Composition, surface treatment agent, article, and method for producing article
Patent Information
- Authority / Receiving Office
- JP · JP
- Patent Type
- Applications
- Filing Date
- 2024-10-07
- Publication Date
- 2025-04-10
AI Technical Summary
The prior art is difficult to achieve good wear durability in the surface treatment layer, affecting surface performance and visibility.
Using a combination of the first and second compounds, the first compound having a double-chain group and a reactive silicon group connected at one end of the double-chain group, and the second compound having a double-chain group and a reactive silicon group connected at both ends of the double-chain group, a surface treatment layer with excellent wear durability and water repelllent properties is formed by adjusting the ratio of the two compounds.
The high wear durability and non-slip properties of the surface treatment layer are achieved, and the surface performance and visibility are improved, and suitable for applications requiring high wear resistance and easy cleaning.
Abstract
Description
Composition, surface treatment agent, article, and method for manufacturing article
[0001] The present disclosure relates to compositions, surface treatments, articles, and methods for making articles.
[0002] In recent years, there has been a demand for technologies that make surfaces of articles less susceptible to fingerprints and that make them easier to remove stains, in order to improve performance such as appearance and visibility. As a specific method, a method of performing a surface treatment on the surface of an article using a surface treatment agent is known.
[0003] For example, Patent Document 1 describes the use of a silane compound containing a siloxane group having a specific structure as a surface treatment agent.
[0004] International Publication No. 2023 / 017830
[0005] In view of the above, the present disclosure provides a composition and a surface treatment agent capable of forming a surface treatment layer having excellent abrasion resistance, an article having a surface treatment layer having excellent abrasion resistance, and a method for producing the same.
[0006] Means for solving the above problems include the following aspects: <1> A composition comprising: a first compound having a divalent chain group and a reactive silyl group linked to only one end of the divalent chain group; and a second compound having a divalent chain group and reactive silyl groups linked to both ends of the divalent chain group, wherein the amount of the second compound relative to the total amount of the first compound and the second compound is more than 35 mol % and not more than 95 mol %. <2> The composition according to <1>, wherein the first compound is a compound having a chain organo(poly)siloxane residue and a reactive silyl group linked to only one end of the chain organo(poly)siloxane residue, and the second compound is a compound having a chain organo(poly)siloxane residue and reactive silyl groups linked to both ends of the chain organo(poly)siloxane residue. <3> The composition according to <1> or <2>, wherein the reactive silyl groups in the first compound and the second compound are each independently represented by the following formula (S1) or formula (S3): —Si(R 2) n L 3-n ...(S1) -[Si(L 2 ) 2 -P] r1 -Si(L 2 ) 3 ...(S3) In formula (S1), R 2 are each independently a hydrocarbon group, L is each independently a hydrolyzable group, a group having a hydrolyzable group, or a hydroxyl group, and n is an integer of 0 to 2. In formula (S3), L 2 are each independently a hydrolyzable group, a group having a hydrolyzable group, a hydroxyl group, or a hydrocarbon group; 2 At least four L 2 represents a hydrolyzable group, a group having a hydrolyzable group, or a hydroxyl group, each P independently represents an oxygen atom or an organic group having one carbon atom bonded to adjacent Si atoms on both sides, and r1 is an integer of 1 to 3. <4> The composition according to <2> or <3> dependent on <2>, wherein the chain organo(poly)siloxane residues in the first compound and the second compound are each independently represented by the following formula (B1) or (B2): In formula (B1), R 3 are each independently a hydrocarbon group, k1 is a number of 1 or more, and * is a bonding site to an adjacent atom. In formula (B2), R 4 are each independently a hydrocarbon group or T 11 -B r -(SiR 3 2 -O) k1 - and T 11 are each independently a monovalent group; B is each independently -O- or -C(=O)-; r is each independently 0 or 1; R 3are each independently a hydrocarbon group, k1 is each independently a number of 1 or more, and * is a bonding site to an adjacent atom. <5> The composition according to <4>, wherein in formula (B1) or (B2), k1 is a number of 1 to 600. <6> The composition according to <1> or <3>, wherein the first compound includes a compound represented by the following formula (C), (C2), (E), or (E2): In formula (C), T 11 is a monovalent group that does not contain a reactive silyl group, each B is independently —O— or —C(═O)—, each r is independently 0 or 1, and R 3 are each independently a hydrocarbon group, k1 is each independently a number of 1 or more, p1 is an integer of 1 or more, and A 11 is a (p1+q1)-valent linking group, q1 is an integer of 1 or more, R 2 are each independently a hydrocarbon group, L is each independently a hydrolyzable group, a group having a hydrolyzable group, or a hydroxyl group, and n is each independently an integer of 0 to 2. 2 are each independently a hydrolyzable group, a group having a hydrolyzable group, a hydroxyl group, or a hydrocarbon group; 2 At least four L 2 represents a hydrolyzable group, a group having a hydrolyzable group, or a hydroxyl group; each P is independently an oxygen atom or an organic group having one carbon atom bonded to adjacent Si atoms on both sides; r1 is an integer of 1 to 3; T 11 , B, r, R 3 , k1, p1, A 11 The definitions of q and q1 are the same as those in formula (C). In formula (E), B 11 is a monovalent group containing at least one selected from the group consisting of Si, Ge, and Sn, to which a hydroxyl group or a hydrolyzable group is not directly bonded; or a monovalent group containing a branched alkyl group, provided that B 11 does not contain a reactive silyl group, u1 is an integer of 1 or more, A13 is a (q1+u1)-valent linking group, q1 is an integer of 1 or more, R 2 are each independently a hydrocarbon group, L is each independently a hydrolyzable group, a group having a hydrolyzable group, or a hydroxyl group, and n is each independently an integer of 0 to 2. 2 are each independently a hydrolyzable group, a group having a hydrolyzable group, a hydroxyl group, or a hydrocarbon group; 2 At least four L 2 represents a hydrolyzable group, a group having a hydrolyzable group, or a hydroxyl group; each P independently represents an oxygen atom or an organic group having one carbon atom bonded to adjacent Si atoms on both sides; each r1 independently represents an integer of 1 to 3; 11 , u1, A 13 The definitions of q1 and q2 are the same as those in formula (E). <7> The composition according to <6>, wherein in formulas (C), (C2), (E), and (E2), q1 is an integer of 1 to 4. <8> The composition according to any one of <1> to <7>, wherein the second compound includes a compound represented by the following formula (D) or (D2): In formula (D), R 4 are each independently a hydrocarbon group or T 11 -B r -(SiR 3 2 -O) k1 - and T 11 are each independently a monovalent group; B is each independently -O- or -C(=O)-; r is each independently 0 or 1; R 3 are each independently a hydrocarbon group; k1 is each independently a number of 1 or more; A 12 are each independently a (q1+1)-valent linking group, each q1 is independently an integer of 1 or more, R 2 are each independently a hydrocarbon group, L is each independently a hydrolyzable group, a group having a hydrolyzable group, or a hydroxyl group, and n is each independently an integer of 0 to 2.2 are each independently a hydrolyzable group, a group having a hydrolyzable group, a hydroxyl group, or a hydrocarbon group; 2 At least four L 2 is a hydrolyzable group, a group having a hydrolyzable group, or a hydroxyl group; each P is independently an oxygen atom or an organic group having one carbon atom bonded to adjacent Si atoms on both sides; each r1 is independently an integer of 1 to 3; 4 , k1, A 12 The definitions of and q1 are the same as those in formula (D). <9> The composition according to <8>, wherein in formulas (D) and (D2), q1 each independently represents an integer of 1 to 4. <10> The composition according to any one of <1> to <9>, further comprising a liquid medium. <11> A surface treatment agent comprising the composition according to any one of <1> to <10>. <12> A method for producing an article, comprising treating a substrate with the surface treatment agent according to <11> to produce an article having a surface treatment layer formed on the substrate. <13> An article comprising a substrate and a surface treatment layer disposed on the substrate and surface-treated with the surface treatment agent according to <11>. <14> The article according to <13>, which is an optical member. <15> The article according to <13> or <14>, which is a display or a touch panel.
[0007] According to one embodiment of the present disclosure, there are provided a composition and a surface treatment agent capable of forming a surface treatment layer having excellent abrasion resistance, an article having a surface treatment layer having excellent abrasion resistance, and a method for producing the same.
[0008] Hereinafter, modes for carrying out embodiments of the present disclosure will be described in detail. However, the embodiments of the present disclosure are not limited to the following embodiments. In the following embodiments, components (including element steps, etc.) are not essential unless otherwise specified. The same applies to numerical values and their ranges, and they do not limit the embodiments of the present disclosure.
[0009] 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 as long as the purpose of the process is achieved. In this disclosure, numerical ranges indicated using "to" include the numerical values before and after "to" 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. Furthermore, in numerical ranges described in this disclosure, the upper or lower limit of that numerical range may be replaced with a value shown in the examples. In this disclosure, each component may contain multiple corresponding substances. When multiple substances corresponding to each component are present in a composition, the content or amount of each component refers to the total content or amount of the multiple substances present in the composition, unless otherwise specified. In this disclosure, a "surface treatment layer" refers to a layer formed on the surface of a substrate by surface treatment. In the present disclosure, when a compound or group is represented by a specific formula (X), the compound or group represented by the formula (X) may be referred to as compound (X) or compound X, and group (X) or group X, respectively. In the present disclosure, an organo(poly)siloxane residue refers to an organosiloxane residue or an organopolysiloxane residue. In the present disclosure, "Me" may refer to a methyl group.
[0010] [Composition] The composition of the present disclosure comprises: a first compound having a divalent chain group and a reactive silyl group linked to only one end of the divalent chain group; and a second compound having a divalent chain group and a reactive silyl group linked to each end of the divalent chain group, wherein the amount of the second compound relative to the total amount of the first compound and the second compound is more than 35 mol% and not more than 95 mol%. In one embodiment, the first compound is preferably a compound having a chain organo(poly)siloxane residue and a reactive silyl group linked to only one end of the chain organo(poly)siloxane residue. In one embodiment, the second compound is preferably a compound having a chain organo(poly)siloxane residue and a reactive silyl group linked to each end of the chain organo(poly)siloxane residue. In the present disclosure, the description of the first compound also applies when the "first compound" is read as "a compound having a linear organo(poly)siloxane residue and a reactive silyl group linked to only one end of the linear organo(poly)siloxane residue," unless there is a contradiction. Furthermore, the description of the second compound also applies when the "second compound" is read as "a compound having a linear organo(poly)siloxane residue and a reactive silyl group linked to both ends of the linear organo(poly)siloxane residue," unless there is a contradiction. When applied to a substrate as a surface treatment agent, the composition of the present disclosure can form a surface treatment layer with excellent abrasion resistance. The first compound and the second compound exhibit different properties, such as water and oil repellency, of the surface treatment layer formed due to differences in the arrangement of the reactive silyl groups, and development is underway to utilize the respective properties. However, to date, no attention has been paid to improving properties by using the first compound and the second compound in combination. The inventors have found that, according to the composition of the present disclosure, a surface treatment layer having excellent abrasion resistance can be formed by using the first compound and the second compound in combination in a specific ratio.The reason for this is not entirely clear, but one possible reason is that the first compound has a reactive silyl group at only one end, thereby imparting excellent water repellency to the surface treatment layer, and the second compound has reactive silyl groups at both ends, thereby forming a strong surface treatment layer.
[0011] In one embodiment, when the composition of the present disclosure is applied to a substrate as a surface treatment agent, it tends to form a surface treatment layer that combines excellent water repellency and slip resistance. Non-slip resistance refers to the degree of friction between the surface treatment layer and other materials in contact with it, and is useful in applications where a non-slip surface is desired. The reason for this is not entirely clear, but one possible reason is that the first compound, which can impart excellent water repellency to the surface treatment layer by having a reactive silyl group only at the terminal, and the second compound, which can impart slip resistance to the surface of the surface treatment layer by having reactive silyl groups at both terminals, are well balanced. Each component contained in the composition will be described in detail below.
[0012] [First Compound] The first compound has a divalent chain group and a reactive silyl group linked to only one end of the divalent chain group. In one embodiment, the first compound is preferably a compound having a chain organo(poly)siloxane residue and a reactive silyl group linked to only one end of the chain organo(poly)siloxane residue. In the present disclosure, "a reactive silyl group linked to only one end of the divalent chain group" or "a reactive silyl group linked to only one end of the chain organo(poly)siloxane residue" respectively refer to a reactive silyl group linked directly or indirectly via another chemical structure to only one end of the divalent chain group or chain organo(poly)siloxane residue. In addition, "the first compound has a divalent chain group" means that the first compound partially contains a divalent chain group. For example, even if the overall structure when another atom or group is bonded to the divalent chain group is not a divalent group, it is sufficient that the divalent chain group is partially contained. In the first compound, a reactive silyl group is directly or indirectly linked to one end of the partially contained divalent chain group, and a reactive silyl group is not directly or indirectly linked to the other end.
[0013] (Divalent Chain Group) The first compound contains a divalent chain group. The divalent chain group may be linear without a branch, or may contain a branch. The first compound may have another structure, for example, a cyclic structure, as long as it contains a divalent chain group.
[0014] The divalent chain group is not particularly limited as long as it has a chain structure in which two or more atoms are linked, and may include a chain hydrocarbon group; a chain organo(poly)siloxane residue; —O—, —S—, —C(═O)NH—, —NHC(═O)—, —N(R d )-, -C(=O)O-, -OC(=O)-, -C(=O)S-, -SC(=O)-, -S(=O) 2 NH-, -NHS (=O) 2 -, -S(=O) 2 -, -S(=O) 2 O-, -OS (=O) 2-, and a group having at least one selected from the group consisting of a phenylene group; and combinations thereof. d is a hydrogen atom or an alkyl group (preferably having 1 to 10 carbon atoms).
[0015] Examples of the chain hydrocarbon group include linear or branched chain hydrocarbon groups having 2 to 100 carbon atoms, preferably 5 to 90 carbon atoms, and more preferably 10 to 80 carbon atoms. As the chain hydrocarbon group, an alkylene group is preferred, and an alkylene group having the above carbon number is more preferred. From the viewpoint of forming a surface treatment layer that is excellent in acid resistance, hot water resistance, abrasion resistance, etc., the chain hydrocarbon group is preferably an alkylene group having 13 or more carbon atoms. At the terminal or between carbon atoms of the chain hydrocarbon group, -O-, -S-, -C(=O)NH-, -NHC(=O)-, -N(R d )-, -C(=O)O-, -OC(=O)-, -C(=O)S-, -SC(=O)-, -S(=O) 2 NH-, -NHS (=O) 2 -, -S(=O) 2 -, -S(=O) 2 O-, -OS (=O) 2 The number of carbon atoms of the group having at least one selected from the group consisting of - and phenylene groups is the same as above. d is a hydrogen atom or an alkyl group (preferably having 1 to 10 carbon atoms).
[0016] In one embodiment, the divalent chain group is preferably a chain organo(poly)siloxane residue. The chain organo(poly)siloxane residue will be described in detail below.
[0017] (Linear Organo(Poly)siloxane Residue) In one embodiment, the first compound preferably contains a linear organo(poly)siloxane residue. The linear organo(poly)siloxane residue contained in the first compound may be one or two or more. When the first compound contains two or more linear organo(poly)siloxane residues, the two or more linear organo(poly)siloxane residues may be the same or different. When the first compound contains two or more linear organo(poly)siloxane residues, it is sufficient that there is no linear organo(poly)siloxane residue having reactive silyl groups linked to both terminals, and that at least one linear organo(poly)siloxane residue has a reactive silyl group linked to one terminal.
[0018] Examples of the linear organo(poly)siloxane residue include linear organo(poly)siloxane residues represented by the following formula (B1) or (B2).
[0019]
[0020]
[0021] In formula (B1), R 3 are each independently a hydrocarbon group, k1 is a number of 1 or more, and * is a bonding site to an adjacent atom.
[0022] In formula (B2), R 4 are each independently a hydrocarbon group or T 11 -B r -(SiR 3 2 -O) k1 - and T 11 are each independently a monovalent group; B is each independently -O- or -C(=O)-; r is each independently 0 or 1; R 3 are each independently a hydrocarbon group; each k1 is independently a number of 1 or more; * is a bonding site to an adjacent atom.
[0023] In formulas (B1) and (B2), R 3Examples of the hydrocarbon group represented by the formula (I) include an aliphatic hydrocarbon group and an aromatic hydrocarbon group. Among these, the hydrocarbon group is preferably an aliphatic hydrocarbon group, and more preferably an alkyl group. The alkyl group may be any of a linear alkyl group, a branched alkyl group, and a cyclic alkyl group, but a linear alkyl group is preferred, and a methyl group, an ethyl group, an n-propyl group, or an n-butyl group is more preferred, and a methyl group is even more preferred. Furthermore, the aromatic hydrocarbon group is preferably a phenyl group.
[0024] In formulas (B1) and (B2), k1 is a number of 1 or more, preferably a number from 1 to 600, more preferably a number from 1 to 500, still more preferably a number from 3 to 500, particularly preferably a number from 9 to 50, extremely preferably a number from 11 to 30, and most preferably a number from 11 to 25.
[0025] In formula (B2), R 4 are each independently a hydrocarbon group or T 11 -B r -(SiR 3 2 -O) k1 -, and a hydrocarbon group is preferred. Details of the hydrocarbon group are as follows: R 3 The hydrocarbon group is the same as the hydrocarbon group represented by the following formula:
[0026] T 11 are each independently a monovalent group, and specific embodiments thereof are as shown in T in formula (C) described later. 11 Specific embodiments of B and r are the same as those of B and r in formula (C) described below.
[0027] (Reactive Silyl Group) The number of reactive silyl groups contained in the first compound is 1 or more, and from the viewpoint of further improving the abrasion resistance of the surface treatment layer, it is preferably 1 to 18, more preferably 1 to 12, even more preferably 1 to 8, particularly preferably 1 to 6, and extremely preferably 1 to 4. In one embodiment, the number of reactive silyl groups contained in the first compound is preferably 2 to 18, more preferably 2 to 12, even more preferably 2 to 8, and particularly preferably 2 to 6. The number of reactive silyl groups may be 1.
[0028] The reactive silyl group means a group in which a reactive group is bonded to a Si atom. The reactive group is preferably a hydrolyzable group, a group having a hydrolyzable group, or a hydroxyl group.
[0029] The hydrolyzable group is a group that becomes a hydroxyl group through a hydrolysis reaction. 1 (L 1 The hydrolyzable silyl groups represented by (wherein ) are hydrolyzable groups become silanol groups represented by Si—OH through a hydrolysis reaction. The silanol groups further react with each other to form Si—O—Si bonds. The silanol groups can also undergo a dehydration condensation reaction with silanol groups derived from oxides present on the surface of the substrate to form Si—O—Si bonds.
[0030] Examples of the hydrolyzable group include an alkoxy group, an aryloxy group, a halogen atom, an acyl group, an acyloxy group, an amino group, and —O—N═CR r 2 and an isocyanato group (-NCO). 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 a heteroaryl group. 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 are each independently an alkyl group having 1 to 10 carbon atoms.
[0031] Examples of the group having a hydrolyzable group include the groups having a hydrolyzable group exemplified above. A -L B is preferred. A is an alkylene group, and L B is a hydrolyzable group. The alkylene group preferably has 1 to 10 carbon atoms. B The hydrolyzable group represented by the formula (I) has the same meaning as the hydrolyzable group described above, and the preferred embodiments are also the same.
[0032] The reactive silyl group is preferably a group represented by the following formula (S1): —Si(R 2 ) n L 3-n ...(S1)
[0033] In formula (S1), R 2 are each independently a monovalent hydrocarbon group; each L is independently a hydrolyzable group, a group having a hydrolyzable group, or a hydroxyl group; and n is an integer of 0 to 2.
[0034] When a molecule contains a plurality of reactive silyl groups, the plurality of reactive silyl groups may be the same or different from each other. From the viewpoints of availability of raw materials and ease of production of the compound, it is preferable that the plurality of reactive silyl groups are the same.
[0035] R 2 are each independently a monovalent hydrocarbon group, and preferably a monovalent saturated hydrocarbon group. 2 The number of carbon atoms is preferably 1 to 6, more preferably 1 to 3, and even more preferably 1 or 2.
[0036] Each L is independently a hydrolyzable group, a group having a hydrolyzable group, or a hydroxyl group. Details of the hydrolyzable group and the group having a hydrolyzable group are as described above.
[0037] Among these, from the viewpoint of ease of production of the compound, L is preferably an alkoxy group having 1 to 4 carbon atoms or a halogen atom. L is preferably an alkoxy group having 1 to 4 carbon atoms, more preferably an ethoxy group or a methoxy group, from the viewpoint of less outgassing during coating and better storage stability of the compound.
[0038] n is an integer of 0 to 2, preferably 0 or 1, and more preferably 0. The presence of a plurality of Ls strengthens the adhesion of the surface treatment layer to the substrate.
[0039] When n is 1 or less, the plurality of L's present in one molecule may be the same or different from each other. From the viewpoint of availability of raw materials and ease of production of the compound, it is preferable that the plurality of L's are the same. When n is 2, the plurality of R's present in one molecule may be different from each other. 2may be the same or different from each other. From the viewpoint of availability of raw materials and ease of production of the compound, it is preferable to use a plurality of R 2 are preferably the same.
[0040] From the viewpoint of excellent uniformity and durability of the surface treatment layer, the reactive silyl group is preferably an alkoxysilyl group or a trichlorosilyl group. From the viewpoint of ease of handling of by-products generated in the reaction with the substrate, the reactive silyl group is more preferably an alkoxysilyl group. As the alkoxysilyl group, a dialkoxysilyl group or a trialkoxysilyl group is preferred, and a trialkoxysilyl group is more preferred.
[0041] The reactive silyl group may be a group represented by the following formula (S2): >SiL 2 ...(S2) L is the same as L in formula (S1).
[0042] The reactive silyl group is also preferably a group represented by the following formula (S3): -[Si(L 2 ) 2 -P] r1 -Si(L 2 ) 3 ...(S3)
[0043] In formula (S3), L 2 are each independently a hydrolyzable group, a group having a hydrolyzable group, a hydroxyl group, or a hydrocarbon group; 2 At least four L 2 represents a hydrolyzable group, a group having a hydrolyzable group, or a hydroxyl group; each P is independently an oxygen atom or an organic group having one carbon atom bonded to adjacent Si atoms on both sides; and r1 is an integer of 1 to 3.
[0044] When a molecule contains a plurality of groups (S3), the groups (S3) may be the same or different from each other. From the viewpoint of availability of raw materials and ease of production of the compound, it is preferable that the groups (S3) are the same.
[0045] L 2are each independently a hydrolyzable group, a group having a hydrolyzable group, a hydroxyl group, or a hydrocarbon group. Details of the hydrolyzable group and the group having a hydrolyzable group are as described above. 2 From the viewpoint of ease of production of the compound, the hydrolyzable group or the group having a hydrolyzable group in L is preferably an alkoxy group having 1 to 4 carbon atoms, an alkylene oxide-modified alkoxy group, or a halogen atom. 2 From the viewpoints of reducing outgassing during application and improving the storage stability of the compound, L is preferably an alkoxy group having 1 to 4 carbon atoms, and more preferably an ethoxy group or a methoxy group. 2 Examples of the hydrocarbon group represented by the formula (I) include an alkyl group, a cycloalkyl group, an alkenyl group, and an allyl group. From the viewpoint of ease of synthesis, a saturated hydrocarbon group is preferred, and an alkyl group is more preferred. The number of carbon atoms in the hydrocarbon group is preferably 1 to 6, more preferably 1 to 3, and even more preferably 1 or 2.
[0046] r1 is an integer of 1 to 3, and from the viewpoint of ease of synthesis, 1 or 2 is preferred, and 1 is more preferred.
