WO2023204021A1 - Compound, composition, surface treatment agent, method for manufacturing article, and article - Google Patents

Abstract

A compound containing at least one selected from the group consisting of polydialkylsiloxane residues and C10 or higher alkylene chains, a polyoxyalkylene chain, and a reactive silyl group; a composition and a surface treatment agent containing said compound; and an article and a method for manufacturing an article in which said surface treatment agent is used.

Description

Compounds, compositions, surface treatment agents, methods for producing articles, and articles

The present disclosure relates to compounds, compositions, surface treatment agents, methods of manufacturing articles, and articles.

In recent years, in order to improve performance such as appearance and visibility, there has been a demand for technology that makes it difficult for fingerprints to form on the surface of articles and technology that makes it easier to remove dirt. As a specific method, a method is known in which the surface of an article is subjected to surface treatment using a surface treatment agent.

For example, Patent Document 1 discloses that the polydialkylsiloxane skeleton contains a carbon atom to silicon atom ratio (C/Si) measured by X-ray photoelectron spectroscopy, which is 0.93 or more and less than 1.38 on a molar basis. A composition for forming a film is described. Patent Document 2 describes a method for producing an organic thin film using an organic solvent solution containing a metal surfactant having at least one hydrolyzable group or hydroxyl group.

Japanese Patent Application Publication No. 2017-201010 International Publication No. 2008/016029

On the other hand, compositions used as surface treatment agents and the like are required to have oil repellency as well as water repellency for the surface treatment layer formed.

The present disclosure has been made in view of the above circumstances, and the problem to be solved by an embodiment of the present invention is to form a surface treatment layer that has both water repellency and oil repellency on a base material. An object of the present invention is to provide novel compounds and compositions useful as surface treatment agents.
The problem to be solved by an embodiment of the present invention is to provide a surface treatment agent that can form a surface treatment layer that is both water repellent and oil repellent on a base material.
An object of an embodiment of the present invention is to provide an article having a surface treatment layer that is both water repellent and oil repellent, and a method for manufacturing the same.

The present disclosure includes the following aspects.
<1> A compound containing at least one selected from the group consisting of a polydialkylsiloxane residue and an alkylene chain having 10 or more carbon atoms, a polyoxyalkylene chain, and a reactive silyl group.
<2> A compound represented by the following formula (1).

 

In formula (1),
T ¹ and T ² are each independently a hydrogen atom or a monovalent group,
Z is each independently a polydialkylsiloxane residue or an alkylene chain having 10 or more carbon atoms,
A is a polyoxyalkylene chain,
Y ¹ is a (p+q+g)-valent linking group,
R ¹ is each independently a monovalent hydrocarbon group,
L ² is each independently a hydrolyzable group or a hydroxyl group,
p is an integer from 1 to 3,
q is an integer from 1 to 3,
n is an integer from 0 to 2,
g is an integer of 1 or more.
<3> The compound according to <2>, wherein p and q in the formula (1) are both 1.
<4> A composition comprising the compound according to any one of <1> to <3> and a liquid medium. <5> A surface treatment agent containing the compound according to any one of <1> to <3>.
<6> The surface treatment agent according to <5>, further comprising a liquid medium.
<7> A method for manufacturing an article, comprising performing a surface treatment on a base material using the surface treatment agent described in <5> to manufacture an article having a surface treatment layer formed on the base material.
<8> A method for manufacturing an article, comprising performing a surface treatment on a base material using the surface treatment agent according to <6> to manufacture an article having a surface treatment layer formed on the base material.
<9> An article comprising a base material and a surface treatment layer disposed on the base material and surface treated with the surface treatment agent according to <5>.
<10> The article according to <9>, wherein the article is an optical member.
<11> The article according to <9>, wherein the article is a display or a touch panel.

According to one embodiment of the present invention, novel compounds and compositions useful as a surface treatment agent capable of forming a surface treatment layer that is both water repellent and oil repellent on a substrate are provided.
According to one embodiment of the present invention, a surface treatment agent is provided that can form a surface treatment layer that is both water repellent and oil repellent on a base material.
According to one embodiment of the present invention, an article having a surface treatment layer that is both water repellent and oil repellent, and a method for manufacturing the article are provided.

Hereinafter, one embodiment of the present invention will be described in detail. However, the present invention is not limited to the following embodiments. In the following embodiments, the constituent elements (including elemental steps and the like) 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 invention.

In the present disclosure, numerical ranges indicated using "~" include the numerical values written before and after "~" as minimum and maximum values, respectively.
In the present disclosure, each component may contain multiple types of corresponding substances. If there are multiple types of substances corresponding to each component in the composition, the content rate or content of each component is the total content rate or content of the multiple types of substances present in the composition, unless otherwise specified. means quantity.
In the numerical ranges described step by step in the present disclosure, the upper limit or lower limit described in one numerical range may be replaced with the upper limit or lower limit of another numerical range described step by step. Furthermore, in the numerical ranges described in this disclosure, the upper limit or lower limit of the numerical range may be replaced with the values shown in the Examples.
In this disclosure, the term "layer" or "film" refers to the case where the layer or film is formed only in a part of the region, in addition to the case where the layer or film is formed in the entire region when observing the region where the layer or film is present. This also includes cases where it is formed.
In the present disclosure, the term "surface treated layer" refers to a layer formed on the surface of a base material 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 a compound (X) and a group (X), respectively.
In the present disclosure, a (poly)oxyalkylene group means an oxyalkylene group or a polyoxyalkylene group.

[Compound]
The compound of the present disclosure includes at least one selected from the group consisting of a polydialkylsiloxane residue and an alkylene chain having 10 or more carbon atoms, a polyoxyalkylene chain, and a reactive silyl group. Hereinafter, at least one selected from the group consisting of polydialkylsiloxane residues and alkylene chains having 10 or more carbon atoms will be referred to as "chain Z", and the polyoxyalkylene chain will also be referred to as "chain A".
When the surface of a substrate is treated with a composition containing the compound of the present disclosure, a surface treatment layer that is both water repellent and oil repellent can be formed. Although the reason for this is not certain, it is assumed as follows.
The compound of the present disclosure has a reactive silyl group that has high adhesion to the substrate, and thus can form a surface treatment layer that adheres to the surface of the substrate. The polydialkylsiloxane residue and the alkylene chain having 10 or more carbon atoms in the compound of the present disclosure have hydrophobicity, and the polyoxyalkylene chain has hydrophilicity. In other words, the compound of the present disclosure has both a hydrophobic chain Z and a hydrophilic chain A in one molecule in addition to having a reactive silyl group, thereby exhibiting water repellency and oil repellency. It is considered that a surface treatment layer that achieves both of these can be formed on the substrate.

