, 9H), 1.50 - 1.01 (m, 54H), 0.63 - 0.51 (m, 2H), 0.44 (t, J = 7.7 Hz, 2H), 0.39 - -0.24 (m, 27H).

[0115] [Synthesis Example 2: Synthesis of Compound 1-B] Compound 1-A-3 (1.1 g) was dissolved in decane (10 g). Then, a toluene solution of platinum / 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (platinum content: 3% by mass, 4.1 mg), aniline (2.6 mg), and dimethoxysilyltrimethyl silicate (1.0 g) were added, and the mixture was stirred at 50°C for 2 hours. By removing the solvent under reduced pressure, 1.3 g of compound 1-B was obtained.

[0116]

[0117] 1 H NMR (500 MHz, CDCl3) δ 3.72 - 3.21 (m, 15H), 1.58 - 1.04 (m, 54H), 0.85 - 0.43(m, 4H), 0.12 - -0.15 (m, 27H).

[0118] [Synthesis Example 3: Synthesis of Compound 1-C] Compound 1-C was obtained according to the method described in International Publication No. 2023 / 017830. In the formula, "18" is the average value.

[0119]

[0120] [Synthesis Example 4: Synthesis of Compound 1-D] Compound 1-D was obtained according to the method described in Japanese Patent Publication No. 2017-201010. The average value of the number of repeating units n was 17.

[0121]

[0122] [Synthesis of Compound 1-E] Compound 1-E was synthesized using the method described in International Publication No. 2024 / 262627. The average value of n was 7.

[0123] (1-E)

[0124] [Silica Particles] The following silica particles SP-1 to SP-6 were purchased and used in the preparation of the composition. SP-1 to SP-3 were all isopropanol dispersions of standard grade organosilica sol, with a solid content concentration of 30% by mass. ・SP-1: "IPA-ST" manufactured by Nissan Chemical Corporation, average particle size 12 nm. ・SP-2: "IPA-ST-L" manufactured by Nissan Chemical Corporation, average particle size 45 nm. ・SP-3: "IPA-ST-ZL" manufactured by Nissan Chemical Corporation, average particle size 80 nm. ・SP-4: Silica gel particles with an average particle size of 30 μm and a pore diameter of 100 Å (angstrom). ・SP-5: Silica gel particles with an average particle size of 50 μm and a pore diameter of 60 Å. ・SP-6: Silica gel particles with an average particle size of 75 μm and a pore diameter of 120 Å.

[0125] [Preparation of Compositions] A specific compound, silica particles, hydrochloric acid (concentration 2 mol / L), and isopropanol (IPA) were added to a polypropylene container equipped with a stirrer and thermometer. The amount of each component added was adjusted so that the content of each component in the resulting composition was as shown in Table 1 below. The resulting mixture was stirred at 25°C for 30 minutes to obtain the compositions (surface treatment agents) of Examples 1 to 17.

[0126] [Manufacturing of Articles] As a base material, a glass substrate (water contact angle: 5 degrees, 100 mm x 100 mm) whose surface was cleaned by plasma treatment was prepared. The composition for each example was applied to the plasma-treated surface of the glass substrate by spray coating. In the application of the composition, the amount of composition applied relative to the surface area of ​​the glass substrate was 0.074 mL / cm². ２ The amount of composition applied was adjusted accordingly. Next, the resulting coating film was heat-treated at 140°C for 30 minutes. After that, it was kept in a constant temperature and humidity chamber set to 90°C and 60% humidity for 100 hours. The surface of the formed coating film was wiped with a paper cloth soaked in ethanol to obtain an article having a glass substrate and a surface layer formed on the surface of the glass substrate using the composition of each example.

[0127] [Evaluation] <Water Repellency> Approximately 2 μL of distilled water was dropped onto the surface layer of each example's article, and the initial water contact angle (°) was measured using a contact angle measuring device (product name "DM-500", manufactured by Kyowa Interface Science Co., Ltd.). The arithmetic mean of the contact angle measurements taken at five locations on the surface layer was taken, and the resulting average value was defined as the water contact angle. The 2θ method was used to calculate the water contact angle. Based on the obtained initial water contact angles, the water repellency of the surface layer of each example's article was evaluated according to the evaluation criteria below. A larger initial water contact angle indicates better water repellency of the surface layer. The evaluation results for each example are shown in the table below.