[0047] A plurality of Ls in one group (S3) 2 Among these, at least four are hydrolyzable groups, groups having a hydrolyzable group, or hydroxyl groups. This allows the group (S3) to bond more firmly to the substrate, resulting in a surface treatment layer with excellent durability. From this viewpoint, the number of hydrolyzable groups, groups having a hydrolyzable group, and hydroxyl groups in the group (S3) is preferably 4 to 9, more preferably 4 to 7, and even more preferably 4 or 5. In addition, when multiple Ls exist in one molecule, 2 may be the same or different from each other. For example, 2 may be the same hydrolyzable group.
[0048] Each P is independently an oxygen atom or an organic group having one carbon atom that bonds to adjacent Si on both sides. Here, "an organic group having one carbon atom that bonds to adjacent Si on both sides" means that Si is linked to itself via one carbon atom. Examples of P include hydrocarbon groups, such as -CH 2 -, -C(CH3 ) 2 From the viewpoint of durability of the surface treatment layer, P may be an oxygen atom, —CH 2 -, or -C(CH 3 ) 2 - is preferred, and an oxygen atom or -CH 2 - is more preferred, and an oxygen atom is even more preferred.
[0049] From the viewpoint of excellent durability of the surface treatment layer, the group (S3) is -[Si(OR 12 ) 2 -O] r1 -Si(OR 12 ) 3 is preferred, and among these, -Si(OR 12 ) 2 —O—Si(OR 12 ) 3 is particularly preferred. 12 R are each independently a hydrocarbon group. Examples of the hydrocarbon group include an alkyl group, a cycloalkyl group, an alkenyl group, and an allyl group. From the viewpoint of ease of synthesis, a saturated hydrocarbon group is preferred, and an alkyl group is more preferred. 12 The number of carbon atoms is preferably 1 to 6, more preferably 1 to 3, and even more preferably 1 or 2.
[0050] Specific examples of the group (S3) 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(OCH2 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(OCH 2 CH 3 ) 3 ,-Si(OCH 2 CH 3 ) 2 -CH 2 -Si(OCH 2 CH 3 ) 3 ,-Si(OCH 2 CH 3 ) 2 -C(CH) 3 ) 2 -Si(OCH 3 ) 3 ,-Si(OCH 3 ) 2 -C(CH) 3 ) 2 -Si(OCH 2 CH 3 ) 3 ,-Si(OCH 2 CH 3 ) 2 -C(CH) 3 ) 2 -Si(OCH 2 CH 3 ) 3 ,-Si(OH) 2 -O-Si(OH) 3 ,-Si(OH) 2 -O-Si(OCH 3 ) 3 ,-Si(OCH 3 ) 2 -O-Si(OH) 3 ,-Si(OH) 2 -CH2 -Si(OH) 3 , —Si(OH) 2 -CH 2 -Si(OCH 3 ) 3 , -Si(OCH 3 ) 2 -CH 2 -Si(OH) 3 , —Si(OH) 2 -C(CH 3 ) 2 -Si(OH) 3 , —Si(OH) 2 -C(CH 3 ) 2 -Si(OCH 3 ) 3 , -Si(OCH 3 ) 2 -C(CH 3 ) 2 -Si(OH) 3 etc.
[0051] (Compound (C)) The first compound is preferably represented by the following formula (C).
[0052]
[0053] In formula (C), T 11 is a monovalent group that does not contain a reactive silyl group, each B is independently —O— or —C(═O)—, each r is independently 0 or 1, and R 3 are each independently a hydrocarbon group, k1 is each independently a number of 1 or more, p1 is an integer of 1 or more, and A 11 is a (p1+q1)-valent linking group, q1 is an integer of 1 or more, R 2 are each independently a hydrocarbon group; each L is independently a hydrolyzable group, a group having a hydrolyzable group, or a hydroxyl group; and each n is independently an integer of 0 to 2.
[0054] In formula (C), R 3 and k1 is R in formula (B1). 3 and k1. R 2 , L, and n are R in formula (S1).2 , L, and n.
[0055] In formula (C), T 11 is a monovalent group. 11 Examples of the alkyl group include alkyl groups, T 1 3 M 1 - (where M 1 is Si, Sn, or Ge, and T 1 are each independently a hydrocarbon group or a trialkylsilyloxy group; T 1 3 M 1 -R 1 - (where M 1 is Si, Sn, or Ge, and T 1 are each independently a hydrocarbon group or a trialkylsilyloxy group, and R 1 represents an alkylene group), a monovalent cyclic polysiloxane residue or a monovalent cage-like polysiloxane residue, and a combination of a monovalent cyclic polysiloxane residue or a monovalent cage-like polysiloxane residue with a divalent hydrocarbon group.
[0056] T 11 The alkyl group represented by the formula (I) may be any of a linear alkyl group, a branched alkyl group, and a cyclic alkyl group, with a linear alkyl group or a branched alkyl group being preferred. The alkyl group may have 1 carbon atom or 2 or more carbon atoms. When the alkyl group has 2 or more carbon atoms, the number of carbon atoms is preferably 2 to 30, more preferably 3 to 28, and even more preferably 4 to 22.
[0057] T 1 3 M 1 - and T 1 3 M 1 -R 1 M in - 1 As the element, Si is preferred.
[0058] T 1 3 M 1 - and T 1 3 M 1 -R 1T in - 1 As the group, an alkyl group or a trialkylsilyloxy group is preferable, and a methyl group, a butyldimethylsilyloxy group, a trimethylsilyloxy group, or a triethylsilyloxy group is more preferable.
[0059] R 1 As the alkylene group, an alkylene group having 1 to 20 carbon atoms is preferable, an alkylene group having 1 to 10 carbon atoms is more preferable, an alkylene group having 1 to 5 carbon atoms is even more preferable, and an ethylene group is particularly preferable.
[0060] In one embodiment, T 11 is preferably an alkyl group or a trialkylsilyl group, more preferably a methyl group or a trimethylsilyl group.
[0061] The monovalent cyclic polysiloxane residue is preferably a group represented by the following formula (T1): T are each independently a hydrocarbon group or a hydrocarbon group having a substituent, and s is an integer of 1 to 4.
[0062]
[0063] R T Examples of the hydrocarbon group represented by the formula (I) include an aliphatic hydrocarbon group and an aromatic hydrocarbon group. Among these, the hydrocarbon group is preferably an aliphatic hydrocarbon group, and more preferably an alkyl group.
[0064] R T Among the hydrocarbon groups represented by the formula (I), the alkyl group may be any of a linear alkyl group, a branched alkyl group, and a cyclic alkyl group, but a linear alkyl group is 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. Specifically, the alkyl group is preferably a methyl group, an ethyl group, an n-propyl group, or an n-butyl group, and more preferably a methyl group.
[0065] R TExamples of the hydrocarbon group contained in the hydrocarbon group having a substituent represented by the formula (I) include an aliphatic hydrocarbon group and an aromatic hydrocarbon group. Among these, the hydrocarbon group is preferably an aliphatic hydrocarbon group, and more preferably an alkyl group. The alkyl group may be any of a linear alkyl group, a branched alkyl group, and a cyclic alkyl group, but a linear alkyl group is preferred. The number of carbon atoms in the alkyl group contained in the substituted alkyl group is preferably 1 to 10, more preferably 1 to 8, and even more preferably 2 to 4.
[0066] R T Examples of the substituent in the hydrocarbon group having a substituent represented by the formula (I) include a halogen atom, a hydroxyl group, an alkoxy group, a trialkylsilyl ether group, a trialkylsilyl group, an amino group, a nitro group, a cyano group, a sulfonyl group, and a trifluoromethyl group.
[0067] Multiple R T may be the same or different from each other, but from the viewpoint of ease of production, it is preferable that they are the same.
[0068] Examples of the monovalent cyclic polysiloxane residue include the following groups.
[0069]
[0070] The monovalent cage-like polysiloxane residue is preferably a group represented by the following formula (T2): 5 are each independently a hydrocarbon group or a trialkylsilyloxy group.
[0071]
[0072] R 5Examples of the hydrocarbon group represented by the formula (I) include an aliphatic hydrocarbon group and an aromatic hydrocarbon group. Among these, the hydrocarbon group is preferably an aliphatic hydrocarbon group, and more preferably an alkyl group. The alkyl group may be any of a linear alkyl group, a branched alkyl group, and a cyclic alkyl group, but a linear alkyl group or a branched alkyl group is preferred, and a methyl group, an ethyl group, an n-propyl group, an n-butyl group, or an isobutyl group is more preferred, and an isobutyl group is even more preferred.
[0073] R 5 The alkyl group contained in the trialkylsilyloxy group represented by the formula (R) may be any of a linear alkyl group, a branched alkyl group, and a cyclic alkyl group, but is preferably a linear alkyl group, more preferably a methyl group, an ethyl group, an n-propyl group, or an n-butyl group, and even more preferably a methyl group. 5 is a trialkylsilyloxy group, the three alkylsilyloxy groups may be the same or different from one another, but from the viewpoint of ease of production, they are preferably the same.
[0074] Examples of the monovalent cage-like polysiloxane residue include the following groups.
[0075]
[0076] The divalent hydrocarbon group in the combination of the monovalent cyclic polysiloxane residue or the monovalent cage polysiloxane residue with the divalent hydrocarbon group is, for example, an alkylene group, preferably having 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, and even more preferably 1 to 5 carbon atoms.
[0077] In formula (C), each B is independently —O— or —C(═O)—, and —O— is preferred.
[0078] In formula (C), p1 is an integer of 1 or more, preferably an integer of 1 to 3, more preferably 1 or 2, and even more preferably 1. When p1 is 2 or more, a plurality of T 11 -B r -[Si(R 3 ) 2 -O] k1 -Si(R3 ) 2 - may be the same or different from each other.
[0079] In formula (C), A 11 is a (p1+q1)-valent linking group. 11 Examples of the alkylene group include an alkylene group, an organo(poly)siloxane residue, a polyalkylene oxide group, and a combination thereof; and a combination thereof with a (p1+1)-valent group and / or a (q1+1)-valent group. Examples of the alkylene group include an etheric oxygen atom, a sulfur atom, -C(=O)NH-, -NHC(=O)-, -N(R d )-, -C(=O)O-, -OC(=O)-, -C(=O)S-, -SC(=O)-, -S(=O) 2 NH-, -NHS (=O) 2 -, -S(=O) 2 -, -S(=O) 2 O-, -OS (=O) 2 Examples of the organo(poly)siloxane residue include a group represented by the formula (B1) above. Examples of the polyalkylene oxide group include a group represented by the formula (XO) m Here, X is independently an alkylene group having 1 to 5 carbon atoms, and m is an integer of 1 or more. The number of carbon atoms in X is preferably 1 to 4, more preferably 2 or 3. m is preferably 1 to 200, more preferably 1 to 20, and even more preferably 1 to 10. A 11 As the compound represented by the formula A(Si(R 2 ) n L 3-n ) q1 Examples of the A in the above formula include:
[0080] In formula (C), q1 is an integer of 1 or more, preferably 1 to 18, more preferably 1 to 12, even more preferably 1 to 8, particularly preferably 1 to 6, and extremely preferably 1 to 4. In one embodiment, q1 is preferably 2 to 18, more preferably 2 to 12, even more preferably 2 to 8, particularly preferably 2 to 6, and extremely preferably 2 to 4. q1 may be 1. When q1 is an integer of 2 or more, a plurality of [Si(R 2 ) n L 3-n ] may be the same or different from each other.
[0081] In one embodiment, T in formula (C) 11 is preferably a trialkylsilyl group or an alkyl group, more preferably a trimethylsilyl group or a methyl group. B is preferably O, and r is 0 or 1. 3 is preferably a methyl group. k1 is preferably 1 to 100. p1 is preferably 1. A 11 represents an alkylene group having 1 to 30 carbon atoms, or a group selected from the group (3-1A) to Si(R 2 ) n L 3-n is preferably an alkylene group having 1 to 30 carbon atoms, or a group selected from the group (3-1A-4) to Si(R 2 ) n L 3-n It is more preferable that q1 is a group excluding the following:
[0082] (Compound (C2)) In a further embodiment, the first compound is preferably represented by the following formula (C2).
[0083]
[0084] In formula (C2), L 2 are each independently a hydrolyzable group, a group having a hydrolyzable group, a hydroxyl group, or a hydrocarbon group; 2 At least four L 2 represents a hydrolyzable group, a group having a hydrolyzable group, or a hydroxyl group; each P is independently an oxygen atom or an organic group having one carbon atom bonded to adjacent Si atoms on both sides; r1 is an integer of 1 to 3; T 11 , B, r, R 3 , k1, p1, A 11 The definitions of q and q1 are the same as those in formula (C).
[0085] In formula (C2), T 11 , B, r, R 3 , k1, p1, A 11 Specific embodiments of q1 and q2 are the same as those in formula (C). 2 Specific embodiments of P and r1 are as follows: 2 , P and r1 are the same as specific embodiments thereof.
[0086] (Compound (E)) In one embodiment, the first compound may be a compound represented by formula (E).
[0087]
[0088] In formula (E), B 11 is a monovalent group containing at least one selected from the group consisting of Si, Ge, and Sn, to which a hydroxyl group or a hydrolyzable group is not directly bonded; or a monovalent group containing a branched alkyl group, provided that B 11 does not contain a reactive silyl group, u1 is an integer of 1 or more, A 13 is a (q1+u1)-valent linking group, q1 is an integer of 1 or more, R 2 are each independently a hydrocarbon group; each L is independently a hydrolyzable group, a group having a hydrolyzable group, or a hydroxyl group; and each n is independently an integer of 0 to 2.
[0089] In formula (E), R 2 , L, and n are R in formula (S1). 2 , L, and n are the same as q1 in formula (C).
[0090] B 11is a monovalent group containing at least one selected from the group consisting of Si, Ge, and Sn to which a hydroxyl group or a hydrolyzable group is not directly bonded; or a monovalent group containing a branched alkyl group. The monovalent group containing at least one selected from the group consisting of Si, Ge, and Sn to which a hydroxyl group or a hydrolyzable group is not directly bonded may or may not contain Si, Ge, or Sn to which a hydroxyl group or a hydrolyzable group is directly bonded.
[0091] In one embodiment, B 11 may be a group having group (a) or group (b).
[0092]
[0093]
[0094] In formula (a), R 51 is -(R 61 -SiR 53 2 ) ma -R 53 where R 61 are each independently an oxygen atom or an alkylene group having 1 to 6 carbon atoms, and R 53 are each independently a hydrocarbon group or R 51’ and R 51’ is R 51 and ma is an integer of 1 to 5, provided that R 51 Medium, R 51’ The number of is 20 or less, and R 52 is a hydrocarbon group, na is an integer of 1 to 3, z is 0 or 1, and * represents a bonding site with an adjacent atom.
[0095] In formula (b), R 54 are each independently a hydrocarbon group, nb is an integer of 1 to 5, z is 0 or 1, and * represents a bonding site to an adjacent atom.
[0096] R 61The alkylene group having 1 to 6 carbon atoms in the formula (I) may be linear or branched. The alkylene group having 1 to 6 carbon atoms is preferably an alkylene group having 1 to 4 carbon atoms, and more preferably an alkylene group having 2 to 4 carbon atoms.
[0097] R 53 The hydrocarbon group represented by the formula (I) is preferably an alkyl group or an aryl group. The alkyl group may be linear or branched. The alkyl group is preferably an alkyl group having 1 to 6 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms, and even more preferably a methyl group, an ethyl group, an n-propyl group, an isopropyl group, or a tert-butyl group.
[0098] R 52 The hydrocarbon group represented by the formula (I) is preferably an alkyl group or an aryl group. The alkyl group may be linear or branched. The alkyl group is preferably an alkyl group having 1 to 6 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms, and even more preferably a methyl group, an ethyl group, an n-propyl group, an isopropyl group, or a tert-butyl group.
[0099] R 54 The hydrocarbon group represented by the formula (I) is preferably an alkyl group or an aryl group. The alkyl group may be linear or branched. The alkyl group is preferably an alkyl group having 1 to 6 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms, and even more preferably a methyl group, an ethyl group, an n-propyl group, an isopropyl group, or a tert-butyl group.
[0100] nb is an integer of 1 to 5, preferably 2 or 3.
[0101] Examples of the group having the group (a) or the group (b) include the group (a) or the group (b) alone, and groups in which a chain group is linked to the group (a) or the group (b). Examples of the chain group include a chain hydrocarbon group; a chain organo(poly)siloxane residue; -O-, -S-, -C(=O)NH-, -NHC(=O)-, -N(R d )-, -C(=O)O-, -OC(=O)-, -C(=O)S-, -SC(=O)-, -S(=O) 2 NH-, -NHS (=O) 2-, -S(=O) 2 -, -S(=O) 2 O-, -OS (=O) 2 -, and a group having at least one selected from the group consisting of a phenylene group; and combinations thereof. d is a hydrogen atom or an alkyl group (preferably having 1 to 10 carbon atoms).
[0102] Examples of the chain hydrocarbon group include linear or branched chain hydrocarbon groups having 2 to 100 carbon atoms, preferably 5 to 90 carbon atoms, and more preferably 10 to 80 carbon atoms. The chain hydrocarbon group is preferably an alkylene group, and from the viewpoint of forming a surface treatment layer excellent in acid resistance, hot water resistance, abrasion resistance, etc., the chain hydrocarbon group is preferably an alkylene group having 13 or more carbon atoms. The chain hydrocarbon group may have at its terminal or between carbon atoms -O-, -S-, -C(=O)NH-, -NHC(=O)-, -N(R d )-, -C(=O)O-, -OC(=O)-, -C(=O)S-, -SC(=O)-, -S(=O) 2 NH-, -NHS (=O) 2 -, -S(=O) 2 -, -S(=O) 2 O-, -OS (=O) 2 The number of carbon atoms of the group having at least one selected from the group consisting of - and phenylene groups is the same as above. d is a hydrogen atom or an alkyl group (preferably having 1 to 10 carbon atoms).
[0103] Examples of the linear organo(poly)siloxane residue include the examples of the linear organo(poly)siloxane residue in the first compound described above.
[0104] In one embodiment, B 11 may be a group having group (c). 31 (R 31 ) 2 -...(c) In formula (c), M 31 is Sn or Ge, R 31 are each independently a hydrocarbon group or a trialkylsilyloxy group.
[0105] M 31is Sn or Ge. Ge has a larger atomic size than Sn, and can further reduce the surface free energy, thereby forming a surface treatment layer with excellent fingerprint removal properties. 31 is preferably Ge.
[0106] R 31 R is a hydrocarbon group or a trialkylsilyloxy group. Examples of the hydrocarbon group include an alkyl group, a cycloalkyl group, an alkenyl group, and an allyl group. From the viewpoint of ease of synthesis, a saturated hydrocarbon group is preferred, and an alkyl group is more preferred. 31 The number of carbon atoms in —CH is preferably 1 to 6, more preferably 1 to 3, and particularly preferably —CH 3 or -CH 2 CH 3 The trialkylsilyloxy group is preferably —O—SiR 40 3 Preferably, R 40 are each independently a hydrocarbon group. 40 The hydrocarbon group in R is preferably an alkyl group or an aryl group, and more preferably an alkyl group. 40 The number of carbon atoms in R is preferably 1 to 6, more preferably 1 to 4, and even more preferably 1 or 2. 40 Specific examples of the hydrocarbon group in 3 , -CH 2 CH 3 , -C(CH 3 ) 3 Examples include:
[0107] The group having the group (c) may be the group (c) alone or a group (c) M 31 Examples of the organic group include a monovalent organic group, a divalent organic group, and a combination thereof. However, the monovalent organic group is not connected to both sides. Examples of the monovalent organic group include a hydrocarbon group, a trialkylsilyloxy group, and an organopolysiloxane group. The group (c) is M 31 (R 31 ) 3The divalent organic group may be a chain hydrocarbon group; a chain organo(poly)siloxane residue; -O-, -S-, -C(=O)NH-, -NHC(=O)-, -N(R d )-, -C(=O)O-, -OC(=O)-, -C(=O)S-, -SC(=O)-, -S(=O) 2 NH-, -NHS (=O) 2 -, -S(=O) 2 -, -S(=O) 2 O-, -OS (=O) 2 -, and a group having at least one selected from the group consisting of a phenylene group; and combinations thereof. d is a hydrogen atom or an alkyl group (preferably having 1 to 10 carbon atoms).
[0108] Examples of the chain hydrocarbon group include linear or branched chain hydrocarbon groups having 2 to 100 carbon atoms, preferably 5 to 90 carbon atoms, and more preferably 10 to 80 carbon atoms. Examples of the chain hydrocarbon group include alkyl groups and alkylene groups. From the viewpoint of forming a surface treatment layer that is excellent in acid resistance, hot water resistance, abrasion resistance, etc., the chain hydrocarbon group is preferably an alkylene group having 13 or more carbon atoms. The chain hydrocarbon group may have at its terminal or between carbon atoms -O-, -S-, -C(=O)NH-, -NHC(=O)-, -N(R d )-, -C(=O)O-, -OC(=O)-, -C(=O)S-, -SC(=O)-, -S(=O) 2 NH-, -NHS (=O) 2 -, -S(=O) 2 -, -S(=O) 2 O-, -OS (=O) 2 The number of carbon atoms of the group having at least one selected from the group consisting of - and phenylene groups is the same as above. d is a hydrogen atom or an alkyl group (preferably having 1 to 10 carbon atoms).
[0109] Examples of the linear organo(poly)siloxane residue include the examples of the linear organo(poly)siloxane residue in the first compound described above.
[0110] In one embodiment, B 11may be a monovalent group containing a branched alkyl group. The branched alkyl group is preferably unsubstituted. The branched alkyl group is preferably a tert-butyl group or contains a tert-butyl group. The branched alkyl group may contain one branch or multiple branches. The number of branches in the branched alkyl group may be 1 to 30, 1 to 20, 1 to 10, or 1 to 5.
[0111] Examples of branched alkyl groups include groups represented by the following formula: [(CH 3 ) 3 C-R 22 -] m22 C(CH 3 ) 3-m22 - In the formula, R 22 are each independently an alkylene group having 1 to 6 carbon atoms; and m22 is an integer of 0 to 3.
[0112] Examples of the monovalent group containing a branched alkyl group include a group in which a chain group is linked to a carbon atom that is a branch point of the branched alkyl group. Examples of the chain group include a chain hydrocarbon group; a chain organo(poly)siloxane residue; -O-, -S-, -C(=O)NH-, -NHC(=O)-, -C(=O)O-, -OC(=O)-, -C(=O)S-, -SC(=O)-, and -S(=O) 2 NH-, -NHS (=O) 2 -, -S(=O) 2 O-, -OS (=O) 2 -, and a group having at least one selected from the group consisting of a phenylene group; and combinations thereof.
[0113] Examples of the chain hydrocarbon group include linear or branched chain hydrocarbon groups having 2 to 100 carbon atoms, preferably 5 to 90 carbon atoms, and more preferably 10 to 80 carbon atoms. The chain hydrocarbon group is preferably an alkylene group, and from the viewpoint of forming a surface treatment layer excellent in acid resistance, hot water resistance, abrasion resistance, etc., the chain hydrocarbon group is preferably an alkylene group having 13 or more carbon atoms. The chain hydrocarbon group may have at its terminal or between carbon atoms -O-, -S-, -C(=O)NH-, -NHC(=O)-, -N(R d)-, -C(=O)O-, -OC(=O)-, -C(=O)S-, -SC(=O)-, -S(=O) 2 NH-, -NHS (=O) 2 -, -S(=O) 2 -, -S(=O) 2 O-, -OS (=O) 2 The number of carbon atoms of the group having at least one selected from the group consisting of - and phenylene groups is the same as above. d is a hydrogen atom or an alkyl group (preferably having 1 to 10 carbon atoms).