In the compound of the present disclosure, chain Z and chain A are preferably bonded to a reactive silyl group via a linking group. In other words, the compound of the present disclosure comprises a reactive silyl group, a linking group bonded to the reactive silyl group, a polydialkylsiloxane residue bonded to the reactive silyl group via the linking group, and a carbon number of 10 or more. The compound preferably contains at least one type selected from the group consisting of alkylene chains, and a polyoxyalkylene chain bonded to the reactive silyl group via the linking group.

When chain Z and chain A are bonded to the reactive silyl group via a linking group, the linking group present between chain Z and chain A and the reactive silyl group may be any group that does not impede the purpose of the present disclosure. For example, a polyvalent linking group illustrated as Y ¹ in formula (1) below may be mentioned.
In addition, when chain Z is an alkylene chain and chain Z and chain A are directly bonded to one carbon atom, the one carbon atom serving as a branching point is an atom constituting the linking group.

When chain Z and chain A, which will be described later, are bonded to a reactive silyl group via a linking group, chain Z and chain A may be bonded to the same atom constituting the linking group, or may be bonded to different atoms. May be combined. From the viewpoint of ease of synthesis, chain Z and chain A are preferably bonded to the same atom constituting the linking group.
When two or more chains Z are bonded to a reactive silyl group via a linking group, the two or more chains Z may be bonded to the same atom constituting the linking group, or may be bonded to different atoms. good.
When two or more chains A are bonded to a reactive silyl group via a linking group, the two or more chains A may be bonded to the same atom constituting the linking group, or may be bonded to different atoms. good.
When two or more reactive silyl groups are bonded to chain Z and chain A via a linking group, the two or more reactive silyl groups may be bonded to the same atom constituting the linking group, or may be different from each other. May be bonded to atoms. From the viewpoint of ease of synthesis, two or more reactive silyl groups are preferably bonded to different atoms constituting the linking group.

(Chain Z)
The compound of the present disclosure includes at least one type (ie, chain Z) selected from the group consisting of a polydialkylsiloxane residue and an alkylene chain having 10 or more carbon atoms.

The number of chains Z in the compound of the present disclosure may be 1 or more, and from the viewpoint of obtaining a surface treated layer with excellent wear resistance, the number is preferably 1 to 3, more preferably 1 to 2, and even more preferably 1.
The compound of the present disclosure may have only a polydialkylsiloxane residue as the chain Z, may have only an alkylene chain having 10 or more carbon atoms, or may have a polydialkylsiloxane residue and an alkylene chain having 10 or more carbon atoms. It may have both chains. From the viewpoint of ease of synthesis, it is preferable that the chain Z is only a polydialkylsiloxane residue or only an alkylene chain having 10 or more carbon atoms.

The number of atoms constituting the main chain in chain Z is preferably 10 or more, more preferably 12 or more, even more preferably 16 or more, particularly preferably 18 or more, from the viewpoint of obtaining a surface treated layer with excellent water repellency. Further, the number of constituent atoms of the main chain in chain Z is preferably 500 or less, more preferably 250 or less, further preferably 100 or less, and particularly preferably 50 or less, from the viewpoint of obtaining a surface treatment layer with excellent wear resistance. The number of constituent atoms of the main chain in chain Z is preferably 10 to 500, more preferably 12 to 250, even more preferably 16 to 100, particularly preferably 18 to 50.
When the compound of the present disclosure has two or more chains Z, the number of constituent atoms of the main chain in the two or more chains Z may be the same or different.

Here, the "number of atoms constituting the main chain" refers to the number of atoms constituting the longest straight chain in chain Z. For example, when chain Z is a polydialkylsiloxane residue, the total number of silicon atoms and oxygen atoms that constitute the main chain and are alternately bonded is defined as the number of atoms constituting the main chain. Further, for example, when the chain Z is an alkylene chain having 10 or more carbon atoms, the total number of carbon atoms constituting the main chain is defined as the number of atoms constituting the main chain.

<Polydialkylsiloxane residue>
The polydialkylsiloxane residue is a divalent chain organopolysiloxane residue.
As the polydialkylsiloxane residue, a partial structure represented by the following formula (B1) is preferable.

 

In formula (B1), R ³ is each independently an alkyl group, and X 2 is an integer of 1 or more.

The alkyl group represented by R ³ may be any of a linear alkyl group, a branched alkyl group, and a cyclic alkyl group, and among these, a linear alkyl group or a cyclic alkyl group is preferable, and a linear alkyl group or a cyclic alkyl group is preferable. More preferred are alkyl groups.
The number of carbon atoms in the alkyl group represented by R ³ is, for example, 1 to 5, preferably 1 to 3, more preferably 1 to 2, and even more preferably 1.
The alkyl group represented by R ³ is more preferably a methyl group, an ethyl group, an n-propyl group, or an n-butyl group, and even more preferably a methyl group.
The (2×X2+2) R ³ 's included in formula (B1) may be the same or different.

X2 is an integer of 1 or more, and from the viewpoint of obtaining a surface treated layer with excellent water repellency, it is preferably 5 to 200, more preferably 5 to 100, and even more preferably 10 to 80. From the viewpoint of obtaining a surface treated layer with excellent wear resistance, X2 is preferably from 9 to 50, more preferably from 11 to 30, particularly preferably from 11 to 25.

When the compound of the present disclosure has two or more polydialkylsiloxane residues, the number of dialkylsiloxane units in the two or more polydialkylsiloxane residues may be the same or different.

<Alkylene chain>
The number of carbon atoms in the alkylene chain is 10 or more, preferably 12 or more, more preferably 16 or more, and even more preferably 18 or more from the viewpoint of improving the water repellency of the surface treatment layer. The number of carbon atoms in the alkylene chain may be 21 or more. The number of carbon atoms in the alkylene chain is preferably 100 or less, more preferably 60 or less, and even more preferably 40 or less, from the viewpoint of obtaining a surface treatment layer with excellent wear resistance. The alkylene chain preferably has 10 to 100 carbon atoms, more preferably 12 to 100 carbon atoms, even more preferably 16 to 60 carbon atoms, and particularly preferably 18 to 40 carbon atoms.
The alkylene chain may be linear, branched, or cyclic, and from the viewpoint of improving the water repellency of the surface treatment layer, linear or branched is preferable, and linear is more preferable. .