[0128] (Evaluation criteria for water repellency) A: Initial water contact angle is 140° or higher B: Initial water contact angle is 120° or higher but less than 140° C: Initial water contact angle is less than 120°

[0129] <Fingerprint Removal Test> A 1 kg weight equipped with a 2 cm diameter red rubber stopper to serve as the fingerprint stamp portion was prepared. Next, 70 μL of artificial fingerprint solution (manufactured by Isekyu Co., Ltd.) was dropped onto a cloth, and the fingerprint stamp was left in the solution for 1 minute. To remove excess artificial fingerprint solution from the fingerprint stamp, it was left in a new cloth for 20 seconds. After that, an item with a surface layer formed on it was placed on a hot plate heated to 23°C. The fingerprint stamp was pressed onto the surface layer. The item with the artificial fingerprint solution attached was placed in a sliding device (product name "HHS-2000", manufactured by Shinto Kagaku Co., Ltd.). A flat indenter with an area of ​​1 cm square was attached to a wiping cloth (Savina Minimax, manufactured by KB Seiren Co., Ltd.) using double-sided tape, and placed in the sliding device. With a load of 500 g, the attached artificial fingerprint solution was wiped off the surface layer in one direction with the wiping cloth. The haze on the wiped area was measured using a haze meter (product name "NDH7000SP", manufactured by Nippon Denshoku Industries Co., Ltd.). The fingerprint removal performance was evaluated based on the measured haze values ​​according to the following evaluation criteria.

[0130] (Evaluation criteria for fingerprint removal performance) A: Haze value less than 0.3% B: Haze value 0.3% or more and less than 1.0% C: Haze value 1.0% or more

[0131] <Sweat Resistance> Samples for sweat resistance evaluation were prepared by cutting each example's item into 1 cm x 1 cm squares. 0.79 parts by mass of disodium hydrogen phosphate / dodecahedra, 0.79 parts of sodium chloride, 0.5 parts by mass of acetic acid, and 97.92 parts by mass of deionized water were mixed until homogeneous to prepare an artificial sweat solution (pH 8.0 at 25°C). The obtained samples were immersed in the artificial sweat solution at 20°C for 100 hours. After that, the samples were removed from the artificial sweat solution, washed with ethanol, dried, and the water contact angle was measured according to the procedure described above. The difference in water contact angle before and after the immersion test was calculated by subtracting the water contact angle measured after the immersion test in the artificial sweat solution from the initial water contact angle. A smaller calculated difference indicates less reduction in water repellency due to the immersion test using alkaline artificial sweat solution, and thus better sweat resistance. Based on the difference in water contact angle before and after the immersion test, the sweat resistance of the surface layer of each example's item was evaluated according to the evaluation criteria below. The evaluation results for each example are shown in the table below.

[0132] (Evaluation criteria for sweat resistance) A: The decrease in the water contact angle before and after the immersion test is 10° or less. B: The decrease in the water contact angle before and after the immersion test is more than 10°.

[0133] The following table shows the types and amounts of each component contained in each example composition, as well as the evaluation results. In the table, the "Content [Si equivalent] [parts by mass]" column for "Silica particles" indicates the amount of Si atoms in the silica particles contained in each composition. ２ This shows the silica particle content obtained by converting it to [amount].

[0134]

[0135] As shown in Table 1, it was confirmed that a surface layer with excellent water repellency can be formed by using a composition containing a specific compound and silica particles (Examples 1 to 15).

[0136] The articles of this disclosure have excellent water repellency. Examples of articles of this disclosure include optical articles, touch panels, anti-reflective films, anti-reflective glass, and SiO2, which are used as parts of the following products. ２It 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.

[0137] This application claims priority based on Japanese Patent Application No. 2025-56520, filed on 28 March 2025, and Japanese Patent Application No. 2025-62891, filed on 7 April 2025, and incorporates all of their disclosures herein.

[0138] 10 Substrate with undercoat 12 Substrate 14 Undercoat 20 Article 22 Surface layer

Claims

1. A composition comprising: silica particles; and a specific compound selected from the group consisting of a compound represented by formula (1-1) and a compound represented by formula (1-2), wherein A ａ１ -L ａ１ -Q ａ１ -(T ａ１ ) ｍａ１    (1-1)    (T ａ１ ) ｍａ１ -Q ａ１ -L ａ２ -Q ａ１ -(T ａ１ ) ｍａ１    (1-2) wherein, A ａ１ is an alkyl group, or a group containing at least one element selected from the group consisting of Si, Ge and Sn and having no reactive silyl group, L ａ１ is a chain group, L ａ２ is a chain group, Q ａ１ is a single bond or a (ma1+1)-valent group, T ａ１ is a group containing a reactive silyl group, and ma1 is an integer of 1 or more.