[0114] Examples of the linear organo(poly)siloxane residue include the examples of the linear organo(poly)siloxane residue in the first compound described above.
[0115] In formula (E), u1 is an integer of 1 or more. From the viewpoint of ease of production, u1 is preferably 1 to 6, and more preferably 1 to 4.
[0116] In formula (E), A 13 is a (q1+u1)-valent linking group. 13 As for A in formula (C), 11 Similar examples include:
[0117] Compound (E) includes B 11 is a group (a) or M 31 (R 31 ) 3 -, u1 is 1, and A 13 between carbon atoms is —O—, —S—, —C(═O)NH—, —NHC(═O)—, —N(R d )-, -C(=O)O-, -OC(=O)-, -C(=O)S-, -SC(=O)-, -S(=O) 2 NH-, -NHS (=O) 2 -, -S(=O) 2 -, -S(=O) 2 O-, -OS (=O) 2 Compound (E) may be a compound in which q1 is 1 and the compound is an alkylene group having 1 to 30 carbon atoms, which may or may not have at least one selected from the group consisting of phenylene groups. 11 is a group (a) or M 31 (R31 ) 3 -, u1 is 1, and A 13 between carbon atoms is —O—, —S—, —C(═O)NH—, —NHC(═O)—, —N(R d )-, -C(=O)O-, -OC(=O)-, -C(=O)S-, -SC(=O)-, -S(=O) 2 NH-, -NHS (=O) 2 -, -S(=O) 2 -, -S(=O) 2 O-, -OS (=O) 2 -, and a phenylene group, and may or may not have at least one selected from the group consisting of a chain hydrocarbon group having 1 to 30 carbon atoms, and q1 is 2 or 3. d is a hydrogen atom or an alkyl group (preferably having 1 to 10 carbon atoms).
[0118] Specific examples of compound (E) include the following compounds: In the following formula, sa is preferably 1 to 30, more preferably 4 to 20, and even more preferably 5 to 15.
[0119]
[0120] (Compound (E2)) In one embodiment, the first compound may be a compound represented by formula (E2).
[0121] In formula (E2), L 2 are each independently a hydrolyzable group, a group having a hydrolyzable group, a hydroxyl group, or a hydrocarbon group; 2 At least four L 2 represents a hydrolyzable group, a group having a hydrolyzable group, or a hydroxyl group; each P independently represents an oxygen atom or an organic group having one carbon atom bonded to adjacent Si atoms on both sides; each r1 independently represents an integer of 1 to 3; 11 , u1, A 13 The definitions of q and q1 are the same as those in formula (E).
[0122] B 11 , u1, A 13Specific embodiments of q1 and q2 are the same as those in formula (E). 2 , P, and r1 are the same as those in formula (S3).
[0123] The number average molecular weight (Mn) of the first compound is preferably 500 to 20,000, more preferably 600 to 18,000, and even more preferably 700 to 15,000. In one embodiment, the Mn of the first compound may be 500 to 5,000 or 500 to 3,000. When Mn is 500 or more, the abrasion resistance of the surface treatment layer is superior. When Mn is 20,000 or less, the viscosity can be easily adjusted within an appropriate range, and solubility is improved, resulting in excellent handling during film formation.
[0124] The composition of the present disclosure may contain only one type of first compound, or may contain two or more types.
[0125] The composition of the present disclosure may contain impurities such as by-products produced in the manufacturing process of the first compound.
[0126] The content of the first compound is preferably 0.001 to 50 mass%, more preferably 0.01 to 20 mass%, and even more preferably 0.1 to 10 mass%, relative to the total amount of the composition of the present disclosure. In the case of a composition of the present disclosure used in a wet coating method, the content of the first compound may be 0.01 to 10 mass%, 0.02 to 5 mass%, 0.03 to 3 mass%, or 0.05 to 2 mass%, relative to the total amount of the composition of the present disclosure.
[0127] The content of the first compound is preferably 5% by mass or more and less than 65% by mass, more preferably 10 to 64% by mass, may be 20 to 60% by mass, or may be 30 to 50% by mass, relative to the total solid content of the composition of the present disclosure.
[0128] [Second Compound] The second compound has a divalent chain group and reactive silyl groups linked to both ends of the divalent chain group. In one embodiment, the second compound preferably has a chain organo(poly)siloxane residue and reactive silyl groups linked to both ends of the chain organo(poly)siloxane residue. In this disclosure, "reactive silyl groups linked to both ends of the divalent chain group" or "reactive silyl groups linked to both ends of the chain organo(poly)siloxane residue" refer to reactive silyl groups linked directly or indirectly via other chemical structures to both ends of the divalent chain group or the chain organo(poly)siloxane residue, respectively. In addition, "the second compound has a divalent chain group" means that the second compound partially contains a divalent chain group. In the second compound, reactive silyl groups are directly or indirectly linked to both ends of the divalent chain group contained in the part.
[0129] (Divalent Chain Group) The second compound contains a divalent chain group. Details of the divalent chain group are the same as those of the divalent chain group in the first compound. In one embodiment, the divalent chain group is preferably a chain organo(poly)siloxane residue.
[0130] (Linear Organo(Poly)siloxane Residue) In one embodiment, the second compound preferably contains a linear organo(poly)siloxane residue. The linear organo(poly)siloxane residue contained in the second compound may be one or two or more. When the second compound contains two or more linear organo(poly)siloxane residues, the two or more linear organo(poly)siloxane residues may be the same or different. When the second compound contains two or more linear organo(poly)siloxane residues, it is sufficient that reactive silyl groups are linked to both terminal sides of at least one linear organo(poly)siloxane residue.
[0131] Details of the linear organo(poly)siloxane residue are as described above in the section on compound 1. In particular, the linear organo(poly)siloxane residue is preferably represented by formula (B1) or (B2), and more preferably represented by formula (B1).
[0132] (Reactive Silyl Group) Details of the reactive silyl group are as described above in the section on the first compound. The number of reactive silyl groups contained in the second compound is 1 or more per one end of a divalent chain group (e.g., a chain organo(poly)siloxane residue), and from the viewpoint of further improving the abrasion resistance of the surface treatment layer, the number per one end of a divalent chain group (e.g., a chain organo(poly)siloxane residue) is preferably 1 to 18, more preferably 1 to 12, even more preferably 1 to 8, particularly preferably 1 to 6, and extremely preferably 1 to 4. In one aspect, the number of reactive silyl groups contained in the second compound is preferably 2 to 18, more preferably 2 to 12, even more preferably 2 to 8, and particularly preferably 2 to 6 per one end of a divalent chain group (e.g., a chain organo(poly)siloxane residue). The number of reactive silyl groups may be one per one end of the divalent chain group (chain organo(poly)siloxane residue).
[0133] (Compound (D)) The second compound is preferably represented by the following formula (D).
[0134]
[0135] In formula (D), R 4 are each independently a hydrocarbon group or T 11 -B r -(SiR 3 2 -O) k1 - and T 11 are each independently a monovalent group; B is each independently -O- or -C(=O)-; r is each independently 0 or 1; R 3 are each independently a hydrocarbon group; k1 is each independently a number of 1 or more; A 12 are each independently a (q1+1)-valent linking group, each q1 is independently an integer of 1 or more, R 2 are each independently a hydrocarbon group; each L is independently a hydrolyzable group, a group having a hydrolyzable group, or a hydroxyl group; and each n is independently an integer of 0 to 2.
[0136] In formula (D), R 4 and k1 is R in formula (B2). 4 and k1. R 2 , L, and n are R in formula (S1). 2 , L, and n.
[0137] A 12 Examples of the alkylene group include an alkylene group, an organo(poly)siloxane residue, a polyalkylene oxide group, and a combination thereof; and a combination thereof with a (q1+1)-valent group. Examples of the alkylene group include an etheric oxygen atom, a sulfur atom, -C(=O)NH-, -NHC(=O)-, -N(R d )-, -C(=O)O-, -OC(=O)-, -C(=O)S-, -SC(=O)-, -S(=O) 2 NH-, -NHS (=O) 2 -, -S(=O) 2 -, -S(=O) 2 O-, -OS (=O) 2 Examples of the organo(poly)siloxane residue include a group represented by the above formula (B1) or (B2). Examples of the polyalkylene oxide group include a group represented by the formula (XO): m Here, X is independently an alkylene group having 1 to 5 carbon atoms, and m is an integer of 1 or more. The number of carbon atoms in X is preferably 1 to 4, more preferably 2 or 3. m is preferably 1 to 100, more preferably 1 to 10, and even more preferably 1 to 5. A 12 As the compound represented by the formula A(Si(R 2 ) n L 3-n ) q1 In the above formula, A is a (q1+1)-valent group.
[0138] Each q1 is independently an integer of 1 or more, and each q1 is independently preferably 1 to 18, more preferably 1 to 12, even more preferably 1 to 8, particularly preferably 1 to 6, and extremely preferably 1 to 4. In one embodiment, q1 is preferably 2 to 18, more preferably 2 to 12, even more preferably 2 to 8, particularly preferably 2 to 6, and extremely preferably 2 to 4. q1 may be 1. When q1 is an integer of 2 or more, a plurality of [Si(R 2 ) n L 3-n ] may be the same or different from each other.
[0139] In one embodiment, R 4 is preferably a methyl group. k1 is preferably a number from 1 to 100. 12 represents an alkylene group having 1 to 30 carbon atoms, or a group selected from the group (3-1A) to Si(R 2 ) n L 3-n is preferably an alkylene group having 1 to 30 carbon atoms, or a group selected from the group (3-1A-4) to Si(R 2 ) n L 3-n It is more preferable that q1 is a group excluding the following:
[0140] (Compound (D2)) In a further embodiment, the second compound is preferably represented by the following formula (D2).
[0141]
[0142] In formula (D2), L 2 are each independently a hydrolyzable group, a group having a hydrolyzable group, a hydroxyl group, or a hydrocarbon group; 2 At least four L 2 is a hydrolyzable group, a group having a hydrolyzable group, or a hydroxyl group; each P is independently an oxygen atom or an organic group having one carbon atom bonded to adjacent Si atoms on both sides; each r1 is independently an integer of 1 to 3; 4 , k1, A 12 The definitions of q and q1 are the same as those in formula (D).
[0143] In formula (D2), R 4 , k1, A 12 Specific embodiments of q1 and q2 are the same as those in formula (D). 2 Specific embodiments of P and r1 are L in formula (S3). 2 , P and r1 are the same as specific embodiments thereof.
[0144] The number average molecular weight (Mn) of the second compound is preferably 500 to 20,000, more preferably 600 to 18,000, and even more preferably 700 to 15,000. In one embodiment, the Mn of the second compound may be 500 to 5,000, or may be 500 to 3,000.
[0145] If Mn is 500 or more, the abrasion resistance of the surface treatment layer is superior. If Mn is 20,000 or less, the viscosity can be easily adjusted within an appropriate range, and the solubility is improved, resulting in excellent handling properties during film formation.
[0146] The composition of the present disclosure may contain only one type of second compound, or may contain two or more types.
[0147] The compositions of the present disclosure may contain impurities such as by-products produced in the manufacturing process of the second compound.
[0148] The content of the second compound is preferably 0.001 to 50% by mass, more preferably 0.01 to 20% by mass, and even more preferably 0.1 to 10% by mass, relative to the total amount of the composition of the present disclosure. In the case of a composition of the present disclosure used in a wet coating method, the content of the second compound may be 0.01 to 10% by mass, 0.02 to 5% by mass, 0.03 to 3% by mass, or 0.05 to 2% by mass, relative to the total amount of the composition of the present disclosure.
[0149] The content of the second compound is preferably more than 35% by mass and not more than 95% by mass, more preferably 36 to 90% by mass, may be 40 to 80% by mass, or may be 50 to 70% by mass, relative to the total solid content of the composition of the present disclosure.
[0150] In the composition of the present disclosure, the amount of the second compound relative to the total amount of the first compound and the second compound is more than 35 mol% and not more than 95 mol% from the viewpoint of obtaining a surface treatment layer with excellent abrasion resistance. That is, the amount of the first compound relative to the total amount of the first compound and the second compound is 5 mol% or more and less than 65 mol%. The amount of the second compound is preferably 36 mol% or more, may be 40 mol% or more, or may be 50 mol% or more. The amount of the second compound is preferably 90 mol% or less, or may be 80 mol% or less. The amount of the second compound is preferably 36 to 90 mol%, may be 40 to 80 mol%, or may be 50 to 70 mol%.
[0151] In the composition of the present disclosure, the combination of the first compound and the second compound may be any combination. For example, a first compound having one reactive silyl group at one end may be combined with a second compound having one reactive silyl group at each end. A first compound having one reactive silyl group at one end may be combined with a second compound having multiple reactive silyl groups at at least either end. A first compound having multiple reactive silyl groups at one end may be combined with a second compound having one reactive silyl group at each end. A first compound having multiple reactive silyl groups at one end may be combined with a second compound having multiple reactive silyl groups at at least either end.
[0152] In addition, one type of first compound may be combined with one type of second compound, one type of first compound may be combined with multiple types of second compounds, multiple types of first compounds may be combined with one type of second compound, or multiple types of first compounds may be combined with multiple types of second compounds.
[0153] In one embodiment, the molecular weights of the first compound and the second compound are preferably relatively close. For example, the Mn of both the first compound and the second compound is preferably 500 to 20,000, more preferably 600 to 18,000, and even more preferably 700 to 15,000. In one embodiment, the Mn of both the first compound and the second compound may be 500 to 5,000, or may be 500 to 3,000.
[0154] The total content of the first compound and the second compound is preferably 0.001 to 50 mass%, more preferably 0.01 to 20 mass%, and even more preferably 0.1 to 10 mass%, relative to the total amount of the composition of the present disclosure. In the case of a composition of the present disclosure used in a wet coating method, the total content of the first compound and the second compound may be 0.01 to 10 mass%, 0.02 to 5 mass%, 0.03 to 3 mass%, or 0.05 to 2 mass%, relative to the total amount of the composition of the present disclosure.
[0155] The total content of the first compound and the second compound is preferably 80 to 100 mass %, more preferably 90 to 100 mass %, and even more preferably 95 to 100 mass %, based on the total solid content of the composition of the present disclosure.
[0156] [Partial Structure of the First Compound and the Second Compound] Hereinafter, A in formula (C) 11 (Si(R 2 ) n L 3-n ) q1 , A in formula (D) 12 (Si(R 2 ) n L 3-n ) q1 and A in formula (E) 13 (Si(R 2 ) n L 3-n ) q1 A preferred embodiment of the formula (C) will be described below. 11 (Si(R 2 ) n L 3-n ) q1 , A in formula (D) 12 (Si(R2 ) n L 3-n ) q1 and A in formula (E) 13 (Si(R 2 ) n L 3-n ) q1 A(Si(R 2 ) n L 3-n ) q1 However, in the case of formula (C), A is a (p1+q1)-valent group, in the case of formula (D), A is a (q1+1)-valent group, and in the case of formula (E), A is a (q1+u1)-valent group.
[0157] A(Si(R 2 ) n L 3-n ) q1 The group represented by the formula (3-1A) is preferably the group (3-1A) or the group (3-1B), and more preferably the group (3-1A).
[0158] -Q a -X 31 (-Q b -Si(R 2 ) n L 3-n ) h (-R 31 ) i …(3-1A) -Q c - [CH 2 C (R 32 ) (-Q d -Si(R 2 ) n L 3-n )] y -R 33 ...(3-1B) In addition, in the formula (3-1A) and the formula (3-1B), R 2 , L, and n are defined as above.
[0159] In formula (3-1A), Q a is a single bond or a divalent linking group. Examples of the divalent linking group include a divalent hydrocarbon group, a divalent heterocyclic group, —O—, —S—, and —SO 2 -, -N(R d )-, -C(O)-, -Si(R a ) 2- and groups obtained by combining two or more of these. The divalent hydrocarbon group may be a divalent saturated hydrocarbon group, a divalent aromatic hydrocarbon group, an alkenylene group, or an alkynylene group. The divalent saturated hydrocarbon group may be linear, branched, or cyclic, and examples thereof include alkylene groups. The alkylene group preferably has 1 to 30 carbon atoms, more preferably 1 to 20, even more preferably 4 to 20, and particularly preferably 5 to 15. Furthermore, the divalent aromatic hydrocarbon group preferably has 5 to 20 carbon atoms, and examples thereof include a phenylene group. In addition, the group may be an alkenylene group having 2 to 20 carbon atoms or an alkynylene group having 2 to 20 carbon atoms. The R a is an alkyl group (preferably having 1 to 10 carbon atoms) or a phenyl group. d is a hydrogen atom or an alkyl group (preferably having 1 to 10 carbon atoms). Examples of groups formed by combining two or more of these groups include -OC(O)-, -C(O)O-, -C(O)S-, and -C(O)N(R d ) -, -N(R d )C(O)-,-N(R d )C(O)N(R d ) -, -N(R d )C(O)O-, -OC(O)N(R d ) -, -SO 2 N (R d ) -, -N(R d ) SO 2 -, -C(O)N(R d an alkylene group having —N(R d )C(O)-, an alkylene group having —OC(O)N(R d an alkylene group having —OC(O)—, an alkylene group having —C(O)O—, an alkylene group having —C(O)S—, an alkylene group having —N(R d an alkylene group having —N(R d )C(O)N(R d an alkylene group having —SO 2 N (R d )- and alkylene groups -Si(R a) 2 -phenylene group -Si(R a ) 2 Examples include:
[0160] In formula (3-1A), X 31 is a single bond, an alkylene group, a carbon atom, a nitrogen atom, a silicon atom, a divalent to octavalent organo(poly)siloxane residue, or a group having a (h+i+1)-valent ring. The alkylene group may have -O-, a silphenylene skeleton group, a divalent organo(poly)siloxane residue, or a dialkylsilylene group. The alkylene group may have a plurality of groups selected from the group consisting of -O-, a silphenylene skeleton group, a divalent organo(poly)siloxane residue, and a dialkylsilylene group. X 31 The number of carbon atoms in the alkylene group represented by the formula (I) is preferably 1 to 20, and more preferably 1 to 10. Examples of the divalent to octavalent organo(poly)siloxane residue include a divalent organo(poly)siloxane residue and a (w2+1)-valent organo(poly)siloxane residue described below.
[0161] In formula (3-1A), X 31 is a group having a (h+i+1)-valent ring, Q a , (-Q b -Si(R 2 ) n L 3-n ) and R 31 is directly bonded to an atom constituting the ring, provided that the ring is a ring other than an organopolysiloxane ring. 31The ring in may be any of a monocycle, a fused polycycle, a bridged ring, a spiro ring, and an aggregate polycycle, and the atoms constituting the ring may be a carbocycle consisting of only carbon atoms, or a heterocycle consisting of a heteroatom having a valence of divalent or higher and a carbon atom. The bond between the atoms constituting the ring may be a single bond or a multiple bond. Furthermore, the ring may be an aromatic ring or a non-aromatic ring. As the monocycle, a 4- to 8-membered ring is preferred, and a 5- or 6-membered ring is more preferred. As the fused polycycle, a fused polycycle in which two or more 4- to 8-membered rings are fused is preferred, and a fused polycycle in which two or three rings selected from 5- and 6-membered rings are bonded, and a fused polycycle in which one or two rings selected from 5- or 6-membered rings are bonded to one 4-membered ring are more preferred. The bridged ring is preferably a bridged ring having a 5-membered or 6-membered ring as the largest ring, and the spiro ring is preferably a spiro ring consisting of two 4- to 6-membered rings. The assembled polycycle is preferably an assembled polycycle in which two or three rings selected from the 5-membered and 6-membered rings are bonded via a single bond, 1 to 3 carbon atoms, or one heteroatom having a valence of 2 or 3. In the assembled polycycle, each ring may have a Q a , (-Q b -Si(R 2 ) n L 3-n ) and R 31 (when i = 1 or more) is preferably bonded. As heteroatoms constituting the ring, nitrogen atoms, oxygen atoms, and sulfur atoms are preferred, and nitrogen atoms and oxygen atoms are more preferred. The number of heteroatoms constituting the ring is preferably 3 or less. Furthermore, when the number of heteroatoms constituting the ring is 2 or more, the heteroatoms may be different.
[0162] X 31In terms of ease of production of the compound and further excellent abrasion resistance of the surface treatment layer, the ring in the formula (I) is preferably one selected from the group consisting of a 3- to 8-membered aliphatic ring, a benzene ring, a 3- to 8-membered heterocyclic ring, a fused ring in which two or three of these rings are fused, a bridged ring in which the largest ring is a 5- or 6-membered ring, and an assembled polycyclic ring having two or more of these rings and in which the linking group is a single bond, an alkylene group having 3 or less carbon atoms, an oxygen atom, or a sulfur atom. Preferred rings are a benzene ring, a 5- or 6-membered aliphatic ring, a 5- or 6-membered heterocyclic ring having a nitrogen atom or an oxygen atom, and a fused ring of a 5- or 6-membered carbocyclic ring with a 4- to 6-membered heterocyclic ring. Specific examples of the ring include the rings shown below, as well as a 1,3-cyclohexadiene ring, a 1,4-cyclohexadiene ring, an anthracene ring, a cyclopropane ring, a decahydronaphthalene ring, a norbornene ring, a norbornadiene ring, a furan ring, a pyrrole ring, a thiophene ring, a pyrazine ring, a morpholine ring, an aziridine ring, an isoquinoline ring, an oxazole ring, an isoxazole ring, a thiazole ring, an imidazole ring, a pyrazole ring, a pyran ring, a pyridazine ring, a pyrimidine ring, and an indene ring. Rings having an oxo group (═O) are also shown below.
[0163]
[0164] X 31 The bond that does not constitute the ring of the atom that constitutes the ring in a , (-Q b -Si(R 2 ) n L 3-n ) or R 31 When there are remaining bonds, the remaining bonds are bonded to a hydrogen atom or a substituent. Examples of the substituent include a halogen atom, an alkyl group (which may contain an etheric oxygen atom between carbon atoms), a cycloalkyl group, an alkenyl group, an allyl group, an alkoxy group, and an oxo group (=O). In addition, when one of the carbon atoms constituting the ring is bonded to Q a , (-Q b -Si(R 2 ) n L 3-n ) or R 31When there are two bonds bonded to one of the carbon atoms, Q a and (-Q b -Si(R 2 ) n L 3-n ) may be bonded to two (-Q b -Si(R 2 ) n L 3-n ) may be bonded to a and (-Q b -Si(R 2 ) n L 3-n ) or R 31 It is preferable that h (-Q b -Si(R 2 ) n L 3-n ) may be bonded to different ring-constituting atoms, and two of them may be bonded to one ring-constituting carbon atom, and two (-Q b -Si(R 2 ) n L 3-n There may be two or more ring-constituting carbon atoms to which i R 31 may be bonded to different ring-constituting atoms, two of which may be bonded to one ring-constituting carbon atom, and two R 31 There may be two or more ring-constituting carbon atoms to which is bonded.
[0165] Among them, X 31 From the viewpoint of improving the abrasion resistance of the surface treatment layer, is preferably a carbon atom, a nitrogen atom, a silicon atom, a tetravalent to octavalent organo(poly)siloxane residue, or a group having a (h+i+1)-valent ring, and more preferably a carbon atom.
[0166] In formula (3-1A), Q b is a single bond or a divalent linking group. The definition of a divalent linking group is the same as that of Q a This is the same as the definition explained in
[0167] Among them, Q bis preferably an alkylene group which may have an etheric oxygen atom. The number of carbon atoms in the alkylene group is preferably 1 to 30, more preferably 1 to 20, and even more preferably 2 to 20, and may be 2 to 10, 2 to 6, or 2 to 5. Examples include 2, 3, 8, 9, and 11. The number of carbon atoms may also be 1 to 10.