<Substituent>
Chain Z may have a substituent. The substituent that chain Z has may be any group as long as it does not impair the purpose of the present disclosure, and examples include groups other than the reactive silyl group described below, and are specifically described as T ¹ in formula (1) described below. Examples include monovalent organic groups. The above substituent is bonded, for example, to the end of the chain Z that is opposite to the end bonded to the reactive silyl group via the linking group.
Note that when chain Z is an alkylene chain having 10 or more carbon atoms, the terminal of the above substituent that is bonded to the alkylene chain has a structure other than -CH ₂ -.

(Chain A)
The compounds of the present disclosure include a polyoxyalkylene chain (ie, chain A).
The number of chains A in the compound of the present disclosure may be 1 or more, and from the viewpoint of obtaining a surface treatment layer with excellent wear resistance, the number of chains A is preferably 1 to 3, more preferably 1 to 2, and even more preferably 1.

The number of atoms constituting the main chain in chain A is preferably 10 or more, more preferably 12 or more, even more preferably 16 or more, particularly preferably 18 or more, from the viewpoint of obtaining a surface treatment layer with excellent water repellency. In addition, the number of atoms constituting the main chain in chain A is preferably 500 or less, more preferably 250 or less, further preferably 100 or less, particularly preferably 50 or less, from the viewpoint of obtaining a surface treatment layer with excellent wear resistance. The number of constituent atoms of the main chain in chain A is preferably 10 to 500, more preferably 12 to 250, even more preferably 16 to 100, particularly preferably 18 to 50.
When the compound of the present disclosure has two or more chains A, the number of atoms constituting the main chain in the two or more chains A may be the same or different.
Note that the number of constituent atoms of the main chain in chain A means the total number of carbon atoms and oxygen atoms that constitute the main chain of the polyoxyalkylene chain.

The ratio N _A /N _Z between the number of atoms constituting the main chain in chain A and the number of atoms constituting the main chain in chain Z is not particularly limited, and may be in the range of 0.1 to 10, for example. From this point of view, the range is preferably from 0.2 to 5, and more preferably from 0.5 to 2.
Here, _NA is the number of atoms constituting the main chain in chain A, and when the compound of the present disclosure has two or more chains A, it represents the average number of atoms constituting the main chain in two or more chains A. Further, N _Z is the number of atoms constituting the main chain in chain Z, and when the compound of the present disclosure has two or more chains Z, it represents the average value of the number of atoms constituting the main chain in two or more chains Z.
When the chain Z included in the compound of the present disclosure is only a polydialkylsiloxane residue, the ratio N _A /N _Z is more preferably in the range of 0.6 to 1.7, and more preferably in the range of 0.8 to 1.3. is particularly preferred. Further, when the chain Z contained in the compound of the present disclosure is only an alkylene chain having 10 or more carbon atoms, the ratio N _A /N _Z is more preferably in the range of 0.6 to 1.7, and more preferably in the range of 0.7 to 1. A range of .4 is particularly preferred.

<Polyoxyalkylene chain>
The polyoxyalkylene chain is represented by the following formula (A).
( ^OXh ) _X3 ...(A)
In formula (A), X ^h is each independently an alkylene group, and X3 is an integer of 2 or more.

The number of carbon atoms in the alkylene group is preferably 1 to 6, more preferably 2 to 4, and even more preferably 2 from the viewpoint of improving the oil repellency of the surface treatment layer.
The alkylene group may be linear, branched, or cyclic. Among these, from the viewpoint of improving the oil repellency of the surface treatment layer, the alkylene group is preferably linear or branched. is more preferable.

Specific examples of (OX ^h ) include -OCH ₂ -, -OC ₂ H ₄ -, -OC ₃ H ₆ -, -OC ₄ H ₈ -, -OC ₅ H ₁₀ -, -OC ₆ H ₁₂ -, -OCH(CH ₃ )CH ₂ -, -OCH(CH ₃ )CH ₂ CH ₂ -, -O-cycloC ₄ H ₆ -, -O-cycloC ₅ H ₈ -, and -O-cycloC ₆ H ₁₀ - Can be mentioned.
Here, -cycloC ₄ H ₆ - means a cyclobutanediyl group. Examples of the cyclobutanediyl group include a cyclobutane-1,2-diyl group and a cyclobutane-1,3-diyl group. -cycloC ₅ H ₈ - means a cyclopentanediyl group. Examples of the cyclopentanediyl group include a cyclopentane-1,2-diyl group and a cyclopentane-1,3-diyl group. -cycloC ₆ H ₁₀ - means a cyclohexanediyl group. Examples of the cyclohexanediyl group include a cyclohexane-1,2-diyl group, a cyclohexane-1,3-diyl group, and a cyclohexane-1,4-diyl group.

The repetition number X3 of (OX ^h ) is an integer of 2 or more, preferably an integer of 3 or more, more preferably an integer of 3 to 200, even more preferably an integer of 5 to 150, an integer of 5 to 100. is particularly preferred, and an integer of 5 to 50 is most preferred.

The X3 X ^hs included in formula (A) may be the same or different. That is, (OX ^h ) _X3 may contain two or more types of (OX ^h ).
The order in which two or more types of (OX ^h ) are combined is not limited, and may be arranged randomly, alternately, or in blocks.
Containing two or more types of (OX ^h ) means that there are two or more types of (OX ^h ) with different numbers of carbon atoms in the compound, and even if the number of carbon atoms is the same, the presence or absence of side chains and the side This means that there are two or more types of (OX ^h ) having different chain types (for example, number of side chains, number of carbon atoms in side chains, etc.).
Regarding the arrangement of two or more types of (OX ^h ), for example, the structure represented by {(OCH ₂ ) _m21 (OC ₂ H ₄ ) _m22 } has m21 (OCH ₂ )s and m22 (OC _{2 H 4 )} H ₄ ) are randomly arranged. In addition, the structure represented by (OC ₂ H ₄ -OC ₃ H ₆ ) _m25 means that m25 (OC ₂ H ₄ ) and m25 (OC ₃ H ₆ ) are arranged alternately. represent.