2. The composition according to claim 1, wherein the average particle size of the silica particles is 12 nm or less.

3. The composition according to claim 1, wherein the average particle diameter of the silica particles is 1 μm or more.

4. The specified compound includes the compound represented by formula (1-1), and A in formula (1-1) ａ１ The composition according to claim 1, wherein the group is represented by formula (A1), formula (A2), or formula (A3). ａ２１ ３ M-(Q) ａ１１ ) ｚａ１ - (R ａＳｉ ) ｚａ２ - (A1) However, R ａ２１ Each of these independently comprises a hydrocarbon group, or R ｂ２１ ３ M-R ｂ２２ - and R ｂ２１ Each of these independently comprises a hydrocarbon group, or R ｃ２１ ３ M-R ｃ２２ - and R ｃ２１ Each of these independently comprises a hydrocarbon group, or R ｄ２１ ３ M-R ｄ２２ - and R ｄ２１ Each of these independently comprises a hydrocarbon group, or R ｅ２１ ３ M-R ｅ２２ - and R ｅ２１ Each of these is independently a hydrocarbon group, and R ｂ２２ , R ｃ２２ , R ｄ２２ , R ｅ２２ Each is independently an oxygen atom or an alkylene group having 1 to 6 carbon atoms, R ａ２４ Each of these independently comprises a hydrocarbon group or R ｂ２１ ３ M-R ｂ２２ - and ta11 is an integer from 1 to 5, R ａ２５ Each of these independently comprises a hydrocarbon group or R ｂ２１ ３ M-R ｂ２２ - and M is Si, and Q ａ１１ is -O-, -C(=O)-, or an alkylene group having 1 to 6 carbon atoms, za1 is 0 or 1, za2 is 0 or 1, R ａＳｉ This is a group represented by the following formula (RSi): -(SiR ａ４１ ２ O) ｓａ４１ -SiR ａ４１ ２ - (RSi) However, R ａ４１ Each of these is independently a hydrocarbon group, and sa41 is a number greater than or equal to 0.

5. The specified compound includes the compound represented by formula (1-1), and L in formula (1-1) ａ１ The composition according to claim 1, wherein it contains a group represented by formula (LD). - (CR ａ１３ ２ ) ｓａ４ - (LD) However, R ａ１３ Each of these is independently a hydrocarbon group which may have a hydrogen atom or an ether bond between carbon atoms, and sa4 is an integer from 1 to 200.

6. T in formulas (1-1) and (1-2) ａ１ The composition according to claim 1, wherein the group is represented by the following formula (TA). ａ１ -[Si(R ａ１ ) ２ -Q ａ３ ] ｒａ１ -Si(R ａ１ ) ３ (TA) However, R ａ１ Each of these is independently a hydrolyzable group, a group having a hydrolyzable group, a hydroxyl group, or a hydrocarbon group, R ａ１ At least one of them is a hydrolyzable group, a group having a hydrolyzable group, or a hydroxyl group, Q ａ３ is an oxygen atom, or -CR ａ２ ２ - and R ａ２ is a hydrogen atom or hydrocarbon group, ra1 is an integer from 0 to 3, * ａ１ Q ａ１ This is the connection point.

7. The composition according to claim 1, wherein the mass ratio of the content of the specific compound to the content of the silica particles is 1 / 3 to 10 / 3.

8. The composition according to claim 1, further comprising an acidic component.

9. A surface treatment agent comprising the composition according to any one of claims 1 to 8.

10. The surface treatment agent according to claim 9, further comprising a liquid medium.

11. The surface treatment agent according to claim 9, which is an antifouling coating agent or a waterproof coating agent.

12. The surface treatment agent according to claim 10, which is an antifouling coating agent or a waterproof coating agent.

13. An article having a surface layer formed using the surface treatment agent described in claim 9 on the surface of a substrate.

14. The article according to claim 13, which is an optical component.

15. The article according to claim 13, 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.

16. A method for manufacturing an article, comprising forming a surface layer by a dry coating method using the surface treatment agent described in claim 9.

17. A method for manufacturing an article, comprising forming a surface layer by a dry coating method using the surface treatment agent described in claim 10.

18. A method for manufacturing an article, comprising forming a surface layer by a wet coating method using the surface treatment agent described in claim 10.

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