[0168] In formula (3-1A), R 31 is a hydrogen atom, a hydroxyl group, or an alkyl group. The alkyl group preferably has 1 to 5 carbon atoms, more preferably 1 to 3 carbon atoms, and even more preferably 1 carbon atom.
[0169] X 31 When X is a single bond or an alkylene group, h is 1 and i is 0; 31 is a nitrogen atom, h is an integer of 1 to 2, i is an integer of 0 to 1, and h+i=2 is satisfied; 31 When X is a carbon atom or a silicon atom, h is an integer of 1 to 3, i is an integer of 0 to 2, and h+i=3 is satisfied; 31 When X is a divalent to octavalent organo(poly)siloxane residue, h is an integer of 1 to 7, i is an integer of 0 to 6, and h+i=1 to 7. 31 is a group having a (h+i+1)-valent ring, h is an integer of 1 to 7, i is an integer of 0 to 6, and h+i=1 to 7 is satisfied. b -Si(R) n L 3-n If there are two or more (-Q b -Si(R) n L 3-n ) may be the same or different. 31 If there are two or more, there are two or more (-R 31 ) may be the same or different.
[0170] In particular, it is preferable that i is 0 from the viewpoint of improving the abrasion resistance of the surface treatment layer.
[0171] In formula (3-1B), Q c is a single bond or a divalent linking group. The definition of a divalent linking group is the same as that of Q a This is the same as the definition explained in
[0172] In formula (3-1B), R 32 is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and is preferably a hydrogen atom in view of ease of production of the compound. As the alkyl group, a methyl group is preferred.
[0173] In formula (3-1B), Q d is a single bond or an alkylene group. The number of carbon atoms in the alkylene group is preferably 1 to 10, more preferably 1 to 6. From the viewpoint of ease of production of the compound, Q d is a single bond or CH 2 It is preferable that −.
[0174] In formula (3-1B), R 33 is a hydrogen atom or a halogen atom, and is preferably a hydrogen atom in view of ease of producing the compound.
[0175] y is an integer of 1 to 10, preferably an integer of 1 to 6. 2 C (R 32 ) (-Q d -Si(R 2 ) n L 3-n ) )] may be the same or different.
[0176] As the group (3-1A), groups (3-1A-1) to (3-1A-7) are preferred.
[0177] -(X 32 ) s1 -Q b1 -Si(R 2 ) n L 3-n ...(3-1A-1) -(X 33 ) s2 -Q a2 -N[-Q b2 -Si(R 2 ) n L 3-n ] 2 ...(3-1A-2) -Q a3 -Si(R g ) [-Q b3 -Si(R 2 ) n L 3-n ]2 ...(3-1A-3) -[Q e ] s4 -Q a4 -(O) t4 -C[-(O) u4 -Q b4 -Si(R 2 ) n L 3-n ] 3-w1 (-R 31 ) w1 ...(3-1A-4) -Q a5 -Si[-Q b5 -Si(R 2 ) n L 3-n ] 3 ...(3-1A-5) -[Q e ] v -Q a6 -Z a [-Q b6 -Si(R 2 ) n L 3-n ] w2 ...(3-1A-6) -[Q e ] s4 -Q a4 -(O) t4 -Z c [-(O-Q b4 ) u4 -Si(R 2 ) n L 3-n ] w3 (-OH) w4 ...(3-1A-7) In the formulas (3-1A-1) to (3-1A-7), R 2 , L, and n are defined as above.
[0178] Among these, the group (3-1A) is preferably the group (3-1A-4).
[0179] In the group (3-1A-1), X 32 is -O-, -S-, -N(R d )-, -C(O)-, -C(O)O-, -C(O)S-, -SO 2 N (R d ) -, -N(R d ) SO 2 -, -N(R d)C(O)-,-N(R d )C(O)N(R d )-,-OC(O)N(R d )- or -C(O)N(R d )-; or a combination of these with a divalent linking group (wherein N in the formula is Q b1 (Binds to R d The definition of is as described above. s1 is 0 or 1.
[0180] X 32 However, -O-, -S-, -N(R d )-, -C(O)-, -C(O)O-, -C(O)S-, -SO 2 N (R d ) -, -N(R d ) SO 2 -, -N(R d )C(O)-,-N(R d )C(O)N(R d )-,-OC(O)N(R d )- or -C(O)N(R d )- and a divalent linking group, the divalent linking group is Si(R 3 ) 2 , Si(R 4 ) 2 or B of formula (E) 11 The divalent linking group includes an alkylene group, an organo(poly)siloxane residue, a polyalkylene oxide group, and combinations thereof.
[0181] Q b1 is a single bond or an alkylene group. The alkylene group may have -O-, a silphenylene skeletal group, or a dialkylsilylene group. The alkylene group may have a plurality of groups selected from the group consisting of -O-, a silphenylene skeletal group, a divalent organo(poly)siloxane residue, and a dialkylsilylene group. When the alkylene group has -O-, a silphenylene skeletal group, a divalent organo(poly)siloxane residue, or a dialkylsilylene group, it is preferable that these groups be present between carbon atoms. Q b1The number of carbon atoms in the alkylene group represented by the formula (I) is preferably 1 to 30, more preferably 1 to 20, still more preferably 2 to 20, and particularly preferably 2 to 6. The number of carbon atoms may also be 1 to 10.
[0182] In the group (3-1A-2), X 33 is -O-, -S-, -N(R d )-, -C(O)-, -C(O)O-, -C(O)S-, -SO 2 N (R d ) -, -N(R d ) SO 2 -, -N(R d )C(O)-,-N(R d )C(O)N(R d )-,-OC(O)N(R d )- or -C(O)N(R d )-; or a combination of these with a divalent linking group. d The definition of is as described above. s2 is 0 or 1. s2 is preferably 0 in view of ease of production of the compound.
[0183] X 33 However, -O-, -S-, -N(R d )-, -C(O)-, -C(O)O-, -C(O)S-, -SO 2 N (R d ) -, -N(R d ) SO 2 -, -N(R d )C(O)-,-N(R d )C(O)N(R d )-,-OC(O)N(R d )- or -C(O)N(R d )- and a divalent linking group, the divalent linking group is Si(R 3 ) 2 , Si(R 4 ) 2 or B of formula (E) 11 The divalent linking group includes an alkylene group, an organo(poly)siloxane residue, a polyalkylene oxide group, and combinations thereof.
[0184] Q a2represents a single bond, an alkylene group, -C(O)-, or an etheric oxygen atom, -C(O)-, -C(O)O-, -OC(O)-, -C(O)N(R d ) -, -N(R d )C(O)-,-N(R d )C(O)N(R d ) -, -N(R d )C(O)O-, -OC(O)N(R d ) -, -SO 2 N (R d ) -, -N(R d ) SO 2 -, -C(O)N(R d )- or -NH-. a2 The number of carbon atoms in the alkylene group represented by the formula (I) is preferably 1 to 20, more preferably 1 to 10, even more preferably 1 to 6, and particularly preferably 1 to 3. a2 an etheric oxygen atom between carbon atoms of an alkylene group having two or more carbon atoms, represented by —C(O)—, —C(O)O—, —OC(O)—, —C(O)N(R d ) -, -N(R d )C(O)-,-N(R d )C(O)N(R d ) -, -N(R d )C(O)O-, -OC(O)N(R d ) -, -SO 2 N (R d ) -, -N(R d ) SO 2 -, -C(O)N(R d The group having — or —NH— preferably has 2 to 10 carbon atoms, more preferably 2 to 6 carbon atoms.
[0185] Q a2 is preferably a single bond in terms of ease of production of the compound.
[0186] Q b2 is an alkylene group or a group having a divalent organo(poly)siloxane residue, an etheric oxygen atom, or —NH— between carbon atoms of an alkylene group having two or more carbon atoms. b2The number of carbon atoms in the alkylene group represented by the formula (I) is preferably 1 to 30, more preferably 1 to 20, and even more preferably 2 to 20, and may be 2 to 10 or 2 to 6. Examples include 2, 3, 8, 9, and 11. The number of carbon atoms may also be 1 to 10. Q b2 The number of carbon atoms in the divalent organo(poly)siloxane residue, the etheric oxygen atom, or the group having —NH— between carbon atoms in the alkylene group having 2 or more carbon atoms, represented by the following formula (I), is preferably 2 to 10, and more preferably 2 to 6.
[0187] Q b2 As the compound, -CH 2 CH 2 CH 2 -, -CH 2 CH 2 OCH 2 CH 2 CH 2 - is preferred (where the right side is bonded to Si).
[0188] Two [-Q b2 -Si(R 2 ) n L 3-n ] may be the same or different.
[0189] In the group (3-1A-3), Q a3 is a single bond or an alkylene group which may have an etheric oxygen atom. a3 The alkylene group which may have an etheric oxygen atom preferably has 1 to 10 carbon atoms, and particularly preferably has 2 to 6 carbon atoms.
[0190] R g is a hydrogen atom, a hydroxyl group, or an alkyl group. g From the viewpoint of ease of production of the compound, a hydrogen atom or an alkyl group is preferred. The alkyl group preferably has 1 to 10 carbon atoms, more preferably 1 to 4 carbon atoms, and further preferably is a methyl group.
[0191] Q b3is an alkylene group or a group having an etheric oxygen atom or a divalent organo(poly)siloxane residue between carbon atoms of an alkylene group having two or more carbon atoms. b3 The number of carbon atoms in the alkylene group represented by the formula (I) is preferably 1 to 30, more preferably 1 to 20, and even more preferably 2 to 20, and may be 2 to 10 or 2 to 6. Examples include 2, 3, 8, 9, and 11. The number of carbon atoms may also be 1 to 10. Q b3 The number of carbon atoms in the group having an etheric oxygen atom or a divalent organo(poly)siloxane residue between carbon atoms in the alkylene group having 2 or more carbon atoms, represented by the formula (I), is preferably 2 to 20, more preferably 2 to 10, and even more preferably 2 to 6. b3 is preferably -CH 2 CH 2 -, -CH 2 CH 2 CH 2 - or -CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 - is preferred.
[0192] Two [-Q b3 -Si(R 2 ) n L 3-n ] may be the same or different.
[0193] In the group (3-1A-4), Q e is -C(O)O-, -SO 2 N (R d ) -, -N(R d ) SO 2 -, -N(R d )C(O)- or -C(O)N(R d )-; or a combination of these with a divalent linking group. e is -C(O)O-, -SO 2 N (R d ) -, -N(R d ) SO 2 -, -N(Rd )C(O)- or -C(O)N(R d )- and a divalent linking group, the divalent linking group is Si(R 3 ) 2 , Si(R 4 ) 2 or B of formula (E) 11 Examples of the divalent linking group include an alkylene group, an organo(poly)siloxane residue, a polyalkylene oxide group, and combinations thereof. 31 The definition of is as described above. When w1 is 1 or 2, R 31 is preferably a hydrogen atom. s4 is 0 or 1. Q a4 is a single bond or an alkylene group which may have an etheric oxygen atom. The number of carbon atoms in the alkylene group which may have an etheric oxygen atom is preferably 1 to 20, more preferably 1 to 10, still more preferably 1 to 6, and particularly preferably 1 to 3. t4 is 0 or 1 (provided that Q a4 If -Q is a single bond, it is 0. a4 -(O) t4 When s4 is 0, a single bond or —CH 2 O-, -CH 2 OCH 2 -, -CH 2 OCH 2 CH 2 O-, -CH 2 OCH 2 CH 2 OCH 2 -, -CH 2 OCH 2 CH 2 CH 2 CH 2 OCH 2 When s4 is 1, a single bond or —CH 2 -, -CH 2 CH 2 - is preferred.
[0194] Q b4 is an alkylene group, and the alkylene group is —O—, —C(O)N(R d)-(R d The definition of is as described above. ), may have a silphenylene skeleton group, a divalent organo(poly)siloxane residue, or a dialkylsilylene group. When the alkylene group has -O- or a silphenylene skeleton group, it is preferable that the alkylene group has -O- or a silphenylene skeleton group between carbon atoms. In addition, when the alkylene group is -C(O)N(R d )-, dialkylsilylene group or divalent organo(poly)siloxane residue, carbon atom-carbon atom or (O) u4 It is preferable that these groups are present at the end of the bond with Q. b4 The number of carbon atoms in the alkylene group represented by the formula (I) is preferably 1 to 30, more preferably 1 to 20, and even more preferably 2 to 20, and may be 2 to 10 or 2 to 6. Examples include 2, 3, 8, 9, and 11. The number of carbon atoms may also be 1 to 10.
[0195] u4 is 0 or 1. -(O) u4 -Q b4 As the -, -CH is preferred from the viewpoint of ease of production of the compound. 2 CH 2 -, -CH 2 CH 2 CH 2 -, -CH 2 OCH 2 CH 2 CH 2 -, -CH 2 OCH 2 CH 2 CH 2 CH 2 CH 2 -, -OCH 2 CH 2 CH 2 -, -OSi(CH 3 ) 2 CH 2 CH 2 CH 2 -, -OSi(CH 3 ) 2 OSi(CH 3 ) 2 CH 2 CH 2 CH 2 -, -CH2 CH 2 CH 2 Si(CH 3 ) 2 PhSi(CH 3 ) 2 CH 2 CH 2 - is preferred (where the right side is bonded to Si).
[0196] w1 is an integer of 0 to 2, preferably 0 or 1, and more preferably 0. [-(O) u4 -Q b4 -Si(R 2 ) n L 3-n If there are two or more [-(O) u4 -Q b4 -Si(R 2 ) n L 3-n ] may be the same or different. 31 If there are two or more, there are two or more (-R 31 ) may be the same or different.
[0197] In the group (3-1A-5), Q a5 is an alkylene group which may have an etheric oxygen atom. The alkylene group which may have an etheric oxygen atom preferably has 1 to 10 carbon atoms, and particularly preferably has 2 to 6 carbon atoms. a5 As the compound, -OCH 2 CH 2 CH 2 -, -OCH 2 CH 2 OCH 2 CH 2 CH 2 -, -CH 2 CH 2 -, -CH 2 CH 2 CH 2 - is preferred (where the right side is bonded to Si).
[0198] Q b5is an alkylene group or a group having an etheric oxygen atom or a divalent organo(poly)siloxane residue between carbon atoms of an alkylene group having two or more carbon atoms. b5 The number of carbon atoms in the alkylene group represented by the formula (I) is preferably 1 to 30, more preferably 1 to 20, and even more preferably 2 to 20, and may be 2 to 10 or 2 to 6. Examples include 2, 3, 8, 9, and 11. The number of carbon atoms may also be 1 to 10. Q b5 The number of carbon atoms in the group having an etheric oxygen atom or a divalent organo(poly)siloxane residue between carbon atoms in the alkylene group having 2 or more carbon atoms, represented by the formula (I), is preferably 2 to 20, more preferably 2 to 10, and even more preferably 2 to 6. b5 As the compound, -CH 2 CH 2 CH 2 -, -CH 2 CH 2 OCH 2 CH 2 CH 2 - is preferred (however, the right side is Si(R 2 ) n L 3-n Bind to. ).
[0199] Three [-Q b5 -Si(R 2 ) n L 3-n ] may be the same or different.
[0200] Q in group (3-1A-6) e is as defined in the above group (3-1A-4). v is 0 or 1.
[0201] Q a6 is an alkylene group which may have an etheric oxygen atom. The alkylene group which may have an etheric oxygen atom preferably has 1 to 10 carbon atoms, and particularly preferably has 2 to 6 carbon atoms. a6 As the compound, -CH 2 OCH 2 CH 2 CH 2 -, -CH2 OCH 2 CH 2 OCH 2 CH 2 CH 2 -, -CH 2 CH 2 -, -CH 2 CH 2 CH 2 - is preferred (however, the right side is Z a Bind to. ).
[0202] Z a is a (w2+1)-valent organo(poly)siloxane residue, or a (w2+1)-valent group having an alkylene group between the organo(poly)siloxane residues. w2 is an integer of 2 to 7. Examples of the (w2+1)-valent organo(poly)siloxane residue and the (w2+1)-valent group having an alkylene group between the organo(poly)siloxane residues include the following groups. However, R in the following formula a * indicates a binding site.
[0203]
[0204] Q b6 is an alkylene group or a group having an etheric oxygen atom or a divalent organo(poly)siloxane residue between carbon atoms of an alkylene group having two or more carbon atoms. b6 The number of carbon atoms in the alkylene group represented by the formula (I) is preferably 1 to 30, more preferably 1 to 20, and even more preferably 2 to 20, and may be 2 to 10 or 2 to 6. Examples include 2, 3, 8, 9, and 11. The number of carbon atoms may also be 1 to 10. Q b6 The number of carbon atoms in the group having an etheric oxygen atom or a divalent organo(poly)siloxane residue between carbon atoms in the alkylene group having 2 or more carbon atoms, represented by the formula (I), is preferably 2 to 20, more preferably 2 to 10, and even more preferably 2 to 6. b6 As the compound, -CH 2 CH 2 -, -CH 2 CH2 CH 2 - is preferred. w2 [-Q b6 -Si(R 2 ) n L 3-n ] may be the same or different.
[0205] In the group (3-1A-7), Z c is a hydrocarbon group having a valence of (w3+w4+1). w3 is an integer of 4 or more. w4 is an integer of 0 or more. Q e , s4, Q a4 , t4, Q b4 The definitions and preferred ranges of u4 and u5 are the same as those of the respective symbols in group (3-1A-4).
[0206] Z c may be composed of a hydrocarbon chain, and may have an etheric oxygen atom between carbon atoms in the hydrocarbon chain, and is preferably composed of a hydrocarbon chain. c The valence of Z is preferably from 5 to 20, more preferably from 5 to 10, still more preferably from 5 to 8, and particularly preferably from 5 to 6. c The number of carbon atoms in [-(O-Q b4 ) u4 -Si(R 2 ) n L 3-n If there are two or more [-(O-Q b4 ) u4 -Si(R 2 ) n L 3-n ] may be the same or different.
[0207] Formula A(Si(R 2 ) n L 3-n ) q1 A in the formula may be any of the groups (g2-1) to (g2-7).
[0208]
[0209] (-A 1 -Q 12 -) e1 C (R e2 ) 4-e1-e2 (-Q 22 -) e2 ... (g2-2) -A 1 -Q 13 -N(-Q 23 -) 2 ...(g2-3) (-A 1 -Q 14 -) h1 Z 4 (-Q 24 -) h2 ...(g2-4) (-A 1 -Q 15 -) i1 Si(R e3 ) 4-i1-i2 (-Q 25 -) i2 ... (g2-5) -A 1 -Q 26 - (g2-6) -A 1 -Q 12 -CH(-Q 22 -)-Si(R e3 ) 3-i3 (-Q 25 -) i3 …(g2-7)
[0210] However, in formulas (g2-1) to (g2-7), A 1 The side is Si(R 3 ) 2 , Si(R 4 ) 2 , or B 11 and Q 22 , Q 23 , Q 24 , Q 25 or Q 26 The side is [-Si(R 2 ) n L 3-n ]. 1 represents a single bond, -C(O)NR 6 -, -C(O)-, -OC(O)O-, -NHC(O)O-, -NHC(O)NR6 -, -O- or SO 2 NR 6 - is. 11 represents a single bond, —O—, an alkylene group, or —C(O)NR between carbon atoms of an alkylene group having two or more carbon atoms. 6 -, -C(O)-, -NR 6 - or O- containing group. 12 represents a single bond, an alkylene group, or an alkylene group having two or more carbon atoms with —C(O)NR between carbon atoms. 6 -, -C(O)-, -NR 6 - or O-, and A is Q 12 If there are two or more, there are two or more Q 12 may be the same or different. 13 is a single bond (where A 1 is —C(O)—), an alkylene group, an alkylene group having 2 or more carbon atoms having —C(O)NR between carbon atoms. 6 -, -C(O)-, -NR 6 Q is a group having - or O-, or a group having -C(O)- at the N-terminal of the alkylene group. 14 Is, Q 14 Z to which 4 If the atom in is a carbon atom, Q 12 and Q 14 Z to which 4 When the atom in is a nitrogen atom, Q 13 and A is Q 14 If there are two or more, there are two or more Q 14 may be the same or different. 15 represents an alkylene group or an alkylene group having two or more carbon atoms with —C(O)NR between carbon atoms. 6 -, -C(O)-, -NR 6 - or O-, and A is Q 15 If there are two or more, there are two or more Q 15 may be the same or different. 22 represents an alkylene group, an alkylene group having 2 or more carbon atoms, and a —C(O)NR group between carbon atoms. 6 -, -C(O)-, -NR 6a group having - or O-, and -C(O)NR at the end of the alkylene group not connected to Si; 6 -, -C(O)-, -NR 6 A group having - or O-, or an alkylene group having 2 or more carbon atoms having -C(O)NR between carbon atoms. 6 -, -C(O)-, -NR 6 - or O- and -C(O)NR at the end not connected to Si 6 -, -C(O)-, -NR 6 - or O-, and A is Q 22 If there are two or more, there are two or more Q 22 may be the same or different. 23 represents an alkylene group or an alkylene group having two or more carbon atoms with —C(O)NR between carbon atoms. 6 -, -C(O)-, -NR 6 - or O-, and two Q 23 may be the same or different. 24 Is, Q 24 Z to which 4 If the atom in is a carbon atom, Q 22 and Q 24 Z to which 4 When the atom in is a nitrogen atom, Q 23 and A is Q 24 If there are two or more, there are two or more Q 24 may be the same or different. 25 represents an alkylene group or an alkylene group having two or more carbon atoms with —C(O)NR between carbon atoms. 6 -, -C(O)-, -NR 6 - or O-, and A is Q 25 If there are two or more, there are two or more Q 25 may be the same or different. 26 represents an alkylene group or an alkylene group having two or more carbon atoms with —C(O)NR between carbon atoms. 6 -, -C(O)-, -NR 6 - or O- containing group. 22 , Q 23 , Q 24 , Q 25 , Q26 When Z is an alkylene group, it preferably has 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, and even more preferably 1 to 6 carbon atoms. 4 Is, Q 14 has a carbon atom or nitrogen atom to which Q is directly bonded, 24 is a group having a (h1+h2)-valent ring structure having a carbon atom or nitrogen atom to which R is directly bonded. e1 is a hydrogen atom or an alkyl group, and A is R e1 When there are two or more R e1 may be the same or different. e2 is a hydrogen atom, a hydroxyl group, an alkyl group, or an acyloxy group. e3 is an alkyl group. 6 is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group.
[0211] d1 is an integer of 0 to 3, preferably 1 or 2. d2 is an integer of 0 to 3, preferably 1 or 2. d1 + d2 is an integer of 1 to 3. d3 is an integer of 0 to 3, preferably 0 or 1. d4 is an integer of 0 to 3, preferably 2 or 3. d3 + d4 is an integer of 1 to 3. d1 + d3 is an integer of 1 to 5, preferably 1 or 2. d2 + d4 is an integer of 1 to 5, preferably 4 or 5. e1 + e2 is 3 or 4. e1 is an integer of 1 to 3, preferably 1 or 2. e2 is an integer of 1 to 3, preferably 2 or 3. h1 is an integer of 1 or more, preferably 1 or 2. h2 is an integer of 1 or more, preferably 2 or 3. i1 + i2 is 3 or 4. i1 is an integer of 1 to 3, and preferably 1 or 2. i2 is an integer of 1 to 3, and preferably 2 or 3. i3 is 2 or 3.
[0212] Q 11 , Q 12 , Q 13 , Q 14 , Q 15 , Q 22 , Q 23, Q 24 , Q 25 and Q 26 The number of carbon atoms in the alkylene group is preferably 1 to 30, more preferably 1 to 20, and even more preferably 2 to 20, from the viewpoints of ease of production of the compound and further superior abrasion resistance of the surface treatment layer, and may be 2 to 10 or 2 to 6. Examples include 2, 3, 8, 9, and 11. The number of carbon atoms may also be 1 to 10, 1 to 6, or 1 to 4. However, when a specific bond is present between carbon atoms, the lower limit of the number of carbon atoms in the alkylene group is 2.