_{Among them , ( OX} ^h _{) _ _ _ _ _ _ _ _ _ _ _ m16} (O-cycloC ₄ H ₆ ) _m17 (O-cycloC ₅ H ₈ ) _m18 (O-cycloC ₆ H ₁₀ ) _m19 ] are preferred.
m11, m12, m13, m14, m15, m16, m17, m18, and m19 are each independently an integer of 0 or more, and preferably 100 or less.
m11 + m12 + m13 + m14 + m15 + m16 + m17 + m18 + m19 is an integer of 2 or more, more preferably an integer of 2 to 200, more preferably an integer of 5 to 150, even more preferably an integer of 5 to 100, particularly preferably an integer of 10 to 50.

Among these, m12 is preferably an integer of 2 or more, particularly preferably an integer of 2 to 200.
In addition, C ₃ H ₆ , C ₄ H ₈ , C ₅ H ₁₀ , and C ₆ H ₁₂ may be linear or branched, but they may affect the oil repellency of the surface treatment layer. From the viewpoint of improvement, a straight chain shape is preferable.

Note that the above formula represents the type and number of units, but does not represent the arrangement of the units. That is, m11 to m19 represent the number of units; for example, (OCH ₂ ) _m11 does not represent a block containing m11 consecutive (OCH ₂ ) units. Similarly, the order in which (OCH ₂ ) to (O-cycloC ₆ H ₁₀ ) are written does not indicate that they are arranged in the order in which they are written.
In the above formula, when 2 or more of m11 to m19 are not 0 (that is, when ( _OX ^h ) or a combination of these arrangements.

(OX ^h ) _X3 preferably has the following structure.
(OC ₂ H ₄ ) _m21 ,
(OC ₃ H ₆ ) _m22 ,
(OC ₂ H ₄ ) _m23 (OC ₃ H ₆ ) _m24 ,
(OC ₂ H ₄ -OC ₃ H ₆ ) _m25 .
However, m21 is an integer of 2 or more, m22 is an integer of 2 or more, m23 and m24 are each independently an integer of 1 or more, m25 is an integer of 1 or more, and m26 and m27 are each an integer of 1 or more. independently an integer greater than or equal to 1;

From the viewpoint of improving the oil repellency of the surface treatment layer, the polyoxyalkylene chain preferably contains an oxyethylene unit represented by _OC2H4 , more preferably contains two or more oxyethylene units, and contains an oxyethylene unit _. It is more preferable to include in the range of 2 to 200. From the viewpoint of improving the oil repellency of the surface treatment layer, the polyoxyalkylene chain preferably includes a polyoxyethylene chain, and more preferably a polyoxyethylene chain.

<Substituent>
Chain A may have a substituent. The substituent that chain A has may be any group as long as it does not impair the purpose of the present disclosure, and examples include groups other than the reactive silyl group described below, and are specifically described as T ² in formula (1) described below. Examples include monovalent groups. The monovalent group is bonded, for example, to the end of chain A that is opposite to the end bonded to the reactive silyl group via the linking group.
Note that it is preferable that the terminal of the substituent group bonded to chain A has a structure other than -O-.

(Reactive silyl group)
Compounds of the present disclosure contain reactive silyl groups. The reactive silyl group is located at the end of the compound.
A 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 or a hydroxyl group.
A hydrolyzable group is a group that becomes a hydroxyl group through a hydrolysis reaction. That is, the hydrolyzable silyl group represented by Si-L becomes a silanol group represented by Si-OH through a hydrolysis reaction. The silanol groups further react among themselves to form Si--O--Si bonds. Further, the silanol group can undergo a dehydration condensation reaction with a silanol group derived from an oxide present on the surface of the base material to form a Si--O--Si bond. Examples of the hydrolyzable group include an alkoxy group, an aryloxy group, a halogen atom, an acyl group, an acyloxy group, and an isocyanato group (-NCO). The alkoxy group is preferably an alkoxy group having 1 to 4 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.
From the viewpoint of easy production of a uniform film and excellent durability, the reactive silyl group is preferably an alkoxysilyl group or a trichlorosilyl group. From the viewpoint of ease of handling by-products generated in the reaction with the base material, the reactive silyl group is more preferably an alkoxysilyl group. The alkoxysilyl group is preferably a dialkoxysilyl group or a trialkoxysilyl group, and more preferably a trialkoxysilyl group.

The number of reactive silyl groups possessed by the compound of the present disclosure is 1 or more, and from the viewpoint of further improving the wear resistance of the surface treatment layer, the number is preferably 1 to 18, more preferably 2 to 12, and 2 to 8. More preferred. The number of reactive silyl groups that the compound of the present disclosure has may be one.

As the reactive silyl group, a group represented by the following formula (2) is preferable.
-Si(R ¹ ) _n L ² _3-n (2)
In formula (2), R ¹ is each independently a monovalent hydrocarbon group, L ² is each independently a hydrolyzable group or a hydroxyl group, and n is an integer of 0 to 2.

When there are multiple reactive silyl groups in one molecule, the multiple reactive silyl groups may be the same or different from each other. From the viewpoint of easy availability of raw materials and ease of manufacturing the compound, it is preferable that the plurality of reactive silyl groups are the same.

Each R ¹ is independently a monovalent hydrocarbon group, and a monovalent saturated hydrocarbon group is preferable. The number of carbon atoms in R ¹ is preferably 1 to 6, more preferably 1 to 3, and even more preferably 1 to 2.

Each L ² is independently a hydrolyzable group or a hydroxyl group. As the hydrolyzable group, those mentioned above are preferred.

Among these, L ² is preferably an alkoxy group or a halogen atom, more preferably an alkoxy group having 1 to 4 carbon atoms or a halogen atom, from the viewpoint of ease of manufacturing the compound. L ² is preferably an alkoxy group having 1 to 4 carbon atoms, from the viewpoint of less outgassing during coating and better storage stability of the compound. When long-term storage stability of the compound is required, L ² is more preferably an ethoxy group. When the reaction time after coating is to be shortened, L ² is more preferably a methoxy group. In formula (2), at least one of L ² is preferably the above group, and more preferably all of L ² are the above groups.

n is an integer of 0 to 2, preferably 0 or 1, and more preferably 0. When the compound of the present disclosure is used as a surface treatment agent, the presence of a plurality of L ² makes the adhesion of the surface treatment layer to the base material stronger.
When n is 1 or less, the plurality of ^L2s present in one molecule may be the same or different from each other. From the viewpoint of easy availability of raw materials and ease of manufacturing the compound, it is preferable that the plurality of L ² 's are the same. When n is 2, a plurality of R ^1s present in one molecule may be the same or different from each other. From the viewpoint of easy availability of raw materials and ease of manufacturing the compound, it is preferable that a plurality of R ¹ 's are the same.