[0213] Z 4 Examples of the ring structure in Z include the ring structures described above, and the preferred embodiments are also the same. 4 The ring structure in 14 YaQ 24 is directly bonded to the ring structure, for example, an alkylene group is linked to the alkylene group, and Q 14 YaQ 24 are never connected.
[0214] R e1 , R e2 or R e3 The number of carbon atoms in the alkyl group of R is preferably 1 to 6, more preferably 1 to 3, and particularly preferably 1 or 2, from the viewpoint of ease of production of the compound. e2 The number of carbon atoms in the alkyl group portion of the acyloxy group is preferably 1 to 6, more preferably 1 to 3, and particularly preferably 1 or 2, from the viewpoint of ease of production of the compound. h1 is preferably 1 to 6, more preferably 1 to 4, even more preferably 1 or 2, and particularly preferably 1, from the viewpoint of ease of production of the compound and further excellent abrasion resistance of the surface treatment layer. h2 is preferably 2 to 6, more preferably 2 to 4, and particularly preferably 2 or 3, from the viewpoint of ease of production of the compound and further excellent abrasion resistance of the surface treatment layer.
[0215] Formula A(Si(R 2 ) n L 3-n ) q1 Other forms of A in the above formula include groups (g2-8) to (g2-14).
[0216]
[0217] (-A 1 -Q 12 -) e1 C (R e2 ) 4-e1-e2 (-Q 22 -G 1 ) e2 ... (g2-9) -A 1 -Q 13 -N(-Q 23 -G 1 ) 2 ...(g2-10) (-A 1 -Q 14 -) h1 Z 4 (-Q 24 -G 1 ) h2 ...(g2-11) (-A 1 -Q 15 -) i1 Si(R e3 ) 4-i1-i2 (-Q 25 -G 1 ) i2 ...(g2-12) -A 1 -Q 26 -G 1 ...(g2-13) -A 1 -Q 12 -CH(-Q 22 -G 1 )-Si(R e3 ) 3-i3 (-Q 25 -G 1 ) i3 …(g2-14)
[0218] However, in formulas (g2-8) to (g2-14), A 1 The side is Si(R 3 ) 2 , Si(R 4 ) 2 , or B 11 and binds to G 1 The side is [-Si(R 2 ) n L 3-n ] and combine.
[0219] G 1is the following group (g3), and A has two or more G 1 may be the same or different. 1 The symbols other than are the same as those in formulas (g2-1) to (g2-7). 13 ) 3-k3 (-Q 3 -) k3 ...(g3) In the group (g3), the Si side is Q 22 , Q 23 , Q 24 , Q 25 and Q 26 Connect to Q 3 The side is [-Si(R 2 ) n L 3-n ]. 13 is an alkyl group. 3 represents an alkylene group, an alkylene group having 2 or more carbon atoms, and a —C(O)NR group between carbon atoms. 6 -, -C(O)-, -NR 6 - or -O- containing group, or (OSi(R 9 ) 2 ) p -O-, and two or more Q 3 may be the same or different. k3 is 2 or 3. R 6 is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group. 9 is an alkyl group, a phenyl group, or an alkoxy group, and two R 9 may be the same or different. p is an integer of 0 to 5, and when p is 2 or more, there are two or more (OSi(R 9 ) 2 ) may be the same or different.
[0220] Q 3The number of carbon atoms in the alkylene group is preferably 1 to 30, more preferably 1 to 20, and even more preferably 2 to 20, from the viewpoint of ease of production of the compound and further superior abrasion resistance of the surface treatment layer, and may be 2 to 10 or 2 to 6. Examples include 2, 3, 8, 9, and 11. The number of carbon atoms may be 1 to 10, 1 to 6, or 1 to 4. However, when there is a specific bond between carbon atoms, the lower limit of the number of carbon atoms in the alkylene group is 2. R 13 The number of carbon atoms in the alkyl group of R is preferably 1 to 6, more preferably 1 to 3, and even more preferably 1 or 2, from the viewpoint of ease of production of the compound. 9 The number of carbon atoms in the alkyl group of R is preferably 1 to 6, more preferably 1 to 3, and even more preferably 1 or 2, from the viewpoint of ease of production of the compound. 9 In view of excellent storage stability of the compound, the number of carbon atoms in the alkoxy group is preferably 1 to 6, more preferably 1 to 3, and particularly preferably 1 or 2. p is preferably 0 or 1.
[0221] [Examples of the first compound and the second compound] Specific examples of the first compound and the second compound are described in detail below. Specific examples of the first compound include the following compounds (1) to (3), (4A), and (5). Specific examples of the second compound include the following compound (4B).
[0222] Compound (1) A compound containing the following group 1a, a chain organo(poly)siloxane residue, a partial structure which is an alkylene chain or polyalkylene oxide chain having 3 or more carbon atoms, and the following group 1b. Group 1a: -M 1 T 1 3 Group 1b: -Si(R 2 ) n L 3-n M 1 is Si, Sn, or Ge, and T 1 are each independently a hydrocarbon group or a trialkylsilyloxy group, R 2are each independently a monovalent hydrocarbon group, each L is independently a hydrolyzable group, a group having a hydrolyzable group, or a hydroxyl group, and each n is independently an integer of 0 to 2. 2 , L, and n are R in the above formula (S1). 2 , L, and n are the same as those of the group 1a. 11 T in the explanation of 1 3 M 1 - Details are the same as above.
[0223] Compound (2) A compound containing an alkyl group having two or more carbon atoms, a linear organo(poly)siloxane residue, and a reactive silyl group.
[0224] Compound (3) A compound comprising the following group 3a, a partial structure containing a divalent linear organo(poly)siloxane residue, and the following group 3b, wherein the partial structure is a divalent linear organo(poly)siloxane residue or a combination of a divalent linear organo(poly)siloxane residue and at least one of an alkylene chain and a polyalkylene oxide chain. Group 3a: a monovalent cyclic polysiloxane residue or a monovalent cage polysiloxane residue Group 3b: -Si(R 2 ) n L 3-n R 2 are each independently a monovalent hydrocarbon group, each L is independently a hydrolyzable group, a group having a hydrolyzable group, or a hydroxyl group, and each n is independently an integer of 0 to 2. 2 , L, and n are R in the above formula (S1). 2 , L, and n.
[0225] Compounds (4A) and (4B) Compounds represented by the following formula (4A) or (4B) (R T1 -R S -(-SiR T2 2 -) q4 ) α -X A -R H β ...(4A) R H γ -XA -O p4 -R S -(-SiR T2 2 -) q4 -X A -R H γ ... (4B) In formulas (4A) and (4B), R S are each independently a divalent linear organosiloxane group, and R T1 are each independently a hydrocarbon group, R T2 are each independently a hydrocarbon group, p4 is 0 or 1, q4 is each independently 0 or 1, R H is a group represented by any one of the following formulas (W1) to (W4), H In the present invention, there are two or more Si atoms to which hydroxyl groups or hydrolyzable groups are bonded, and X A are each independently a single bond or a group represented by the following formula (W5), α is an integer of 1 to 9, β is an integer of 1 to 9, and γ is each independently an integer of 1 to 9. -(CH 2 CR 10 (R 15 ) X 11 -Si(R 2 ) n81 L 3-n81 ) t -R 14 ...(W1)-SiR a1 k81 L l81 R c1 m81 ...(W2) -CR d1 k82 R e1 l82 R f1 m82 ... (W3) -NR g1 R h1 ...(W4) In formulae (W1) to (W4), each L is independently a hydrolyzable group, a group having a hydrolyzable group, or a hydroxyl group, and R 2 are each independently a monovalent hydrocarbon group, 81 is (SiR 2 n81L 3-n81 ) units are each independently an integer of 0 to 3, 11 are each independently a single bond or a divalent organic group; R 10 are each independently a hydrogen atom or a monovalent organic group; each t is independently an integer of 2 or more; R 14 are each independently a hydrogen atom, a halogen atom, or -X 11 -Si(R 2 ) n81 L 3-n81 and R 15 are each independently a single bond, an oxygen atom, an alkylene group having 1 to 6 carbon atoms, or an alkyleneoxy group having 1 to 6 carbon atoms; R a1 are each independently -Z 81 -SiR 21 p81 L q81 R 23 r81 and Z 81 are each independently a divalent organic group; R 21 are each independently -Z 1’ -SiR 21’ p1’ L q1’ R 23’ r1’ and R 23 are each independently a monovalent organic group; p81 is each independently an integer of 0 to 3; q81 is each independently an integer of 0 to 3; r81 is each independently an integer of 0 to 3; p81 + q81 + r81 is 3; Z 1’ are each independently a divalent organic group; R 21’ are each independently -Z 1” -SiL q1” R 23” r1” and R 23’ are each independently a monovalent organic group; each p1' is independently an integer of 0 to 3; each q1' is independently an integer of 0 to 3; each r1' is independently an integer of 0 to 3; p1' + q1' + r1' is 3; Z 1”are each independently a divalent organic group; R 23” are each independently a monovalent organic group; q1" is each independently an integer of 0 to 3; r1" is each independently an integer of 0 to 3; q1"+r1" is 3; R c1 are each independently a monovalent organic group; k81 is each independently an integer of 0 to 3; l81 is each independently an integer of 0 to 3; m81 is each independently an integer of 0 to 3; k81 + l81 + m81 is 3; R d1 are each independently -Z 82 -CR 71 p82 R 72 q82 R 73 r82 and Z 82 are each independently a single bond, an oxygen atom, or a divalent organic group; R 71 are each independently -Z 2’ -CR 32’ q2’ R 33’ r2’ and R 72 are each independently -Z 83 -SiL n82 R 35 3-n82 and R 73 are each independently a hydrogen atom, a hydroxyl group or a monovalent organic group; p82 is each independently an integer of 0 to 3; q82 is each independently an integer of 0 to 3; r82 is each independently an integer of 0 to 3; p82 + q82 + r82 is 3; Z 2’ are each independently a single bond, an oxygen atom, or a divalent organic group; R 32’ are each independently -Z 83 -SiL n82 R 35 3-n82 and R 33’are each independently a hydrogen atom, a hydroxyl group, or a monovalent organic group; q2' are each independently an integer of 0 to 3; r2' are each independently an integer of 0 to 3; q2'+r2' is 3; Z 83 are each independently a single bond, an oxygen atom, or a divalent organic group; R 35 are each independently a monovalent organic group; n82 are each independently an integer of 0 to 3; R e1 are each independently -Z 83 -SiL n82 R 35 3-n82 and R f1 are each independently a hydrogen atom, a hydroxyl group, or a monovalent organic group; k82 is each independently an integer of 0 to 3; l82 is each independently an integer of 0 to 3; m82 is each independently an integer of 0 to 3. k82 + l82 + m82 is 3; R g1 and R h1 are each independently -Z 84 -SiL n81 R 2 3-n81 , -Z 84 -SiR a1 k81 L l81 R c1 m81 , or -Z 84 -CR d1 k82 R e1 l82 R f1 m82 and Z 84 are each independently a single bond, an oxygen atom, or a divalent organic group; provided that in formulae (W1), (W2), (W3), and (W4), there are at least two Si atoms bonded to a hydrolyzable group, a group having a hydrolyzable group, or a hydroxyl group. 2 and L is R in the above formula (S1). 2 and L.
[0226] - (R 50 ) p5 -(X 51 ) q5-...(W5) In formula (W5), R 50 is a single bond, -(CH 2 ) s5 - or an o-, m- or p-phenylene group, s5 is an integer of 1 to 20, X 51 is -(X 52 ) l5 - and X 52 each occurrence independently represents an —O—, —S—, o-, m-, or p-phenylene group, —CO—, —C(O)O—, or —CONR 54 --, --O-CONR 54 -, -NR 54 - and - (CH 2 ) n5 - is a group selected from the group consisting of R 54 is independently in each occurrence a hydrogen atom or a monovalent organic group, n5 is independently in each occurrence an integer from 1 to 20, l5 is an integer from 1 to 10, p5 is 0 or 1, q5 is 0 or 1, at least one of p5 and q5 is 1, (R 50 ) p5 and (X 51 ) q5 The order in which they exist is arbitrary.
[0227] X A are each independently a single bond, an alkylene group having 1 to 20 carbon atoms, or —(CH 2 ) s5 -X 53 -, -X 53 - (CH 2 ) t5 - or -(CH 2 ) s5 -X 53 - (CH 2 ) t5 Preferably, X is -. 53 represents a single bond, —O—, —CO—, or —CONR 54 --, --O-CONR 54 -, -O-(CH 2 ) u5 -CONR 54 -, or -O-(CH 2 ) u5 -CO-, and R54 are each independently a hydrogen atom, a phenyl group, an alkyl group having 1 to 6 carbon atoms, or an oxyalkylene-containing group having 1 to 10 carbon atoms, s5 is an integer of 1 to 20, t5 is an integer of 1 to 20, and u5 is an integer of 1 to 20.
[0228] Compound (5) A compound represented by the following formula (5):
[0229]
[0230] In formula (5), Y is a single bond or *-Si(R s2 ) 2 -L s1 -. * represents a bond to an oxygen atom. Z represents an oxygen atom or a divalent hydrocarbon group having 1 to 10 carbon atoms. R a9 each independently represents a hydrocarbon group or a trialkylsilyloxy group. a9 When all of are hydrocarbon groups, R a9 The hydrocarbon group represented by R is an alkyl group. s1 , R s2 each independently represents an alkyl group having 1 to 10 carbon atoms. s1 represents a divalent hydrocarbon group having 1 to 10 carbon atoms. X represents a group represented by any one of the following formulas (X-1) to (X-3). n9 represents a number from 1 to 150.
[0231]
[0232] In formulas (X-1) to (X-3), L x1 and L x2 each independently represents a divalent hydrocarbon group having 1 to 20 carbon atoms, and the methylene group (—CH 2 -) is -O- or -O-Si(R x7 ) 2 - may be replaced by R x1 ~R x7 each independently represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms. a1 each independently represents a hydrolyzable group, a group having a hydrolyzable group, or a trialkoxysilyloxy group.a2 each independently represents a trialkylsilyl-containing group, a hydrocarbon chain-containing group, a siloxane skeleton-containing group, a hydrolyzable group, a group having a hydrolyzable group, or a trialkoxysilyloxy group; X a2 When is a hydrolyzable group, X a2 and X a1 may be the same or different. n2 represents an integer of 1 to 50. n3 represents a number of 2 to 5. n4 represents a number of 0 to 5. In formula (X-3), (Si(R x4 ) (-L x2 -Si(X a2 ) (X a1 ) 2 )—O—) and (Si(R x5 ) (R x6 The units represented by (a)-(O)-) may be in any order.
[0233] Compounds (1) to (5) will be explained below.
[0234] <Compound (1)> Compound (1) is preferably a compound represented by the following formula (1A): [T 1 3 M 1 -(O) r -Z 1 ] p1 A(Si(R 2 ) n L 3-n ) q1 ... (1A) In formula (1A), M 1 is Si, Sn, or Ge, and T 1 are each independently a hydrocarbon group or a trialkylsilyloxy group, r is 0 or 1, and Z 1 are each independently an alkylene chain or a polyalkylene oxide chain, or a combination of an alkylene chain and a divalent linear organo(poly)siloxane residue, A is a single bond or a (p1+q1)-valent linking group, R 2are each independently a monovalent hydrocarbon group, L is each independently a hydrolyzable group, a group having a hydrolyzable group, or a hydroxyl group, n is each independently an integer of 0 to 2, and p1 and q1 are each independently an integer of 1 or more, provided that Z 1 are each independently an alkylene chain or a polyalkylene oxide chain, A is a (p1+q1)-valent linking group containing a linear organo(poly)siloxane residue.
[0235] T 1 and M 1 represents T in the above group 1a 1 and M 1 Since it is the same as 1 is preferably Si. 1 is preferably a trialkylsilyloxy group, more preferably a butyldimethylsilyloxy group, a trimethylsilyloxy group or a triethylsilyloxy group. 2 , L, and n are R in the above formula (S1). 2 , L, and n. 1 The combination of an alkylene chain and a divalent linear organo(poly)siloxane residue represented by the formula (D3), (D4), or (D5) below is preferred.
[0236]
[0237] In formula (D3), Ak 1 and Ak 2 Each independently represents an alkylene chain. 3 is R in formula (B1). 3 k11 is a number of 1 or more. k12 is 0 or 1. In formula (D4), Ak 3 means an alkylene chain. 3 is R in formula (B1). 3 k21 and k22 are each independently a number of 1 or more. In formula (D5), Ak 4 means an alkylene chain. 3 is R in formula (B1). 3In formula (D3), (D4), or (D5), *1 is linked to the group 1a side, and *2 is linked to the group 1b side.
[0238] A may be any group as long as it does not impair the effects of the present disclosure, and examples thereof include alkylene groups which may have an etheric oxygen atom or a divalent linear organo(poly)siloxane residue, carbon atoms, nitrogen atoms, silicon atoms, divalent to octavalent organo(poly)siloxane residues, and Si(R 2 ) n L 3-n A may include a triptycene structure. The triptycene structure refers to a partial structure in which two or more hydrogen atoms have been removed from triptycene.
[0239] Furthermore, A may be any of the above groups (g2-1) to (g2-14).
[0240] p1 is an integer of 1 or more. In order to improve the water repellency of the surface treatment layer, p1 is preferably 1 to 6, and more preferably 2 to 4. p1 may be 1.
[0241] When p1 is 2 or more, a plurality of [T 1 3 M 1 -(O) r -Z 1 ] may be the same or different from each other.
[0242] q1 is an integer of 1 or more. In order to provide a surface treatment layer with better abrasion resistance, q1 is preferably 1 to 15, more preferably 1 to 6, even more preferably 2 to 6, particularly preferably 2 to 4, and extremely preferably 2 or 3. q1 may be 1.
[0243] When q1 is 2 or more, a plurality of [Si(R 2 ) n L 3-n ] may be the same or different from each other.
[0244] The group A (Si(R2 ) n L 3-n ) q1 A preferred embodiment of the present invention is a group A(Si(R 2 ) n L 3-n ) q1 However, the preferred embodiments of the group A(Si(R 2 ) n L 3-n ) q1 A in formula (1A) is [T 1 3 M 1 -(O) r -Z 1 ] p1 Connect to Z 1 When the terminal of the side bonded to A is an alkylene chain, Z of A 1 The end of the bonded side to Z is not an alkylene chain. 1 When the terminal of the side bonded to A is a polyalkylene oxide chain, Z of A 1 The end of the side that is bonded to the alkylene group is not a polyalkylene oxide chain.
[0245] The compound (1) is preferably a compound represented by the following formula (1B):
[0246]
[0247] In formula (1B), T 1 is T in group 1a 1 It is the same as R 3 is R in formula (B1). 3 k31 is the same as k31 in formula (D5). A(Si(R 2 ) n L 3-n ) q1 is the group represented by A(Si(R 2 ) n L 3-n ) q1 Ak is the same as the group represented by 4 is A in formula (D5) 4 is the same as
[0248] The compound (1) is preferably a compound represented by the following formula (1C), formula (1D), or formula (1E).
[0249]
[0250]
[0251]
[0252] In formula (1C), formula (1D), and formula (1E), R 3 is R in formula (B1). 3 k31 is the same as k31 in formula (D5). A(Si(R 2 ) n L 3-n ) q1 is the group represented by A(Si(R 2 ) n L 3-n ) q1 Ak is the same as the group represented by 4 is A in formula (D5) 4 is the same as
[0253] Specific examples of compound (1) include the following compounds:
[0254] In the following formula, n10 is a number of 1 or more, and n10 is preferably a number of 1 to 60, may be a number of 3 to 50, may be a number of 5 to 30, or may be a number of 7 to 25.
[0255]
[0256] In the following formula, k is preferably 1 to 80, more preferably 3 to 50, and even more preferably 3 to 30. m is preferably 1 to 30, more preferably 3 to 20, and even more preferably 3 to 10. t is preferably 1 to 30, more preferably 3 to 20, and even more preferably 3 to 10. In the following formula, n10 is a number of 1 or more, and n10 is preferably a number of 1 to 60, but may be a number of 3 to 50, a number of 5 to 30, or a number of 7 to 25.
[0257]
[0258] In the following formula, n10 is a number of 1 or more, and n10 is preferably a number of 1 to 60, may be a number of 3 to 50, may be a number of 5 to 30, or may be a number of 7 to 25.
[0259]
[0260] <Compound (2)> In compound (2), the alkyl group means an unsubstituted alkyl group. The alkyl group may be any of a linear alkyl group, a branched alkyl group, and a cyclic alkyl group, but a linear alkyl group or a branched alkyl group is preferred. The alkyl group preferably has 2 to 30 carbon atoms, more preferably 3 to 28 carbon atoms, and even more preferably 4 to 22 carbon atoms. The compound may contain only one alkyl group, or two or more alkyl groups. Since the alkyl group is a monovalent group, it is located at the terminal of the compound.
[0261] The compound (2) is preferably a compound represented by the following formula (2A): (T 2 -Z 2 ) p1 A(Si(R 2 ) n L 3-n ) q1 ... (2A) In formula (2A), T 2 is an alkyl group having two or more carbon atoms; Z 2 is a divalent chain organo(poly)siloxane residue, A is a single bond or a (p1+q1)-valent linking group, R 2 are each independently a monovalent hydrocarbon group; each L is independently a hydrolyzable group, a group having a hydrolyzable group, or a hydroxyl group; n is an integer of 0 to 2; and p1 and q1 are each independently an integer of 1 or greater.
[0262] T 2 Preferred embodiments of the alkyl group having 2 or more carbon atoms represented by the formula: are as described above. 2 The divalent chain organo(poly)siloxane residue represented by the formula (B1) is preferably a group represented by the formula (B1). 2 , L, and n are R in the above formula (S1). 2, L, and n. A(Si(R 2 ) n L 3-n ) q1 In addition to the contents shown below, the group represented by A(Si(R 2 ) n L 3-n ) q1 p1 and q1 are the same as p1 and q1 in the above formula (1A).
[0263] A(Si(R 2 ) n L 3-n ) q1 The group represented by the formula (3-1A) is preferably the group (3-1A) or the group (3-1B), and more preferably the group (3-1A). a is a single bond or a divalent linking group. a Z 2 The end of the bonded side is not an oxysilyl group.
[0264] In formula (3-1A), X 31 is a single bond, an alkylene group, a carbon atom, a nitrogen atom, a silicon atom, a divalent to octavalent organo(poly)siloxane residue, or a group having a (h+i+1)-valent ring. a When is a single bond, X 31 Z 2 The terminal on the side bonding to X is not an oxysilyl group. 31 may be terminated with an oxysilyl group.
[0265] In formula (3-1A), Q b is a single bond or a divalent linking group. a and X 31 If is a single bond, Q b Z 2 The terminal of the bonded side is not an oxysilyl group. b The terminal of may be an oxysilyl group. b When Q is an alkylene group, a -X 31 Q b The side terminal is not an alkylene group.
[0266] In formula (3-1B), Q c is a single bond or a divalent linking group. c Z 2 The end of the bonded side is not an oxysilyl group.
[0267] As the group (3-1A), groups (3-1A-1) to (3-1A-7) are preferred. However, Z 2 The end of the bonded side is not an oxysilyl group.
[0268] In the group (3-1A-1), X 32 is -O-, -S-, -N(R d )-, -C(O)O-, -C(O)S-, -N(R d )C(O)N(R d )-,-OC(O)N(R d )-, or -C(O)N(R d )- is preferred, and —C(O)O— or —C(O)N(R d )- is more preferred. s1 is preferably 0, and Q b1 is preferably an alkylene group having 2 to 6 carbon atoms.
[0269] In the group (3-1A-2), X 33 is —O—, —C(O)O—, or —C(O)N(R d )- is preferred.
[0270] A in formula (2A) may be any of groups (g2-1) to (g2-7).
[0271] However, in formulas (g2-1) to (g2-7), A 1 Side is Z 2 and Q 22 , Q 23 , Q 24 , Q 25 or Q 26 The side is [-Si(R 2 ) n L 3-n ] and combine.
[0272] Other embodiments of A include groups (g2-8) to (g2-14).
[0273] However, in formulas (g2-8) to (g2-14), A 1 Side is Z 2 and binds to G 1 The side is [-Si(R 2 ) n L 3-n ] and combine.
[0274] The compound (2) is preferably a compound represented by the following formula (2B):
[0275] In formula (2B), R 51 is an alkyl group having two or more carbon atoms. 52 and R 54 are each independently an alkylene group. 53 is -C(O)O-, -SO 2 N (R d ) -, -N(R d ) SO 2 -, -N(R d )C(O)- or -C(O)N(R d )-. R 3 is R in formula (B1). 3 k1 is the same as k1 in formula (B1). X 31 (-Q b -Si(R 2 ) n L 3-n ) h (-R 31 ) i is X in group (3-1A). 31 (-Q b -Si(R 3 ) n L 3-n ) h (-R 31 ) i t1 is 0 or 1.
[0276] R 51 Preferred embodiments of the alkyl group represented by the formula (I) are as explained above in the section on alkyl groups. 52The alkylene group represented by the formula (I) may be linear, branched, or cyclic. The alkylene group preferably has 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, even more preferably 4 to 20 carbon atoms, and particularly preferably 5 to 15 carbon atoms. 54 The alkylene group represented by the formula (I) may be linear, branched, or cyclic. The alkylene group preferably has 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, even more preferably 1 to 6 carbon atoms, and particularly preferably 1 to 3 carbon atoms.
[0277] Examples of compound (2) include the following compounds: In the following formula, n10 is a number of 1 or more, and n10 is preferably a number of 1 to 60, may be a number of 3 to 50, may be a number of 5 to 30, or may be a number of 7 to 25.
[0278]
[0279]
[0280]
[0281]
[0282]
[0283] <Compound (3)> Compound (3) is preferably a compound represented by the following formula (3A): [T 3 -(O) r -Z 3 ] p1 A(Si(R 2 ) n L 3-n ) q1 ...(3A) In formula (3A), T 3 is a monovalent cyclic polysiloxane residue or a monovalent cage-like polysiloxane residue, r is 0 or 1, Z 3 is a divalent linear organo(poly)siloxane residue or a combination of a divalent linear organo(poly)siloxane residue and at least one of an alkylene chain and a polyalkylene oxide chain, A is a single bond or a (p1+q1)-valent linking group, R 2are each independently a monovalent hydrocarbon group; each L is independently a hydrolyzable group, a group having a hydrolyzable group, or a hydroxyl group; n is an integer of 0 to 2; and p1 and q1 are each independently an integer of 1 or greater.
[0284] R 2 , L, and n are R in the above formula (S1). 2 , L, and n. A(Si(R 2 ) n L 3-n ) q1 In addition to the contents shown below, the group represented by A(Si(R 2 ) n L 3-n ) q1 p1 and q1 are the same as p1 and q1 in the above formula (1A).
[0285] The details of the monovalent cyclic polysiloxane residue or the monovalent cage-like polysiloxane residue are as follows: T 11 This is as described above in the description of the first embodiment.
[0286] A(Si(R 2 ) n L 3-n ) q1 The group represented by the formula (3-1A) is preferably the group (3-1A) or the group (3-1B), and more preferably the group (3-1A).
[0287] In formula (3-1A), Q a is a single bond or a divalent linking group. a Z 3 The terminal on the side bonding to Z is not an alkylene group, a polyalkylene oxide chain, or a divalent organo(poly)siloxane residue. 3 When the A-side terminal of is an alkylene chain, Q a represents a divalent hydrocarbon group other than an alkylene group, a divalent heterocyclic group, —O—, —S—, —SO 2 -, -N(R d )-, -C(O)-, -Si(R a ) 2 -, -OC(O)-, -C(O)O-, -C(O)S-, -C(O)N(R d) -, -N(R d )C(O)-,-N(R d )C(O)N(R d ) -, -N(R d )C(O)O-, -OC(O)N(R d ) -, -SO 2 N (R d ) -, -N(R d ) SO 2 -, -C(O)N(R d an alkylene group having —N(R d )C(O)-, an alkylene group having —OC(O)N(R d an alkylene group having —OC(O)—, an alkylene group having —C(O)O—, an alkylene group having —C(O)S—, an alkylene group having —N(R d an alkylene group having —N(R d )C(O)N(R d )- or -SO 2 N (R d )- is preferred, and an alkylene group having —OC(O)—, —C(O)N(R d )-, an alkylene group having —OC(O)N(R d an alkylene group having —C(O)O—, an alkylene group having —C(O)S—, an alkylene group having —N(R d an alkylene group having —N(R d )C(O)N(R d An alkylene group having —C(O)O— or —C(O)N(R d Alkylene groups having Z are more preferred. 3 When the A-side terminal of Q is a polyalkylene oxide chain, a represents a divalent hydrocarbon group other than an alkylene group, a divalent heterocyclic group, or —SO 2 -, -C(O)-, -Si(R a ) 2 -, -C(O)O-, -C(O)S-, -C(O)N(R d ) -, -SO2 N (R d )-, -C(O)N(R d an alkylene group having —C(O)O—, or —SO 2 N (R d An alkylene group having —C(O)— is preferred, and —C(O)— is more preferred. 3 When the A-terminal of Q is a divalent linear organo(poly)siloxane residue, a represents a divalent hydrocarbon group other than an alkylene group, a divalent heterocyclic group, —O—, —S—, —SO 2 -, -N(R d )-, -C(O)-, -Si(R a ) 2 -, -OC(O)-, -C(O)O-, -C(O)S-, -C(O)N(R d ) -, -N(R d )C(O)-,-N(R d )C(O)N(R d ) -, -N(R d )C(O)O-, -OC(O)N(R d ) -, -SO 2 N (R d ) -, -N(R d ) SO 2 -, -C(O)N(R d an alkylene group having —N(R d )C(O)-, an alkylene group having —OC(O)N(R d an alkylene group having —OC(O)—, an alkylene group having —C(O)O—, an alkylene group having —C(O)S—, an alkylene group having —N(R d an alkylene group having —N(R d )C(O)N(R d )- or -SO 2 N (R d )-containing alkylene groups are preferred.
[0288] In formula (3-1A), X 31is a single bond, an alkylene group, a carbon atom, a nitrogen atom, a silicon atom, a divalent to octavalent organo(poly)siloxane residue, or a group having a (h+i+1)-valent ring. a When is a single bond, X 31 Z 3 The terminal on the side bonding to X is not an alkylene group, a polyalkylene oxide chain, or a divalent organo(poly)siloxane residue. 31 The terminal of the alkylene group may be any of an alkylene group, a polyalkylene oxide chain, and a divalent organo(poly)siloxane residue.
[0289] In formula (3-1A), Q b is a single bond or a divalent linking group. a and X 31 If is a single bond, Q b Z 3 The terminal on the side bonding to Q is not an alkylene group, a polyalkylene oxide chain, or a divalent organo(poly)siloxane residue. b The terminal of the alkylene group may be any of an alkylene group, a polyalkylene oxide chain, and a divalent organo(poly)siloxane residue.
[0290] In formula (3-1A), Q a , X 31 , and Q b is a single bond, [Si(R 2 ) n L 3-n ] is Z 3 directly bonded to Z 3 is an alkylene chain.
[0291] In formula (3-1B), Q c is a single bond or a divalent linking group. c Z 3 The terminal on the side bonding to is not an alkylene group, a polyalkylene oxide chain, or a divalent organo(poly)siloxane residue.
[0292] As the group (3-1A), groups (3-1A-1) to (3-1A-7) are preferred. However, Z 3The terminal on the side bonding to is not an alkylene group, a polyalkylene oxide chain, or a divalent organo(poly)siloxane residue.
[0293] In the group (3-1A-1), Z 3 When the A-side terminal of X is an alkylene chain, 32 is -O-, -S-, -N(R d )-, -C(O)-, -C(O)O-, -C(O)S-, -SO 2 N (R d ) -, -N(R d ) SO 2 -, -N(R d )C(O)-,-N(R d )C(O)N(R d )-,-OC(O)N(R d )- or -C(O)N(R d )- is preferred, and —O—, —S—, —N(R d )-, -C(O)O-, -C(O)S-, -N(R d )C(O)-,-N(R d )C(O)N(R d )-,-OC(O)N(R d )-, or -C(O)N(R d )- is more preferred, and —C(O)O— or —N(R d )C(O)- is more preferred. 3 When the A-side terminal of X is a polyalkylene oxide chain, 32 is -C(O)-, -C(O)O-, -C(O)S-, -SO 2 N (R d )-, or -C(O)N(R d )- is preferred, and —C(O)- is more preferred. 3 When the A-side terminal of X is a divalent linear organo(poly)siloxane residue, 32 is -O-, -S-, -N(R d )-, -C(O)-, -C(O)O-, -C(O)S-, -SO 2 N (R d ) -, -N(R d ) SO 2 -, -N(R d )C(O)-,-N(R d )C(O)N(Rd )-,-OC(O)N(R d )-, or -C(O)N(R d )- is preferred, and -O- is more preferred.
[0294] Z 3 When the A-side terminal of is an alkylene chain, s1 is 0, and Q b1 is a single bond, or s1 is 1 and Q b1 is preferably an alkylene group having 2 to 6 carbon atoms. 3 When the A-side terminal of is a polyalkylene oxide chain, s1 is 1, and Q b1 is preferably an alkylene group having 2 to 6 carbon atoms. 3 When the A-side terminal of is a divalent chain organo(poly)siloxane residue, s1 is 1, and Q b1 is preferably a single bond.
[0295] In the group (3-1A-2), Z 3 When the A-side terminal of X is an alkylene chain or a divalent linear organo(poly)siloxane residue, 33 is -O-, -S-, -N(R d )-, -C(O)-, -C(O)O-, -C(O)S-, -SO 2 N (R d ) -, -N(R d ) SO 2 -, -N(R d )C(O)-,-N(R d )C(O)N(R d )-,-OC(O)N(R d )- or -C(O)N(R d )- is preferred. 3 When the A-side terminal of X is a polyalkylene oxide chain, 33 is -C(O)O-, -C(O)S-, -SO 2 N (R d )-, or -C(O)N(R d )- is preferred.
[0296] A in formula (3A) may be any of groups (g2-1) to (g2-7).
[0297] However, in formulas (g2-1) to (g2-7), A 1 Side is Z 3 and Q 22 , Q 23 , Q 24 , Q 25 or Q 26 The side is [-Si(R 2 ) n L 3-n ] and combine.
[0298] Other embodiments of A include groups (g2-8) to (g2-14).
[0299] However, in formulas (g2-8) to (g2-14), A 1 Side is Z 3 and binds to G 1 The side is [-Si(R 2 ) n L 3-n ] and combine.
[0300] Specific examples of compound (3) include the following compounds: In the following formula, n10 is a number of 1 or more, and is preferably a number from 1 to 60, and may be a number from 3 to 50, a number from 5 to 30, or a number from 7 to 25.
[0301]
[0302] <Compounds (4A) and (4B)> In the compounds (4A) and (4B), X A are each independently -(CH 2 ) s7 -O-(CH 2 ) t7 -, -(CH 2 ) s7 -CONR 54 - (CH 2 ) t7 -, -(CH 2 ) s7 -O-(CH 2 ) u7 -CO-, or -(CH 2 ) s7 -O-(CH 2 ) u7 -CONR 54 - (CH 2 )t7 It is more preferable that -.
[0303] R 54 are each independently a hydrogen atom, a phenyl group, an alkyl group having 1 to 6 carbon atoms, or an oxyalkylene-containing group having 1 to 10 carbon atoms; s7 is an integer of 1 to 20; t7 is an integer of 1 to 20; and u7 is an integer of 1 to 20.
[0304] X A are each independently a group represented by the following formula (W6): a are each independently a single bond or a divalent organic group.
[0305]
[0306] Specific examples of the compound (4A) include the following compounds: (CH 3 ) 3 Si-(OSi(CH 3 ) 2 ) 19 - (CH 2 ) 10 -CONH-CH 2 C{CH 2 CH 2 CH 2 Si(OCH 3 ) 3} 3
[0307] <Compound (5)> When the surface treatment agent of the present disclosure contains compound (5), it is preferable that the surface treatment agent of the present disclosure further contains a metal compound.
[0308] The metal compound is preferably a compound represented by the following formula (M6a) or (M6b).
[0309]
[0310] In formula (M6a), R k1 represents a siloxane skeleton-containing group, a hydrocarbon chain-containing group, or a hydrolyzable group; k1 each independently represents a hydrolyzable group. k2represents a siloxane skeleton-containing group, a hydrocarbon chain-containing group, or a hydrolyzable group. k1 and X k1 The number of elements in the siloxane skeleton-containing group is (R a9 ) 3 Si-Z-(Si(R s1 ) 2 -O-) n9 The number of elements in the trialkylsilyl group-containing molecular chain represented by -Y- is less than the number of elements in the trialkylsilyl group-containing molecular chain represented by R k1 and X k1 The number of carbon atoms in the longest linear hydrocarbon chain contained in the hydrocarbon chain-containing group in the compound (5) is a9 ) 3 Si-Z-(Si(R s1 ) 2 -O-) n9 The number of elements is less than the number of elements in the trialkylsilyl group-containing molecular chain represented by -Y-. k1 and X k2 is a siloxane skeleton-containing group or a hydrocarbon chain-containing group, R k1 and X k2 may be the same or different. k2 When is a hydrolyzable group, X k2 and X k1 may be the same or different. k1 and X k2 may be the same or different. 4 represents a trivalent or tetravalent metal atom capable of forming a metal alkoxide. 4 represents an integer of 0 or 1 depending on the
[0311]
[0312] In formula (M6b), R k3 represents a hydrolyzable silane oligomer residue, and X k3 represents a hydrolyzable group, a fluorine-containing alkyl group having 1 to 4 carbon atoms, or an alkyl group having 1 to 4 carbon atoms.
[0313] Specific examples of compound (5) include the following compounds: In the following formula, n10 is a number of 1 or more, and is preferably a number from 1 to 60, and may be a number from 3 to 50, a number from 5 to 30, or a number from 7 to 25.
[0314]
[0315] [Liquid Medium] The composition of the present disclosure may contain a liquid medium. The liquid medium may be one type only, or two or more types.
[0316] The liquid medium is preferably an organic solvent. Examples of organic solvents include compounds consisting only of hydrogen atoms and carbon atoms, and compounds consisting only of hydrogen atoms, carbon atoms, and oxygen atoms. Specific examples include hydrocarbon organic solvents, ketone organic solvents, ether organic solvents, ester organic solvents, glycol organic solvents, and alcohol organic solvents. 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. Specific examples of ketone-based 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, 3,3,5-trimethylcyclohexanone, and isophorone.Specific examples of ether-based organic solvents include diethyl ether, cyclopentyl methyl ether, tetrahydrofuran, and 1,4-dioxane.Specific examples of the ester-based organic solvent 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, ethylene glycol monoethyl ether acetate, ethylene glycol monomethyl ether acetate, diethylene glycol Cholesterol monoethyl ether acetate, cyclohexanol acetate, propylene glycol diacetate, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether propionate, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether acetate, propylene glycol monopropyl ether acetate, dipropylene glycol methyl ether acetate, 1,3-butylene glycol diacetate, 1,4-butanediol diacetate, 1,3-butylene glycol diacetate, 1,6-hexanediol diacetate, γ-butyrolactone, triacetin, and 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate.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 mono-tert-butyl ether, ethylene glycol monopropyl ether, ethylene glycol monomethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monobutyl ether, and dipropylene glycol monopropyl ether. Examples of the glycol monopropyl ether include dipropylene glycol monomethyl ether, tripropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, propylene glycol monophenyl ether, 1,3-butylene glycol, propylene glycol n-propyl ether, propylene glycol n-butyl ether, diethylene glycol monoethyl ether, dipropylene glycol n-propyl ether, dipropylene glycol n-butyl ether, tripropylene glycol methyl ether, tripropylene glycol n-butyl 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, dipropylene glycol dimethyl ether pentane, triethylene glycol dimethyl ether, and polyethylene glycol dimethyl ether.Specific examples of alcohol-based 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.
[0317] Examples of the organic solvent include halogen-based organic solvents, nitrogen-containing compounds, sulfur-containing compounds, siloxane compounds, and fluorine-containing organic solvents.
[0318] Specific examples of halogen-based organic solvents include dichloromethane, chloroform, carbon tetrachloride, dichloroethane, chlorobenzene, o-chlorotoluene, m-chlorotoluene, p-chlorotoluene, m-dichlorobenzene, and 1,2,3-trichloropropane.
[0319] Examples of the nitrogen-containing compound include nitrobenzene, acetonitrile, benzonitrile, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, and 1,3-dimethyl-2-imidazolidinone.
[0320] Examples of sulfur-containing compounds include carbon disulfide and dimethyl sulfoxide.
[0321] Examples of the siloxane compound include hexamethyldisiloxane, hexaethyldisiloxane, octamethyltrisiloxane, octaethyltrisiloxane, hexamethylcyclotrisiloxane, hexaethylcyclotrisiloxane, octamethylcyclotetrasiloxane, octaethylcyclotetrasiloxane, and decamethyltetrasiloxane.
[0322] Examples of the fluorine-containing organic solvent include polyfluoroaromatic hydrocarbons (e.g., 1,3-bis(trifluoromethyl)benzene); polyfluoroaliphatic hydrocarbons (e.g., C 6 F 13 CH 2 CH 3 (e.g., Asahiklin (registered trademark) AC-6000 manufactured by AGC Corporation), 1,1,2,2,3,3,4-heptafluorocyclopentane (e.g., Zeorora (registered trademark) H manufactured by Zeon Corporation); hydrofluoroethers (HFEs) (e.g., perfluoropropyl methyl ether (C 3 F 7 OCH 3 ) (e.g., Novec™ 7000 manufactured by Sumitomo 3M Limited), perfluorobutyl methyl ether (C 4 F 9 OCH 3 ) (e.g., Novec (trademark) 7100 manufactured by Sumitomo 3M Limited), perfluorobutyl ethyl ether (C 4 F 9 O.C. 2 H 5 ) (e.g., Novec (trademark) 7200 manufactured by Sumitomo 3M Limited), perfluorohexyl methyl ether (C 2 F 5 CF (OCH 3 ) C 3 F 7 ) (e.g., Novec™ 7300 manufactured by Sumitomo 3M Limited) and other alkyl perfluoroalkyl ethers (the perfluoroalkyl group and the alkyl group may be linear or branched), CF 3 CH 2 OCF 2 CHF 2(e.g., Asahiklin (registered trademark) AE-3000 manufactured by AGC Corporation); and hydrofluoroolefins (HFOs) (e.g., 1-chloro-2,3,3-trifluoro-1-propene (HCFO-1233yd) (e.g., Amorea (registered trademark) AS-300 manufactured by AGC Corporation), Opteon (registered trademark) SF01, SF05, SF10, SF30, SF33, SF70, SF79, SF80 manufactured by Chemours).
[0323] The content of the liquid medium is preferably 50 to 99.999 mass%, more preferably 80 to 99.99 mass%, and even more preferably 90 to 99.9 mass%, based on the total amount of the composition of the present disclosure. In the case of a composition of the present disclosure used in a wet coating method, the content of the liquid medium may be 90 to 99.99 mass%, 95 to 99.98 mass%, 97 to 99.97 mass%, or 98 to 99.95 mass%, based on the total amount of the composition of the present disclosure.
[0324] [Other Components] The composition of the present disclosure may contain other components in addition to the liquid medium, as long as the effects of the present disclosure are not impaired. Examples of other components include known additives such as acid catalysts and basic catalysts that promote the hydrolysis and condensation reaction of reactive silyl groups.
[0325] The catalyst may be any appropriate acid or base, transition metal (e.g., Ti, Ni, Sn, Zr, Al, B, etc.), sulfur-containing compounds having an unshared electron pair in their molecular structure, nitrogen-containing compounds (e.g., sulfoxide compounds, aliphatic amine compounds, aromatic amine compounds, phosphoric acid amide compounds, amide compounds, urea compounds), etc. Examples of acid catalysts include acetic acid, formic acid, trifluoroacetic acid, hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, sulfonic acid, methanesulfonic acid, and p-toluenesulfonic acid. Examples of base catalysts include ammonia, sodium hydroxide, potassium hydroxide, and organic amines such as triethylamine and diethylamine.
[0326] Other components also include metal compounds having a hydrolyzable group (hereinafter, metal compounds having a hydrolyzable group are also referred to as "specific metal compounds"). When the composition of the present disclosure contains a specific metal compound, the slip properties and antifouling properties of the surface treatment layer can be further improved. Examples of the specific metal compounds include those represented by the following formulas (M1) to (M3).
[0327] M (X b1 ) m11 (X b2 ) m12 (X b3 ) m13 ... (M1) Si (X b4 ) (X b5 ) 3 ... (M2) (X b6 ) 3 Si-(Y b1 )-Si(X b7 ) 3 …(M3)
[0328] In formula (M1), M represents a trivalent or tetravalent metal atom. b1 each independently represents a hydrolyzable group. b2 each independently represents a siloxane skeleton-containing group. b3 each independently represents a hydrocarbon chain-containing group, m11 is an integer of 2 to 4, m12 and m13 are each independently an integer of 0 to 2, when M is a trivalent metal atom, m11 + m12 + m13 is 3, and when M is a tetravalent metal atom, m11 + m12 + m13 is 4.
[0329] In formula (M2), X b4 represents a hydrolyzable silane oligomer residue. b5 each independently represents a hydrolyzable group or an alkyl group having 1 to 4 carbon atoms.
[0330] In formula (M3), X b6 and X b7 each independently represents a hydrolyzable group or a hydroxyl group. b1 represents a divalent organic group.
[0331] In formula (M1), the metal represented by M also includes semimetals such as Si and Ge. M is preferably a trivalent metal or a tetravalent metal, more preferably Al, Fe, In, Hf, Si, Ti, Sn, or Zr, still more preferably Al, Si, Ti, or Zr, and particularly preferably Si.
[0332] In formula (M1), X b1 The hydrolyzable group represented by the formula (I) is the reactive silyl group represented by the formula (I). 2 ) n L 3-n Examples of the hydrolyzable group include the same as the hydrolyzable group represented by L in the formula (1).
[0333] X b2 The siloxane skeleton-containing group represented by the formula (I) has a siloxane unit (—Si—O—) and may be linear or branched. Examples of the siloxane unit include a dialkylsilyloxy group, such as a dimethylsilyloxy group or a diethylsilyloxy group. The number of repeating siloxane units in the siloxane skeleton-containing group is 1 or more, preferably 1 to 5, more preferably 1 to 4, and even more preferably 1 to 3. The siloxane skeleton-containing group may contain a divalent hydrocarbon group as part of the siloxane skeleton. Specifically, some oxygen atoms in the siloxane skeleton may be replaced with a divalent hydrocarbon group. Examples of the divalent hydrocarbon group include alkylene groups such as methylene, ethylene, propylene, and butylene. A hydrolyzable group, a hydrocarbon group (preferably an alkyl group), or the like may be bonded to the terminal silicon atom of the siloxane skeleton-containing group. The number of elements in the siloxane skeleton-containing group is preferably 100 or less, more preferably 50 or less, and even more preferably 30 or less. The number of elements is preferably 10 or more. Examples of the siloxane skeleton-containing group include: * -(O-Si(CH 3 ) 2 ) n CH 3 In this case, n is an integer of 1 to 5, and * represents a bonding site with an adjacent atom.