(Compound represented by formula (1))
The compound of the present disclosure is preferably a compound represented by the following formula (1) from the viewpoint of forming a surface treatment layer that has both water repellency and oil repellency.

 

In formula (1),
T ¹ and T ² are each independently a hydrogen atom or a monovalent group,
Z is each independently a polydialkylsiloxane residue or an alkylene chain having 10 or more carbon atoms,
A is a polyoxyalkylene chain,
Y ¹ is a (p+q+g)-valent linking group,
R ¹ is each independently a monovalent hydrocarbon group,
L ² is each independently a hydrolyzable group or a hydroxyl group,
p is an integer from 1 to 3,
q is an integer from 1 to 3,
n is an integer from 0 to 2,
g is an integer of 1 or more.

Since Z in formula (1) is the same as the polydialkylsiloxane residue or alkylene chain having 10 or more carbon atoms described above as chain Z, the explanation will be omitted. When p is 2 or more, two or more Z's contained in the compound represented by formula (1) may be the same or different from each other.
Since A in formula (1) is the same as the polyoxyalkylene chain described above as chain A, the explanation will be omitted. When q is 2 or more, two or more A's contained in the compound represented by formula (1) may be the same or different from each other.
R ¹ , L ² , and n in formula (1) are the same as R ¹ , L, and n in formula (2) described above as the reactive silyl group.

<T ¹ in formula (1)>
T ¹ in formula (1) each independently represents a hydrogen atom or a monovalent organic group. When p is 2 or more, two or more T ¹ 's contained in the compound represented by formula (1) may be the same or different from each other.

The monovalent organic group represented by T ¹ includes substituents such as an alkyl group, a fluoroalkyl group, a pentafluorosulfanyl group, a group -SiR ² ₃ , an aryl group, a fluoroaryl group, and a monovalent polysiloxane residue. , a combination of these substituents and a linking group, and the like. Note that R ² is a hydrocarbon group or a trialkylsilyloxy group.
Linking groups to be combined with the above substituents include alkylene groups, arylene groups, carbonyl groups, ether bonds, thioether bonds, sulfonyl groups, -NR ⁴ -, -SiR ⁴ ₂ -, and the like. Note that R ⁴ is a hydrogen atom or a hydrocarbon group. Two or more of these linking groups may be used in combination, or two or more types of these linking groups may be used in combination. Examples of the linking group that is a combination of two or more of the above linking groups include an ester bond, a thioester bond, an amide bond, a sulfonamide bond, a combination of an arylene group and an ether bond, and the like.
Combinations of the above substituents and linking groups include combinations of alkyl groups and ether bonds, combinations of fluoroalkyl groups and ether bonds, combinations of aryl groups and ether bonds, combinations of fluoroaryl groups and ether bonds, Examples include a combination of a pentafluorosulfanyl group and an arylene group, a combination of a pentafluorosulfanyl group, an arylene group, and an ether bond, a combination of a monovalent polysiloxane residue and an alkylene group, and the like.

The alkyl group that can be included in the monovalent organic group represented by T ¹ may be any of a linear alkyl group, a branched alkyl group, and a cyclic alkyl group, and among them, a linear alkyl group Alternatively, a cyclic alkyl group is preferable, and a linear alkyl group is more preferable. The number of carbon atoms in the alkyl group is, for example, 1 to 6, preferably 1 to 4. The alkyl group is more preferably a methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, or n-hexyl group, and a methyl group, ethyl group, n-propyl group, or n-butyl group is even more preferable.

The fluoroalkyl group that may be included in the monovalent organic group represented by T ¹ may be linear, branched, or cyclic, and among these, a linear fluoroalkyl group is preferred; A linear perfluoroalkyl group is more preferred. The number of carbon atoms in the fluoroalkyl group is, for example, 1 to 5, preferably 1 to 3, more preferably 1 to 2, and even more preferably 1. The fluoroalkyl group is more preferably a trifluoromethyl group, a pentafluoroethyl group, an n-heptafluoropropyl group, or an n-nonafluorobutyl group, and even more preferably a trifluoromethyl group.

Examples of the hydrocarbon group represented by R ² of the group -SiR ² ₃ that can be included in the monovalent organic group represented by T ¹ 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 preferable, and a methyl group, ethyl group, n-propyl group, or n -butyl group is more preferred, and methyl group is even more preferred.

The alkyl group contained in the trialkylsilyloxy group represented by R ² may be any of a linear alkyl group, a branched alkyl group, and a cyclic alkyl group, but a linear alkyl group is preferable. , methyl group, ethyl group, n-propyl group, or n-butyl group, and even more preferably methyl group. When R ² is a trialkylsilyloxy group, the three alkylsilyloxy groups may be the same or different from each other, but from the viewpoint of ease of production, they are preferably the same.
The trialkylsilyloxy group represented by R ² is preferably a trimethylsilyloxy group, a triethylsilyloxy group, a tri-n-propylsilyloxy group, or a tri-n-butylsilyloxy group, and more preferably a trimethylsilyloxy group.

Examples of the group -SiR ² ₃ include methyldiethylsilyl group, methylethylpropylsilyl group, methylethylbutylsilyl group, methyldipropylsilyl group, methylpropylbutylsilyl group, methyldibutylsilyl group, dimethylethylsilyl group, dimethyl Examples include a propylsilyl group, a dimethylbutylsilyl group, a trimethylsilyl group, and a trialkylsilyloxysilyl group having these groups.
Among these, from the viewpoint of improving the water repellency of the surface treatment layer, the group -SiR ² ₃ is preferably a trialkylsilyloxysilyl group, more preferably a trimethylsilyloxysilyl group.

The aryl group that can be included in the monovalent organic group represented by T ¹ is a group obtained by removing one hydrogen from an aromatic ring.
The aromatic ring may be monocyclic or polycyclic, and is preferably monocyclic from the viewpoint of liquid repellency.
Examples of the aromatic ring include a benzene ring, a naphthalene ring, a fluorene ring, an anthracene ring, a furan ring, a thiophene ring, and a pyridine ring.