[0334] X b3The hydrocarbon chain-containing group represented by the formula (I) may be a group consisting of only a hydrocarbon chain, or may be a group having an etheric oxygen atom between carbon atoms in the hydrocarbon chain. The hydrocarbon chain may be a straight chain or a branched chain, with a straight chain being preferred. The hydrocarbon chain may be a saturated hydrocarbon chain or an unsaturated hydrocarbon chain, with a saturated hydrocarbon chain being preferred. The number of carbon atoms in the hydrocarbon chain-containing group is preferably 1 to 3, more preferably 1 to 2, and even more preferably 1. The hydrocarbon chain-containing group is preferably an alkyl group, and more preferably a methyl group, an ethyl group, or a propyl group.
[0335] Preferably, m1 is 3 or 4.
[0336] As the compound represented by formula (M1), compounds represented by the following formulas (M1-1) to (M1-5) in which M is Si are preferred, and the compound represented by formula (M1-1) is more preferred. As the compound represented by formula (M1-1), tetraethoxysilane, tetramethoxysilane, and triethoxymethylsilane are preferred.
[0337] Si(X b1 ) 4 ... (M1-1) CH 3 -Si(X b1 ) 3 …(M1-2) C 2 H 5 -Si(X b1 ) 3 ...(M1-3) n-C 3 H 7 -Si(X b1 ) 3 ...(M1-4) (CH 3 ) 2 CH—Si(X b1 ) 3 …(M1-5)
[0338] In formula (M2), X b4The number of silicon atoms contained in the hydrolyzable silane oligomer residue represented by the formula (I) is preferably 3 or more, more preferably 5 or more, and even more preferably 7 or more. The number of silicon atoms is preferably 15 or less, more preferably 13 or less, and even more preferably 10 or less. The hydrolyzable silane oligomer residue may have an alkoxy group bonded to a silicon atom. Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, and a butoxy group, with a methoxy group and an ethoxy group being preferred. The hydrolyzable silane oligomer residue may have one or more of these alkoxy groups, and preferably has one type. Examples of the hydrolyzable silane oligomer residue include (C 2 H 5 O) 3 Si-(OSi(OC) 2 H 5 ) 2 ) 4 O- * Here, * represents a bonding site with an adjacent atom.
[0339] In formula (M2), X b5 The hydrolyzable group represented by the formula (I) is the reactive silyl group represented by the formula (I). 2 ) n L 3-n Examples of the hydrolyzable group include the same as the hydrolyzable group represented by L in the formula (1), a cyano group, a hydrogen atom, and an allyl group, and an alkoxy group or an isocyanato group is preferred. The alkoxy group is preferably an alkoxy group having 1 to 4 carbon atoms. X b5 As the group, a hydrolyzable group is preferred.
[0340] The compound represented by formula (M2) includes (H 5 C 2 O) 3 -Si-(OSi(OC) 2 H 5 ) 2 ) 4 O.C. 2 H 5 etc.
[0341] The compound represented by formula (M3) is a compound having reactive silyl groups at both ends of a divalent organic group, i.e., a bissilane. b6and X b7 Examples of the hydrolyzable group represented by formula (M3) include an alkoxy group, an acyloxy group, a ketoxime group, an alkenyloxy group, an amino group, an aminoxy group, an amide group, an isocyanato group, and a halogen atom, and an alkoxy group and an isocyanato group are preferred. As the alkoxy group, an alkoxy group having 1 to 4 carbon atoms is preferred, and a methoxy group and an ethoxy group are more preferred. In formula (M3), X b6 and X b7 may be the same group or different groups. b6 and X b7 are preferably the same group.
[0342] In formula (M3), Y b1 is a divalent organic group that connects the reactive silyl groups at both ends. b1 The number of carbon atoms in Y is preferably 1 to 8, and more preferably 1 to 3. b1 Examples of the alkylene group include an alkylene group, a phenylene group, and an alkylene group having an etheric oxygen atom between carbon atoms. 2 CH 2 -, -CH 2 CH 2 CH 2 -, -CH 2 CH 2 CH 2 CH 2 -, -CH 2 CH 2 CH 2 CH 2 CH 2 -, -CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 -, -CH 2 C(CH 3 ) 2 CH 2 -, -C(CH 3 ) 2 CH 2 CH 2 C(CH 3 ) 2 -, -CH 2 CH 2 OCH2 CH 2 -, -CH 2 CH 2 CH 2 OCH 2 CH 2 CH 2 -, -CH(CH 3 ) CH 2 OCH 2 CH (CH 3 ) -, -C 6 H 4 - are listed.
[0343] The compound represented by formula (M3) includes (CH 3 O) 3 Si(CH 2 ) 2 Si(OCH 3 ) 3 , (C 2 H 5 O) 3 Si(CH 2 ) 2 Si(OC 2 H 5 ) 3 , (OCN) 3 Si(CH 2 ) 2 Si(NCO) 3 , Cl 3 Si(CH 2 ) 2 SiCl 3 , (CH 3 O) 3 Si(CH 2 ) 6 Si(OCH 3 ) 3 , (C 2 H 5 O) 3 Si(CH 2 ) 6 Si(OC 2 H 5 ) 3 Examples include:
[0344] The content of other components that may be included in the composition of the present disclosure is preferably 10% by mass or less, and more preferably 1% by mass or less, relative to the total amount of the composition of the present disclosure. When the composition of the present disclosure contains a specific metal compound, the content of the specific 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, relative to the total amount of the composition of the present disclosure.
[0345] The total content of the first compound, the second compound, and other components (hereinafter also referred to as "solid content concentration") is preferably 0.001 to 40 mass%, more preferably 0.01 to 20 mass%, and even more preferably 0.1 to 10 mass%, relative to the total amount of the composition of the present disclosure. The solid content concentration of the composition of the present disclosure is a value calculated from the mass before heating and the mass after heating for 4 hours in a convection dryer at 120°C.
[0346] [Surface Treatment Agent] The surface treatment agent of the present disclosure comprises the composition of the present disclosure described above. The surface treatment agent of the present disclosure is applied to the surface of a substrate and used to form a surface treatment layer. Details of each component contained in the surface treatment agent are the same as details of each component contained in the composition. In one embodiment, the surface treatment agent of the present disclosure is preferably used to form an antifouling layer. In one embodiment, the surface treatment agent of the present disclosure is preferably used to form an antifouling layer to be formed on the outermost surface of an article.
[0347] [Article] In one embodiment, the article of the present disclosure includes a substrate and a surface treatment layer disposed on the substrate and surface-treated with the surface treatment agent of the present disclosure. In one embodiment, the surface treatment layer is preferably an antifouling layer. In one embodiment, the surface treatment layer is preferably an antifouling layer formed on the outermost surface of the article.
[0348] The surface treatment layer may be formed on a part of the surface of the substrate, or may be formed on the entire surface of the substrate. The surface treatment layer may be spread in the form of a film on the surface of the substrate, or may be scattered in the form of dots. In the surface treatment layer, the compound of the present disclosure is contained in a state in which hydrolysis of some or all of the reactive silyl groups has progressed and dehydration condensation reaction of the silanol groups has progressed.
[0349] The thickness of the surface treatment layer is preferably 1 to 100 nm, more preferably 1 to 50 nm. If the thickness of the surface treatment layer is 1 nm or more, the effect of the surface treatment is likely to be sufficient. If the thickness of the surface treatment layer is 100 nm or less, the utilization efficiency is high. The thickness of the surface treatment layer can be calculated from the oscillation period of the interference pattern obtained by X-ray reflectivity using a thin film analysis X-ray diffractometer (product name "ATX-G", manufactured by RIGAKU Corporation).
[0350] The type of substrate is not particularly limited, and examples thereof include substrates that are required to be water-repellent. Examples of substrates include substrates that may be used by contacting other articles (e.g., stylus) or human fingers; substrates that may be held by human fingers during operation; and substrates that may be placed on other articles (e.g., a mounting table). Examples of substrate materials include metal, resin, glass, sapphire, ceramic, semiconductor, stone, fiber, nonwoven fabric, paper, wood, fur, natural leather, artificial leather, ceramics, and composite materials thereof. Glass may be chemically strengthened.
[0351] Examples of the substrate include glass or resin used for building materials, decorative building materials, interior goods, transportation equipment (e.g., automobiles), signs, bulletin boards, drinking vessels, tableware, aquariums, ornamental equipment (e.g., frames, boxes), laboratory equipment, furniture, textile products, packaging containers, art, sports, games, etc., and glass or resin used for the exterior parts (excluding display parts) of devices such as mobile phones (e.g., smartphones), personal digital assistants, game consoles, remote controls, etc. The shape of the substrate may be a plate or a film.
[0352] The substrate is preferably a substrate for a touch panel, a substrate for a display, or a lens for glasses, and is particularly preferably a substrate for a touch panel.The material of the substrate for a touch panel is preferably glass or a transparent resin.
[0353] The substrate may be a substrate whose one or both surfaces have been subjected to a surface treatment such as corona discharge treatment, plasma treatment, or plasma graft polymerization treatment. A surface-treated substrate has better adhesion to the surface treatment layer and further improved abrasion resistance of the surface treatment layer. Therefore, it is preferable to perform the surface treatment on the surface of the substrate that comes into contact with the surface treatment layer. Furthermore, when a base layer described below is provided on the surface-treated substrate, it has better adhesion to the base layer and further improved abrasion resistance of the surface treatment layer. Therefore, when a base layer is provided, it is preferable to perform the surface treatment on the surface of the substrate that comes into contact with the base layer.
[0354] The surface treatment layer may be provided directly on the surface of the substrate, or a primer layer may be provided between the substrate and the surface treatment layer. From the viewpoint of further improving the water repellency and abrasion resistance of the surface treatment layer, the article of the present disclosure preferably includes a substrate, a primer layer disposed on the substrate, and a surface treatment layer surface-treated with the surface treatment agent of the present disclosure, disposed on the primer layer.
[0355] The underlayer is preferably a layer containing an oxide containing silicon and at least one specific element selected from the group consisting of Group 1 elements, Group 2 elements, Group 4 elements, Group 5 elements, Group 13 elements, and Group 15 elements of the periodic table.
[0356] The Group 1 elements of the periodic table (hereinafter also referred to as "Group 1 elements") refer to lithium, sodium, potassium, rubidium, and cesium. As the Group 1 elements, lithium, sodium, and potassium are preferred, and sodium and potassium are more preferred, from the viewpoint of enabling a surface treatment layer to be formed more uniformly on the underlayer without defects, or from the viewpoint of further suppressing variation in the composition of the underlayer between samples. The underlayer may contain two or more types of Group 1 elements.
[0357] The Group 2 elements of the periodic table (hereinafter also referred to as "Group 2 elements") refer to beryllium, magnesium, calcium, strontium, and barium. As the Group 2 elements, magnesium, calcium, and barium are preferred, and magnesium and calcium are more preferred, from the viewpoint of enabling a surface treatment layer to be formed more uniformly on the underlayer without defects, or from the viewpoint of further suppressing variation in the composition of the underlayer between samples. The underlayer may contain two or more Group 2 elements.
[0358] The Group 4 elements of the periodic table (hereinafter also referred to as "Group 4 elements") refer to titanium, zirconium, and hafnium. As the Group 4 elements, titanium and zirconium are preferred, and titanium is more preferred, from the viewpoint of being able to form a surface treatment layer on the underlayer more uniformly without defects, or from the viewpoint of further suppressing variation in the composition of the underlayer between samples. The underlayer may contain two or more types of Group 4 elements.
[0359] The Group 5 elements of the periodic table (hereinafter also referred to as "Group 5 elements") refer to vanadium, niobium, and tantalum. Vanadium is particularly preferred as the Group 5 element from the viewpoint of providing a surface treatment layer with superior abrasion resistance. The underlayer may contain two or more Group 5 elements.
[0360] The Group 13 elements of the periodic table (hereinafter also referred to as "Group 13 elements") refer to boron, aluminum, gallium, and indium. As the Group 13 elements, boron, aluminum, and gallium are preferred, and boron and aluminum are more preferred, from the viewpoint of enabling the surface treatment layer to be formed more uniformly on the underlayer without defects, or from the viewpoint of further suppressing variation in the composition of the underlayer between samples. The underlayer may contain two or more Group 13 elements.
[0361] The Group 15 elements of the periodic table (hereinafter also referred to as "Group 15 elements") refer to nitrogen, phosphorus, arsenic, antimony, and bismuth. As the Group 15 elements, phosphorus, antimony, and bismuth are preferred, and phosphorus and bismuth are more preferred, from the viewpoint of enabling a surface treatment layer to be formed more uniformly on the underlayer without defects, or from the viewpoint of further suppressing variation in the composition of the underlayer between samples. The underlayer may contain two or more Group 15 elements.
[0362] As the specific element contained in the underlayer, Group 1 elements, Group 2 elements, and Group 13 elements are preferred because they provide better abrasion resistance to the surface treatment layer, and Group 1 elements and Group 2 elements are more preferred, with Group 1 elements being even more preferred. The specific element may contain only one type of element or two or more types of elements.
[0363] The oxide contained in the underlayer may be a mixture of oxides of the above elements (silicon and the specific element) alone (for example, a mixture of silicon oxide and an oxide of the specific element), a composite oxide containing two or more of the above elements, or a mixture of an oxide of the above elements alone and a composite oxide.
[0364] From the viewpoint of achieving superior abrasion resistance of the surface treatment layer, the ratio of the total molar concentration of the specific elements in the underlayer to the molar concentration of silicon in the underlayer (specific elements / silicon) is preferably 0.02 to 2.90, more preferably 0.10 to 2.00, and even more preferably 0.20 to 1.80. The molar concentrations (mol %) of each element in the underlayer can be measured, for example, by depth profile analysis by X-ray photoelectron spectroscopy (XPS) using ion sputtering.
[0365] The underlayer may be a single layer or multiple layers. The underlayer may have an uneven surface. The thickness of the underlayer is preferably 1 to 100 nm, more preferably 1 to 50 nm, and even more preferably 2 to 20 nm. When the thickness of the underlayer is equal to or greater than the above lower limit, the adhesion of the underlayer to the surface treatment layer is further improved, and the surface treatment layer has better abrasion resistance. When the thickness of the underlayer is equal to or less than the above upper limit, the underlayer itself has excellent abrasion resistance. The thickness of the underlayer is measured by observing the cross section of the underlayer using a transmission electron microscope (TEM).
[0366] The underlayer can be formed by, for example, a vapor deposition method using a vapor deposition material or a wet coating method.
[0367] The deposition material used in the deposition method preferably contains an oxide containing silicon and a specific element. Specific examples of the form of the deposition material include powder, melt, sintered body, granules, and crushed body, with melt, sintered body, and granules being preferred from the viewpoint of ease of handling. Here, the melt refers to a solid obtained by melting the powder of the deposition material at a high temperature and then cooling and solidifying it. The sintered body refers to a solid obtained by firing the powder of the deposition material. If necessary, a molded body obtained by pressing the powder may be used instead of the powder of the deposition material. The granule refers to a solid obtained by kneading the powder of the deposition material with a liquid medium (e.g., water, organic solvent) to obtain particles, and then drying the particles.
[0368] The vapor deposition material can be produced by, for example, the following methods: A method of mixing silicon oxide powder with a powder of an oxide of a specific element to obtain a vapor deposition material powder. A method of kneading the vapor deposition material powder with water to obtain particles, and then drying the particles to obtain granules of the vapor deposition material. A method of mixing a powder containing silicon (e.g., silicon oxide powder, silica sand, silica gel), a powder containing a specific element (e.g., oxide powder, carbonate, sulfate, nitrate, oxalate, hydroxide of the specific element), and water, drying the mixture, and then firing the dried mixture or a compact obtained by pressing the dried mixture to obtain a sintered body. A method of melting a powder containing silicon (e.g., silicon oxide powder, silica sand, silica gel) and a powder containing a specific element (e.g., oxide powder, carbonate, sulfate, nitrate, oxalate, hydroxide of the specific element) at a high temperature, and then cooling and solidifying the melt to obtain a melt.
[0369] A specific example of a vapor deposition method using a vapor deposition material is a vacuum vapor deposition method. The vacuum vapor deposition method is a method in which a vapor deposition material is evaporated in a vacuum chamber and attached to the surface of a substrate. The temperature during vapor deposition (for example, the temperature of the boat in which the vapor deposition material is placed when a vacuum vapor deposition apparatus is used) is preferably 100 to 3,000°C, and more preferably 500 to 3,000°C. The pressure during vapor deposition (for example, the pressure in the chamber in which the vapor deposition material is placed when a vacuum vapor deposition apparatus is used) is preferably 1 Pa or less, and more preferably 0.1 Pa or less. When forming an underlayer 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.
[0370] Specific examples of evaporation methods for the deposition material include a resistance heating method, in which the deposition material is melted and evaporated on a resistance heating boat made of a high-melting-point metal, and an electron gun method, in which the deposition material is irradiated with an electron beam to directly heat the deposition material, melting and evaporating the surface. The electron gun method is preferred as an evaporation method for the deposition material because it can evaporate high-melting-point substances due to its ability to locally heat the material, and because areas not irradiated by the electron beam are at low temperatures, eliminating the risk of reaction with the container or the inclusion of impurities. The evaporation method for the deposition material may use multiple boats, or all of the deposition materials may be placed in a single boat. The deposition method may be co-evaporation or alternating deposition. Specific examples include mixing silica and a specific source in the same boat, co-evaporating silica and a specific element source in separate boats, or similarly placing them in separate boats and alternately depositing them. The deposition conditions, order, etc., are appropriately selected depending on the composition of the underlayer.
[0371] In the wet coating method, it is preferable to form an undercoat layer on a substrate by a wet coating method using a coating liquid containing a silicon-containing compound, a compound containing a specific element, and a liquid medium.
[0372] Specific examples of the silicon compound include silicon oxide, silicic acid, partial condensates of silicic acid, alkoxysilanes, and partial hydrolysis condensates of alkoxysilanes.
[0373] Specific examples of compounds containing a specific element include oxides of the specific element, alkoxides of the specific element, carbonates of the specific element, sulfates of the specific element, nitrates of the specific element, oxalates of the specific element, and hydroxides of the specific element.
[0374] The liquid medium may be the same as the liquid medium that may be contained in the composition of the present disclosure.
[0375] The content of the liquid medium is preferably 80 to 99.99% by mass, more preferably 90 to 99.9% by mass, based on the total amount of the coating liquid used to form the underlayer.
[0376] Specific examples of wet coating methods for forming the underlayer include spin coating, wipe coating, spray coating, squeegee coating, dip coating, die coating, inkjet coating, flow coating, roll coating, casting, Langmuir-Blodgett coating, and gravure coating.
[0377] After wet-coating the coating liquid, it is preferable to dry the coating film. The drying temperature for the coating film is preferably 20 to 200°C, more preferably 80 to 160°C.
[0378] The article of the present disclosure may be an optical material having a surface treatment layer as the outermost layer. Examples of the optical material include optical materials related to displays and the like, as well as a wide variety of other optical materials. Examples of the optical material include displays such as cathode ray tubes (CRTs; for example, personal computer monitors), liquid crystal displays, plasma displays, organic electroluminescent displays, inorganic thin-film electroluminescent dot matrix displays, rear projection displays, fluorescent display tubes (VFDs), and field emission displays (FEDs), as well as protective plates for such displays, or displays whose surfaces have been treated with an anti-reflection film.
[0379] The article of the present disclosure is preferably an optical component. Examples of optical components include car navigation systems, mobile phones, smartphones, digital cameras, digital video cameras, PDAs, portable audio players, car audio systems, game consoles, eyeglass lenses, camera lenses, lens filters, sunglasses, medical equipment such as gastroscopes, copiers, PCs, displays (e.g., liquid crystal displays, organic EL displays, plasma displays, touch panel displays), touch panels, protective films, and anti-reflection films. Examples of optical components include front protective plates, anti-reflection plates, polarizing plates, and anti-glare plates for displays such as PDPs and LCDs; disc surfaces of optical discs such as Blu-ray (registered trademark) discs, DVD discs, CD-Rs, and MO discs; optical fibers; and the display surfaces of watches. In particular, the article of the present disclosure is preferably a display or a touch panel.
[0380] The article of the present disclosure may be a medical device or a medical material. The article of the present disclosure may also be an automobile interior or exterior component. Examples of exterior components include windows, light covers, and exterior camera covers. Examples of interior components include instrument panel covers, navigation system touch panels, and decorative interior components.
[0381] When the article of the present disclosure is an optical component, the material constituting the surface of the substrate is a material for optical components, such as glass or transparent plastic. When the article of the present disclosure is an optical component, a functional layer such as a hard coat layer or an anti-reflection layer may be formed on the surface (outermost layer) of the substrate. The anti-reflection layer may be either a single-layer anti-reflection layer or a multi-layer anti-reflection layer. Examples of inorganic materials that can be used for the anti-reflection layer include SiO 2 , SiO, ZrO 2 , TiO 2 , TiO, Ti 2 O 3 , Ti 2 O 5 , Al 2 O 3 , Ta 2 O 5 , Ta 3 O 5, Nb 2 O 5 , HfO 2 , Si 3 N 4 , CeO 2 , MgO, Y 2 O 3 , SnO 2 , MgF 2 , and W.O. 3 These inorganic substances may be used alone or in combination of two or more (for example, as a mixture). When a multi-layer antireflection layer is formed, the outermost layer may contain SiO 2 and / or SiO is preferably used. When the article of the present disclosure is an optical glass component for a touch panel, a transparent electrode, for example, a thin film using indium tin oxide (ITO) or indium zinc oxide, may be provided on a portion of the surface of the substrate (glass). Furthermore, the substrate may have an insulating layer, an adhesive layer, a protective layer, a decorative frame layer (I-CON), an atomization film layer, a hard coating film layer, a polarizing film, a phase difference film, a liquid crystal display module, or the like, depending on its specific specifications.
[0382] [Method for manufacturing an article] The method for manufacturing an article according to the present disclosure is, for example, a method for manufacturing an article having a surface-treated layer formed on a substrate by performing a surface treatment on a substrate using the surface treatment agent according to the present disclosure. Examples of the surface treatment include a dry coating method and a wet coating method.
[0383] Examples of dry coating methods include vacuum deposition, CVD, and sputtering. Vacuum deposition is preferred as a dry coating method from the viewpoints of suppressing decomposition of the compound and simplicity of the equipment. For vacuum deposition, a pellet-shaped substance obtained by impregnating a metal porous body such as iron or steel with the compound of the present disclosure may be used. A composition containing the compound of the present disclosure and a liquid medium may be impregnated into a metal porous body such as iron or steel, and the liquid medium may be dried to obtain a pellet-shaped substance impregnated with the compound of the present disclosure.
[0384] 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-Blodgett coating, and gravure coating.
[0385] In order to improve the abrasion resistance of the surface treatment layer, an operation to promote the reaction between the compound of the present disclosure and the substrate may be performed as necessary. Examples of such an operation include heating, humidification, and light irradiation. For example, the substrate on which the surface treatment layer is formed can be heated in a humid atmosphere to promote reactions such as the hydrolysis reaction 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 surface treatment, compounds in the surface treatment layer that are not chemically bonded to other compounds or the substrate may be removed as needed. Examples of removal methods include pouring a solvent over the surface treatment layer and wiping with a cloth soaked in the solvent.
[0386] Next, embodiments of the present disclosure will be described in detail using examples, but the embodiments of the present disclosure are not limited to these examples. Examples 3 to 7, 10 to 17, 19 to 23, 25 to 29, and 31 to 35 are working examples, and Examples 1, 2, 8, 9, 18, 24, and 30 are comparative examples.
[0387] [Preparation of Compounds] The following compounds were prepared.
[0388] <First Compound> (Compound (A1)) The following compound was synthesized by the method described in Example 1 of WO 2023 / 017830. Compound (A1) having an average n10 value of 11 was obtained by column purification.
[0389]
[0390] (Compound (A2)) A compound was synthesized in the same manner as in the case of compound (A1), and compound (A2) having an average n10 value of 33 was obtained by column purification.
[0391] (Compound (A3)) A compound was synthesized in the same manner as in the case of compound (A1), and compound (A3) having an average n10 value of 54 was obtained by column purification.
[0392] (Compound (A4)) Synthesis of Compound (4-1) THF (tetrahydrofuran, 101 g) was added to hexamethylcyclotrisiloxane (65 g) and stirred at 25°C until dissolved. Next, a solution of lithium trimethylsilanol salt (5.1 g) suspended in THF (20 g) was added, and the mixture was stirred at 25°C for 2 hours. Next, chlorodimethylsilane (10.5 g) was added, and the mixture was stirred at 25°C for 1 hour. After extraction with hexane and water, the solvent and low-boiling components were distilled off under reduced pressure, and flash column chromatography using silica gel (developing solvent: hexane / dichloromethane) was performed to obtain 25 g of compound (4-1). The average value of n10 in compound (4-1) was 14. The structure of compound (4-1) was confirmed by the following NMR data.
[0393]
[0394] 1 H-NMR (400MHz, CDCl 3 ) δ: 4.63 (hept, J=2.8Hz, 1H), 0.21-0.08 (m, 6H), 0.07--0.12 (m, 87H).
[0395] Synthesis of Compound (4-2) Dichloromethane (20 g) and 18-bromo-1-octadecene (1.0 g) were added to compound (4-1) (2.0 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 distilling off low-boiling components under reduced pressure, flash column chromatography using silica gel (developing solvent: hexane / dichloromethane) was performed to obtain 1.2 g of compound (4-2). The average value of n10 in compound (4-2) was 14. The structure of compound (4-2) was confirmed by the following NMR data.
[0396]
[0397] 1 H-NMR (400MHz, CDCl 3 ) δ: 3.41 (t, J = 6.9Hz, 2H), 1.85 (p, J = 7.1Hz, 2H), 1.75-0.95 (m, 30H), 0.53 (s, 2H), 0.34- -0.25 (m, 93H).
[0398] Synthesis of Compound (4-3) To compound (4-2) (1.2 g), THF (20 g), allyl magnesium chloride solution (in THF, 2.0 M) (20 mL), and copper (II) chloride (0.02 g) were added, and the mixture was stirred at 50°C for 2 hours. Hydrochloric acid and hexane were added for extraction, and low-boiling point components were distilled off under reduced pressure. Then, flash column chromatography using silica gel (developing solvent: hexane / dichloromethane) was performed to obtain 1.1 g of compound (4-3). In compound 2-2, the average value of n10 was 14. The structure of compound (4-3) was confirmed by the following NMR data.
[0399]
[0400] 1 H-NMR (400MHz, CDCl 3 ) δ: 5.74 (ddt, J=16.9, 10.2, 6.7Hz, 1H), 5.01-4.74 (m, 2H), 2.08-1.84 (m, 2H), 1.75-0.95 (m, 34H), 0.45 (dd, J=9.4, 5.7Hz, 2H) 0.34- -0.25 (m, 93H).
[0401] Synthesis of Compound (A4) Dichloromethane (10 g) was added to compound (4-3) (1.1 g) to dissolve it. Next, a toluene solution of platinum / 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (platinum content: 3 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. The solvent was distilled off under reduced pressure to obtain 1.1 g of compound (A4). The average value of n10 in compound (A4) was 14. The structure of compound (A4) was confirmed by the following NMR data.
[0402]
[0403] 1 H-NMR (400MHz, CDCl 3 ) δ: 3.50 (s, 9H), 1.75-0.95 (m, 38H), 0.62-0.54 (m, 2H), 0.45 (dd, J=9.4, 5.9Hz, 2H), 0.34- -0.25 (m, 93H).
[0404] (Compound (A5)) The following compound (A5) was synthesized by the method described in Synthesis Example 26 of JP-A No. 2024-025757.
[0405]
[0406] <Second Compound> (Compound (B1)) The following compound was synthesized by the method described in Example 3 of WO 2023 / 017830. Compound (B1) having an average n10 value of 6 was obtained by column purification.
[0407]
[0408] (Compound (B2)) A compound was synthesized in the same manner as in the case of compound (A1), and compound (B2) having an average n10 value of 49 was obtained by column purification.
[0409] (Compound (B3)) Compound (B3) was synthesized by the method described in Example 3 of WO 2023 / 017830. Compound (B3) having an average n10 value of 11 was obtained by column purification. Note that 1-amino-10-undecene was used instead of 2,2-diallyl-penten-1-amine used in Synthesis Example 3 of WO 2023 / 017830.
[0410]
[0411] (Compound (B4)) Synthesis of Compound (5-1) The following compound (5-1) was synthesized by the method described in Synthesis Example 1 of JP-A No. 2024-025757.
[0412]
[0413] Synthesis of Compound (5-2) Heptane (20 g) and 1,1,3,3,5,5,7,7-octamethyltetrasiloxane (1.0 g) were added to compound (5-1) (2.0 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 distilling off low-boiling components under reduced pressure, flash column chromatography using silica gel (developing solvent: hexane / dichloromethane) was performed to obtain 1.2 g of compound (5-2). The structure of compound (5-2) was confirmed by the following NMR data.
[0414]
[0415] 1 H-NMR (400MHz, CDCl 3 ) δ: 3.67 (s, 6H), 2,32 (t, 4H), 1.75-0.95 (m, 80H), 0.45 (m, 4H), 0.34--0.25 (m, 24H).
[0416] Synthesis of Compound (5-3) Toluene (10 mL), 4-[2,2-di(2-propylenyl)]pentenylamine (5.0 g), and 1,5,7-triazabicyclo[4.4.0]dec-5-ene (1.0 g) were added to compound (5-2) (1.0 g), and the mixture was stirred at 125°C for 24 hours. The mixture was then washed with aqueous hydrochloric acid, dehydrated with magnesium sulfate, and the low-boiling components were distilled off under reduced pressure. Flash column chromatography using silica gel (developing solvent: hexane / ethyl acetate) was then performed to obtain 0.9 g of compound (5-3). The structure of compound (5-3) was confirmed by the following NMR data.
[0417]
[0418] 1 H-NMR (400MHz, CDCl 3 ) δ: 5.80 (m, 4H), 5.50 (s, 2H), 5.12 (m, 8H), 3.25 (d, J=6.3Hz, 4H), 2,12 (m, 4H), 1.96 (m, 8H), 1.75-0.95 (m, 82H), 0.45 (m, 4H), 0.34- -0.25 (m, 24H).
[0419] Synthesis of Compound (B4) Dichloromethane (10 g), compound (5-3) (0.80 g), 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 (3.0 g) were placed in a 100 mL flask and stirred at 25°C for 2 hours. The solvent was distilled off under reduced pressure to obtain 0.70 g of compound (B4). The structure of compound (B4) was confirmed from the following NMR data.
[0420]
[0421] 1 H-NMR (400MHz, CDCl 3 ) δ: 5.50 (s, 2H), 3.59 (s, 36H), 3.25 (d, J=6.3Hz, 4H), 2,12 (m, 4H), 1.75-0.95 (m, 98H), 0.63 (m, 8H), 0.45 (m, 4H), 0.34- -0.25 (m, 24H).
[0422] [Preparation of Surface Treatment Agent and Fabrication of Article] Each compound listed in Tables 1 to 4 was mixed with heptane to obtain a surface treatment agent containing the first compound and the second compound in the proportions listed in each table, with the total concentration of the first compound and the second compound being 0.2 mass%. A surface treatment was performed on a substrate using the surface treatment agent. A wet coating method was used as the surface treatment method.
[0423] (Wet Coating Method) 30 g of silicon oxide was placed as a deposition source in a copper hearth in a vacuum deposition apparatus (VTR-350M manufactured by ULVAC Kiko Co., Ltd.). A glass substrate was placed in the vacuum deposition apparatus, and the interior of the vacuum deposition apparatus was heated to 5 × 10 -3 The hearth was evacuated to a pressure of 100 Pa or less. The hearth was heated to about 2,000° C., and silicon oxide was vacuum-deposited on the surface of the substrate. As a result, a silicon oxide layer having a thickness of about 20 nm was formed on the substrate.
[0424] The substrate with the silicon oxide layer formed thereon was placed on the sample stage of a spray coater (API-90RS, manufactured by Apiros Co., Ltd.) so that the silicon oxide layer was on the surface. Next, 13 g of the prepared surface treatment agent was placed in 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 / sec. The coated substrate was then heat-treated at 140°C for 30 minutes. This resulted in an article having a surface-treated layer on the surface of the silicon oxide layer. Next, the surface treatment layer of the obtained article was evaluated as follows.
[0425] [Evaluation] <Evaluation of Surface Slipperiness> For a substrate having a surface treatment layer on its surface, the dynamic friction coefficient was measured in accordance with ASTM D4917 using a surface property measuring instrument (FPT-1 manufactured by Labthink) and paper as a friction element. Specifically, the substrate having a surface treatment layer was placed horizontally, and a paper friction element (2 cm x 2 cm) was brought into contact with the exposed surface of the surface treatment layer, and a load of 200 gf was applied thereto. Thereafter, with the load applied, the paper friction element was translated at a speed of 200 mm / sec, and the dynamic friction coefficient was measured.
[0426] <Water contact angle> Approximately 2 μL of distilled water was dropped onto the surface treatment layer of the article, and the water contact angle was measured using a contact angle measuring device (DM-500: product name, manufactured by Kyowa Interface Science Co., Ltd.). The average value measured at five points on the surface treatment layer was taken as the water contact angle. The 2θ method was used to calculate the water contact angle.
[0427] <Abrasion Resistance> An eraser abrasion test was carried out by the following method to measure the abrasion resistance of the surface treatment layer. The surface treatment layer was subjected to a 1 cm eraser abrasion test using a tester (Daiei Scientific Instruments Manufacturing Co., Ltd., flat surface abrasion tester (triple type), model: PA-300A). 2 An eraser (Minoan, manufactured by MIRAE SCIENCE) was attached to the indenter, and rubbed 1,000 times with a load of 1 kg at a stroke width of 20 mm and a speed of 30 mm / sec, after which the water contact angle was measured. The larger the water repellency (water contact angle) after abrasion, the better the abrasion resistance. The rate of change (%) of the water contact angle was calculated using the following formula: Rate of change = {(initial water contact angle) - (water contact angle after abrasion)} / (initial water contact angle) x 100
[0428] The evaluation results of surface slipperiness, initial water contact angle, water contact angle after abrasion resistance test, and rate of change in water contact angle are shown in Tables 1 to 4. In Tables 1 to 4, the ratio of the first compound represents the amount (mol %) of the first compound relative to the total amount of the first compound and the second compound, and the ratio of the second compound represents the amount (mol %) of the second compound relative to the total amount of the first compound and the second compound.
[0429]
[0430]
[0431]
[0432]
[0433] As shown in Tables 1 to 4, the surface-treated layers obtained in Examples 3 to 7, 10 to 17, 19 to 23, 25 to 29, and 31 to 35 had water contact angles of 80 degrees or more after the abrasion resistance test, and the rate of change was 21% or less. In contrast, the surface-treated layers obtained in Examples 1, 2, 8, 9, 18, 24, and 30 had water contact angles of less than 80 degrees after the abrasion resistance test, and the rate of change was 25% or more. It was confirmed that the surface-treated layers obtained in Examples 3 to 7, 10 to 17, 19 to 23, 25 to 29, and 31 to 35 had superior abrasion resistance compared to the surface-treated layers obtained in Examples 1, 2, 8, 9, 18, 24, and 30. Furthermore, it was confirmed that the surface treatment layers obtained in Examples 3 to 7, 10 to 17, 19 to 23, 25 to 29, and 31 to 35 had an initial water contact angle of 100 degrees or more, a surface slipperiness of 0.15 or more, and an excellent balance between water repellency and surface slipperiness.
[0434] The composition and surface treatment agent of the present disclosure can be used for substrates in, for example, display devices such as touch panel displays, optical elements, semiconductor elements, building materials, automotive parts, nanoimprint technology, and the like. The composition and surface treatment agent can also be used for bodies, window glass (windshields, side glass, rear glass), mirrors, bumpers, and the like of transportation equipment such as trains, automobiles, ships, and aircraft. The composition and surface treatment agent can also be used for outdoor items such as building exterior walls, tents, solar power generation modules, soundproofing panels, and concrete; fishing nets, insect nets, and aquariums. The composition and surface treatment agent can also be used for various indoor facilities such as kitchens, bathrooms, sinks, mirrors, and toilet peripherals; ceramics such as chandeliers and tiles; artificial marble, and air conditioners. The composition and surface treatment agent can also be used for antifouling treatments for jigs, interior walls, piping, and the like in factories. The composition and surface treatment agent can also be used for goggles, eyeglasses, helmets, pachinko machines, fibers, umbrellas, playground equipment, and soccer balls. The composition and surface treatment agent can also be used as an anti-adhesion agent for various packaging materials such as food packaging materials, cosmetic packaging materials, the inside of pots, etc. The composition and surface treatment agent can also be used for car navigation systems, mobile phones, smartphones, digital cameras, digital video cameras, PDAs, portable audio players, car audio equipment, game machines, eyeglass lenses, camera lenses, lens filters, sunglasses, medical equipment such as gastroscopes, copiers, PCs, displays (e.g., liquid crystal displays, organic EL displays, plasma displays, touch panel displays), touch panels, protective films, anti-reflection films, and other optical components.
[0435] (Additional Notes) The present disclosure includes the following aspects. <1> A composition comprising: a first compound having a linear organo(poly)siloxane residue and a reactive silyl group linked to only one end of the linear organo(poly)siloxane residue; and a second compound having a linear organo(poly)siloxane residue and reactive silyl groups linked to both ends of the linear organo(poly)siloxane residue, wherein the amount of the second compound relative to the total amount of the first compound and the second compound is more than 35 mol % and not more than 95 mol %. <2> The composition according to <1>, wherein the reactive silyl groups in the first compound and the second compound are each independently represented by the following formula (S1): -Si(R 2 ) n L 3-n ...(S1) R 2 are each independently a hydrocarbon group, each L is independently a hydrolyzable group, a group having a hydrolyzable group, or a hydroxyl group, and n is an integer of 0 to 2. <3> The composition according to <1> or <2>, wherein the chain organo(poly)siloxane residues in the first compound and the second compound are each independently represented by the following formula (B1) or (B2): In formula (B1), R 3 are each independently a hydrocarbon group, k1 is a number of 1 or more, and * is a bonding site to an adjacent atom. In formula (B2), R 4 are each independently a hydrocarbon group or T 11 -B r -(SiR 3 2 -O) k1 - and T 11 are each independently a monovalent group; B is each independently -O- or -C(=O)-; r is each independently 0 or 1; R 3are each independently a hydrocarbon group, k1 is each independently a number of 1 or more, and * is a bonding site to an adjacent atom. <4> The composition according to <3> above, wherein in formula (B1) or (B2), k1 is a number of 1 to 600. <5> The composition according to any one of <1> to <4> above, wherein the first compound includes a compound represented by the following formula (C): In formula (C), T 11 is a monovalent group that does not contain a reactive silyl group, each B is independently —O— or —C(═O)—, each r is independently 0 or 1, and R 3 are each independently a hydrocarbon group, k1 is each independently a number of 1 or more, p1 is an integer of 1 or more, and A 11 is a (p1+q1)-valent linking group, q1 is an integer of 1 or more, R 2 are each independently a hydrocarbon group, L is each independently a hydrolyzable group, a group having a hydrolyzable group, or a hydroxyl group, and n is each independently an integer of 0 to 2. <6> The composition according to <5> above, wherein in formula (C), q1 is an integer of 1 to 4. <7> The composition according to any one of <1> to <6> above, wherein the second compound includes a compound represented by the following formula (D): In formula (D), R 4 are each independently a hydrocarbon group or T 11 -B r -(SiR 3 2 -O) k1 - and T 11 are each independently a monovalent group; B is each independently -O- or -C(=O)-; r is each independently 0 or 1; R 3 are each independently a hydrocarbon group; k1 is each independently a number of 1 or more; A 12 are each independently a (q1+1)-valent linking group, each q1 is independently an integer of 1 or more, R 2are each independently a hydrocarbon group, L is each independently a hydrolyzable group, a group having a hydrolyzable group, or a hydroxyl group, and n is each independently an integer of 0 to 2. <8> The composition according to <7> above, wherein in formula (D), q1 is each independently an integer of 1 to 4. <9> The composition according to any one of <1> to <8> above, further comprising a liquid medium. <10> A surface treatment agent comprising the composition according to any one of <1> to <9> above. <11> A method for producing an article, comprising treating a substrate with the surface treatment agent according to <10> above, and producing an article having a surface treatment layer formed on the substrate. <12> An article comprising a substrate and a surface treatment layer disposed on the substrate and surface-treated with the surface treatment agent according to <10> above. <13> The article according to <12> above, which is an optical member. <14> The article according to <12> above, which is a display or a touch panel.
[0436] The disclosure of Japanese Patent Application No. 2023-174759, filed on October 6, 2023, is incorporated herein by reference in its entirety. All documents, patent applications, and technical standards mentioned herein are incorporated herein by reference to the same extent as if each individual document, patent application, and technical standard was specifically and individually indicated to be incorporated by reference.
Claims
1. A composition comprising: a first compound having a divalent chain group and a reactive silyl group linked to only one end of the divalent chain group; and a second compound having a divalent chain group and a reactive silyl group linked to each of both ends of the divalent chain group, wherein the amount of the second compound relative to the total amount of the first compound and the second compound is more than 35 mol % and not more than 95 mol %.
2. The composition according to claim 1, wherein the first compound is a compound having a linear organo(poly)siloxane residue and a reactive silyl group linked to only one end of the linear organo(poly)siloxane residue, and the second compound is a compound having a linear organo(poly)siloxane residue and a reactive silyl group linked to each of both ends of the linear organo(poly)siloxane residue.
3. The composition according to claim 1, wherein the reactive silyl groups in the first compound and the second compound are each independently represented by the following formula (S1) or formula (S3): -Si(R 2 ) n L 3-n ...(S1) -[Si(L 2 ) 2 -P] r1 -Si(L 2 ) 3 ...(S3) In formula (S1), R 2 are each independently a hydrocarbon group, each L is independently a hydrolyzable group, a group having a hydrolyzable group, or a hydroxyl group, and n is an integer of 0 to 2. 2 each independently represents a hydrolyzable group, a group having a hydrolyzable group, a hydroxyl group, or a hydrocarbon group; 2 At least four L 2 represents a hydrolyzable group, a group having a hydrolyzable group, or a hydroxyl group; each P is independently an oxygen atom or an organic group having one carbon atom bonded to adjacent Si atoms on both sides; and r1 is an integer of 1 to 3.
4. The composition according to claim 2, wherein the linear organo(poly)siloxane residues in the first compound and the second compound are each independently represented by the following formula (B1) or (B2): In formula (B1), R 3 are each independently a hydrocarbon group, k1 is a number of 1 or more, and * is a bonding site with an adjacent atom. In formula (B2), R 4 each independently represents a hydrocarbon group or T 11 -B r -(SiR 3 2 -O) k1 - and T 11 are each independently a monovalent group; B is each independently -O- or -C(=O)-; r is each independently 0 or 1; R 3 are each independently a hydrocarbon group; each k1 is independently a number of 1 or more; and * is a bonding site with an adjacent atom.
5. The composition according to claim 4, wherein in formula (B1) or (B2), k1 is a number from 1 to 600.
6. The composition of claim 1, wherein the first compound comprises a compound represented by formula (C), (C2), (E), or (E2): In formula (C), T 11 is a monovalent group not containing a reactive silyl group, each B is independently -O- or -C(=O)-, each r is independently 0 or 1, R 3 are each independently a hydrocarbon group; k1 is each independently a number of 1 or more; p1 is an integer of 1 or more; A 11 is a (p1+q1)-valent linking group, q1 is an integer of 1 or more, R 2 are each independently a hydrocarbon group, each L is independently a hydrolyzable group, a group having a hydrolyzable group, or a hydroxyl group, and each n is independently an integer of 0 to 2. 2 each independently represents a hydrolyzable group, a group having a hydrolyzable group, a hydroxyl group, or a hydrocarbon group; 2 At least four L 2 is a hydrolyzable group, a group having a hydrolyzable group, or a hydroxyl group; each P is independently an oxygen atom or an organic group having one carbon atom bonded to adjacent Si on both sides; r1 is an integer of 1 to 3; T 11 , B, r, R 3 , k1, p1, A 11 The definitions of q1 and q2 are the same as those in formula (C). In formula (E), B 11 is a monovalent group containing at least one selected from the group consisting of Si, Ge, and Sn to which a hydroxyl group or a hydrolyzable group is not directly bonded; or a monovalent group containing a branched alkyl group, provided that B 11 does not contain a reactive silyl group, u1 is an integer of 1 or more, 13 is a (q1+u1)-valent linking group, q1 is an integer of 1 or more, R 2 each independently represents a hydrocarbon group; each L independently represents a hydrolyzable group, a group having a hydrolyzable group, or a hydroxyl group; each n independently represents an integer of 0 to 2. 2 each independently represents a hydrolyzable group, a group having a hydrolyzable group, a hydroxyl group, or a hydrocarbon group; 2 At least four L 2 is a hydrolyzable group, a group having a hydrolyzable group, or a hydroxyl group; each P is independently an oxygen atom or an organic group having one carbon atom bonded to adjacent Si on both sides; each r1 is independently an integer of 1 to 3; 11 , u1, A 13 The definitions of q1 and q2 are the same as those in formula (E).
7. The composition according to claim 6, wherein in formulas (C), (C2), (E), and (E2), q1 is an integer of 1 to 4.
8. The composition according to claim 1, wherein the second compound comprises a compound represented by formula (D) or (D2): In formula (D), R 4 each independently represents a hydrocarbon group or T 11 -B r -(SiR 3 2 -O) k1 - and T 11 are each independently a monovalent group; B is each independently -O- or -C(=O)-; r is each independently 0 or 1; R 3 are each independently a hydrocarbon group; k1 is each independently a number of 1 or more; 12 are each independently a (q1+1)-valent linking group, each q1 is independently an integer of 1 or more, R 2 each independently represents a hydrocarbon group; each L independently represents a hydrolyzable group, a group having a hydrolyzable group, or a hydroxyl group; each n independently represents an integer of 0 to 2. 2 each independently represents a hydrolyzable group, a group having a hydrolyzable group, a hydroxyl group, or a hydrocarbon group; 2 At least four L 2 is a hydrolyzable group, a group having a hydrolyzable group, or a hydroxyl group; each P is independently an oxygen atom or an organic group having one carbon atom bonded to adjacent Si on both sides; each r1 is independently an integer of 1 to 3; 4 , k1, A 12 The definitions of q1 and q2 are the same as those in formula (D).
9. The composition according to claim 8, wherein in formulas (D) and (D2), q1 each independently represents an integer of 1 to 4.
10. The composition of claim 1, further comprising a liquid medium.
11. A surface treatment agent comprising the composition according to any one of claims 1 to 10.
12. A method for manufacturing an article, comprising: performing a surface treatment on a substrate using the surface treatment agent according to claim 11; and manufacturing an article having a surface treatment layer formed on the substrate.
13. An article comprising a substrate, and a surface treatment layer disposed on the substrate and surface-treated with the surface treatment agent according to claim 11.
14. The article of claim 13 which is an optical component.
15. The article according to claim 13, which is a display or a touch panel.