Examples of the fluoroaryl group that can be included in the monovalent organic group represented by T ¹ include a group in which the hydrogen atom of the above aryl group is replaced with a fluorine atom. The number of fluorine atoms that the fluoroaryl group has is not particularly limited.
The fluoroaryl group is preferably a perfluoroaryl group, and more preferably a pentafluorophenyl group.

Examples of the monovalent polysiloxane residue that can be included in the monovalent organic group represented by T ¹ include monovalent cyclic polysiloxane residues.
Examples of the monovalent cyclic polysiloxane residue include a group represented by the following formula (T1).
In formula (T1), R ⁵ is each independently an alkyl group or an alkyl group having a substituent, and s is an integer of 1 to 4.

 

The alkyl group represented by R ⁵ may be any of a linear alkyl group, a branched alkyl group, and a cyclic alkyl group, but a linear alkyl group is preferable. The alkyl group preferably has 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms, and even more preferably 1 to 4 carbon atoms. Specifically, the alkyl group represented by R ⁵ is preferably a methyl group, an ethyl group, an n-propyl group, or an n-butyl group, and more preferably a methyl group.

The alkyl group contained in the substituted alkyl group represented by R ⁵ may be any of a linear alkyl group, a branched alkyl group, and a cyclic alkyl group, but a linear alkyl group is preferable. 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.

Examples of the substituent in the substituted alkyl group represented by ^R5 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 trimethylsilyl group. Examples include fluoromethyl group.

A plurality of R ⁵ 's may be the same or different from each other, but from the viewpoint of ease of manufacture, it is preferable that they are the same.

Examples of monovalent cyclic polysiloxane residues include the following groups.

 

The alkylene group that can be included in the monovalent organic group represented by T ¹ may be linear, branched, or cyclic, and among them, linear or branched is preferable. Straight chain is more preferable. The number of carbon atoms in the alkylene group is, for example, 1 to 5, preferably 1 to 3, and more preferably 1 to 2.
The arylene group that can be included in the monovalent organic group represented by T ¹ is a group obtained by removing two hydrogen atoms from an aromatic ring, and the aromatic ring is as described above.
Hydrocarbon groups represented by R ⁴ of -NR ⁴ - and -SiR ⁴ ₂ - that may be included in the monovalent organic group represented by T ¹ include, for example, aliphatic hydrocarbon groups and aromatic hydrocarbon groups. Examples include groups. 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 preferable, and a methyl group, ethyl group, n-propyl group, or n -butyl group is more preferred, and methyl group is even more preferred.

When Z in formula (1) is a polydialkylsiloxane residue, ^T1 in formula (1) is an alkyl group, a group represented by formula (T1), and an ether bond, from the viewpoint of ease of manufacturing the compound. or a combination of a group represented by formula (T1) and an alkylene group, preferably an alkyl group, represented by formula (T1), where s is 2 and R ⁵ is a methyl group. A group combining a group and an ether bond, or a group combining an alkylene group and a group represented by formula (T1) in which s is 2 and R ⁵ is a methyl group are more preferable, and an alkyl group or a group of the formula ( More preferred is a group represented by T1) in which s is 2 and R ⁵ is a methyl group in combination with an ethylene group.

When Z in formula (1) is an alkylene chain, T ¹ in formula (1) is a hydrogen atom, a fluoroalkyl group, a pentafluorosulfanyl group, a group -SiR ² ₃ , an aryl group, from the viewpoint of ease of manufacturing the compound. A fluoroaryl group, a fluoroalkyloxy group, an aryloxy group, a fluoroaryloxy group, an alkylaryl group, an alkylaryloxy group, a fluoroalkylaryloxy group, a pentafluorosulfanylaryl group, or a pentafluorosulfanylaryloxy group are preferred. , a hydrogen atom, a fluoroalkyl group, a phenyl group, a fluoroalkyloxy group, a phenyloxy group, a pentafluorosulfanylphenyl group, or a pentafluorosulfanylphenyloxy group. When Z in formula (1) is an alkylene chain, T ¹ in formula (1) has a structure in which the terminal bonded to chain Z is other than -CH ₂ -.

Specific examples of the monovalent organic group represented by T ¹ include organic groups having the following structure. The monovalent organic group represented by T ¹ is not limited to the specific examples below. However, in the following formula, a is each independently an integer of 1 to 5, preferably an integer of 1 to 3. In the following formula, Ph represents a benzene ring, and when it is monovalent, it is a phenyl group, and when it is divalent, it is a phenylene group. In the following formula, * is a bond bonding to chain Z.
* _-CH3 ,
*-(CH ₂ ) _a -CH ₃ ,
*-O-CH ₃ ,
*-O-(CH ₂ ) _a -CH ₃ ,
* _-CF3 ,
*-(CF ₂ ) _a -CF ₃ ,
*-O-CF ₃ ,
*-O-(CF ₂ ) _a -CF ₃ ,
*-Ph,
*-O-Ph,
*-Ph-CH ₃ ,
*-O-Ph-CH ₃ ,
*-SF ₅ ,
*-Ph-SF ₅ ,
*-O-Ph-SF ₅ ,

 

<T ² in formula (1)>
T ² in formula (1) each independently represents a hydrogen atom or a monovalent group. When q is 2 or more, two or more T ² 's contained in the compound represented by formula (1) may be the same or different from each other. T ² in formula (1) is bonded to the oxygen atom of chain A.

Monovalent groups represented by T ² include substituents such as alkyl groups, fluoroalkyl groups, hydroxy groups, amino groups, thiol groups, and -PO ₃ H ₂ groups, and combinations of these substituents and linking groups. Examples include groups such as
Linking groups that can be combined with the above substituents include alkylene groups, carbonyl groups, ether bonds, thioether bonds, sulfonyl groups, -NR ⁷ -, and the like. Note that R ⁷ is a hydrogen atom or a hydrocarbon group. Two or more of these linking groups may be used in combination, or two or more types of these linking groups may be used in combination. Examples of the linking group that is a combination of two or more of the above linking groups include an ester bond, a thioester bond, an amide bond, and a sulfonamide bond.
Combinations of the above substituents and linking groups include a combination of a hydroxy group, a carbonyl group, and an alkylene group (for example, a combination of a carboxy group and an alkylene group), a combination of an amino group and a carbonyl group, and a combination of an amino group and a carbonyl group. and an alkylene group, a combination of a hydroxy group and a sulfonyl group (ie, a sulfo group), a combination of a hydroxy group, a sulfonyl group, and an ether bond, and the like.

The alkyl group that can be included in the monovalent group represented by T ² may be any of a linear alkyl group, a branched alkyl group, and a cyclic alkyl group, and among them, a linear alkyl group is preferable. The number of carbon atoms in the alkyl group is, for example, 1 to 5, preferably 1 to 3, more preferably 1 to 2, and even more preferably 1. The alkyl group is preferably a methyl group, ethyl group, n-propyl group, or n-butyl group, more preferably a methyl group or ethyl group, and even more preferably a methyl group.

The fluoroalkyl group that can be included in the monovalent group represented by T ² may be linear, branched, or cyclic, and among these, a linear fluoroalkyl group is preferable, and a linear fluoroalkyl group is preferable. A perfluoroalkyl group is more preferred. The number of carbon atoms in the fluoroalkyl group is, for example, 1 to 5, preferably 1 to 3, more preferably 1 to 2, and even more preferably 1. The fluoroalkyl group is more preferably a trifluoromethyl group, a pentafluoroethyl group, an n-heptafluoropropyl group, or an n-nonafluorobutyl group, and even more preferably a trifluoromethyl group.

The amino group that can be included in the monovalent group represented by T ² may be a group -NR ⁷ ₂ . Here, R ⁷ is each independently a hydrogen atom or a monovalent hydrocarbon group, preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and more preferably a hydrogen atom or a methyl group. preferable. The above amino group is preferably a group -NH ₂ , a group -NH(CH ₃ ), a group -N(CH ₃ ) ₂ , and more preferably a group -NH ₂ .
The alkylene group that can be included in the monovalent group represented by T ² may be linear, branched, or cyclic, and among these, linear is preferable. The number of carbon atoms in the alkylene group is, for example, 1 to 5, preferably 1 to 3, more preferably 1 to 2, and even more preferably 1.
The hydrocarbon group represented by R ⁷ of -NR ⁷ - that may be included in the monovalent organic group represented by T ² includes an alkyl group having 1 to 3 carbon atoms, and is preferably a methyl group. preferable.

Specific examples of the monovalent group represented by T ² include groups having the following structure. The monovalent group represented by T ² is not limited to the specific examples below. However, in the following formula, a is each independently an integer of 1 to 5, preferably an integer of 1 to 3. In the following formula, * is a bond that binds to chain A.
* _-CH3 ,
*-(CH ₂ ) _a -CH ₃ ,
*-(CH ₂ ) _a -SH,
*-(CH ₂ ) _a -CO-OH,
*-CO-NH ₂ ,
*-(CH ₂ ) _a -CO-NH ₂ ,
*-PO ₃ H ₂ ,
* _-SO3H ,
*-( _CH2 ) _a - _SO3H .

<p and q in formula (1)>
In formula (1), p is an integer of 1 to 3, preferably an integer of 1 to 2, and more preferably 1, from the viewpoint of improving the water repellency and oil repellency of the surface treatment layer.
In formula (1), q is an integer of 1 to 3, preferably an integer of 1 to 2, and more preferably 1, from the viewpoint of improving the water repellency and oil repellency of the surface treatment layer.
In formula (1), p and q are both preferably integers of 1 to 2, more preferably both are 1.

<Y ¹ (-Si(R ¹ ) _n L ² _3-n ) _g in formula (1)>
Y ¹ is a (p+q+g)-valent linking group.
Y ¹ is preferably a linking group represented by the following formula (Y1-1) or formula (Y1-2). That is, the compound (1) is preferably a compound represented by the following formula (3-1) or formula (3-2).

 

In the above formula, ^Z * represents the bonding position with Z, ^A * represents the bonding position with A, * ^Si represents the bonding position with the reactive silyl group, and L ³ and L ⁴ each independently represent It represents a bond or a divalent linking group, L ⁶ represents a single bond or an alkylene group, Y ¹¹ represents a single bond or a (g+1) valent linking group, and Y ¹² represents a (p+q+g) valent linking group.
In the above formula, the definitions of T ¹ , T ² , Z, A, R ¹ , L ² , p, q, n, and g are the same as in formula (1), respectively.
In the above formula, L ⁵ is a carbon atom, a nitrogen atom, a silicon atom, a (p+q+1)-valent organopolysiloxane residue, a (p+q+1)-valent ring, or the remaining bond thereof is bonded to a hydrogen atom or a substituent. This is the basis.

When L ⁵ is a carbon atom or a silicon atom, p+q+1 is 4, and when L ⁵ is a carbon atom or silicon atom whose remaining bond is a hydrogen atom or a group bonded to a substituent, p+q+1 is 3. .
When L ⁵ is a nitrogen atom, both p and q are 1.
When L ⁵ is a (p+q+1)-valent ring and there are remaining bonds among the bonds that do not form a ring in the atoms that make up the ring, the remaining bonds are bonded to a hydrogen atom or a substituent.
The substituents bonded to the remaining bonds include halogen atoms, alkyl groups (which may contain an ether oxygen atom between carbon atoms), cycloalkyl groups, alkenyl groups, allyl groups, and alkoxy groups. , oxo group (=O), and the like.
Details of the organopolysiloxane residue and ring represented by L ⁵ are the same as those of the organopolysiloxane residue and ring represented by X ³¹ , which will be described later.
Among these, L ⁵ is preferably a carbon atom.

The divalent linking groups represented by L ³ and L ⁴ include alkylene groups, carbonyl groups, ether bonds, thioether bonds, sulfonyl groups, -NR ⁴ -, -SiR ⁴ ₂ -, and combinations of two or more of these. The following groups are mentioned. The above R ⁴ is a hydrogen atom or a hydrocarbon group.
In addition, examples of the group that is a combination of two or more of the above-mentioned groups include an ester bond, a thioester bond, an amide bond, a sulfonamide bond, a combination of an alkylene group and an ether bond, and the like.

The alkylene group that can be included in the divalent linking group represented by L ³ and L ⁴ may be either linear or branched, with linear being preferred. The number of carbon atoms in the alkylene group is, for example, 1 to 6, preferably 1 to 4, and more preferably 2 to 3. The alkylene group may have 1 to 30 carbon atoms, 4 to 20 carbon atoms, or 5 to 15 carbon atoms.
Examples of the hydrocarbon group represented by R ⁴ of -NR ⁴ - and -SiR ⁴ ₂ - which may be included in the divalent linking group represented by L ³ and L ⁴ include an aliphatic hydrocarbon group. and an alkyl group is preferred. 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 preferable, and a methyl group, ethyl group, n-propyl group, or n -butyl group is more preferred, and methyl group is even more preferred.

When Z is a polydialkylsiloxane residue, ^L3 bonded to the polydialkylsiloxane residue is preferably an alkylene group or a combination of an alkylene group and an ether bond.
Specific examples of L ³ bonded to the polydialkylsiloxane residue include linking groups having the following structure. The divalent linking group represented by L ³ is not limited to the specific examples below. However, in the following formula, a is each independently an integer of 1 to 5, preferably an integer of 1 to 3. In the following formula, b is an integer of 1 to 3, preferably an integer of 1 to 2, and more preferably 1. In the following formula, ^Z * represents the bonding position with Z, and * ^Y represents the bonding position with ^Y11 .
^Z *-( _CH2 ) _a- * ^Y ,
^Z *-CH ₂ -{O-(CH ₂ ) _a } _b -* ^Y ,

When Z is an alkylene chain, L ³ bonded to the alkylene chain is preferably a single bond.
^L4 bonded to chain A is preferably a single bond.

The alkylene group represented by L ⁶ may be either linear or branched, with linear being preferred. The number of carbon atoms in the alkylene group is, for example, 1 to 6, preferably 1 to 4, and more preferably 2 to 3.
When L ⁵ is a carbon atom or a group in which the remaining bond is bonded to a hydrogen atom or a substituent, L ⁶ is preferably a single bond or an alkylene group having 1 to 4 carbon atoms, and more preferably a single bond.
When L ⁵ is a nitrogen atom, a silicon atom, a (p+q+1)-valent organopolysiloxane residue, a (p+q+1)-valent ring, or a group in which the remaining bond is a hydrogen atom or a group bonded to a substituent, L ⁶ is preferably an alkylene group, more preferably an alkylene group having 1 to 4 carbon atoms.

Y ¹¹ is a single bond or a (g+1)-valent linking group. However, when Y ¹¹ is a single bond, g=1. Y ¹¹ is, for example, a group containing an etheric oxygen atom or an alkylene group which may have a divalent organopolysiloxane residue, a carbon atom, a nitrogen atom, a silicon atom, or a divalent to octavalent organopolysiloxane. Si(R ¹ ) _n L ² _3-n from the residue and formula (3-1A), formula (3-1B), or formula (3-1A-1) to (3-1A-8) described later Examples include groups excluding . However, when L ⁵ is a nitrogen atom and L ⁶ is a single bond, this excludes the case where the terminal of Y ¹¹ that is bonded to L ⁵ , which is a nitrogen atom, is a nitrogen atom.
Y ¹² is a (p+q+g)-valent linking group. Y ¹² is, for example, a group containing an etheric oxygen atom or an alkylene group which may have a divalent organopolysiloxane residue, a carbon atom, a nitrogen atom, a silicon atom, a divalent to octavalent organopolysiloxane. Examples include residues, groups (g2-1) to (g2-5) and groups (g2-8) to (g2-12), which will be described later.

g is an integer of 1 or more. In one embodiment, g is preferably from 1 to 15, more preferably from 1 to 6, from the viewpoint of the abrasion resistance and fingerprint removability of the surface treatment layer. In one embodiment, g is preferably 2 or more, more preferably 2 to 4, and even more preferably 2 or 3 from the viewpoint of excellent wear resistance of the surface treatment layer. In one embodiment, g is preferably 1 to 3, more preferably 1 or 2, and even more preferably 1 from the viewpoint of excellent fingerprint removability of the surface treatment layer.

When g is 2 or more, two or more (-Si(R ¹ ) _n L ² _3-n ) contained in the compound represented by formula (1) may be the same or different from each other. Good too.

The group represented by Y ¹¹ (-Si(R ¹ ) _n L ² _3-n ) _g in formula (3-1) is preferably group (3-1A) or group (3-1B), and group (3-1A) or group (3-1B) is preferable. -1A) is more preferred.

-Q ^a -X ³¹ (-Q ^b -Si(R ¹ ) _n L ² _3-n ) _h (-R ³¹ ) _i ...(3-1A)
-Q ^c -[CH ₂ C(R ³² )(-Q ^d -Si(R ¹ ) _n L ² _3-n )] _y -R ³³
...(3-1B)

Note that the terminal of group (3-1A) or group (3-1B) that is bonded to L ⁶ - in formula (3-1) is not -CH ₂ -.

In formula (3-1A),
Q ^a is a single bond or a divalent linking group,
X ³¹ is a group having a single bond, an alkylene group, a carbon atom, a nitrogen atom, a silicon atom, a 2- to 8-valent organopolysiloxane residue, or a (h+i+1)-valent ring,
Q ^b is a single bond or a divalent linking group,
R ³¹ is a hydrogen atom, a hydroxyl group or an alkyl group,
h is an integer of 1 or more, i is an integer of 0 or more,
The definitions and specific examples of R ¹ , L ² , and n are the same as the definitions and specific examples of each symbol in the reactive silyl group.

In formula (3-1B),
Q ^c is a single bond or a divalent linking group,
R ³² is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms,
Q ^d is a single bond or an alkylene group,
R ³³ is a hydrogen atom or a halogen atom,
y is an integer from 1 to 10,
The definitions and specific examples of R ¹ , L ² , and n are the same as the definitions and specific examples of each symbol in the reactive silyl group.

Q ^a is a single bond or a divalent linking group.
Examples of divalent linking groups include divalent hydrocarbon groups, divalent heterocyclic groups, -O-, -S-, -SO ₂ -, -N(R ^d )-, -C(O) -, -Si(R ^a ) ₂ -, and a combination of two or more thereof.
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 includes, for example, an alkylene group. The divalent saturated hydrocarbon group preferably has 1 to 20 carbon atoms. Furthermore, the divalent aromatic hydrocarbon group preferably has 5 to 20 carbon atoms, such as a phenylene group. In addition, the divalent hydrocarbon group may be an alkenylene group having 2 to 20 carbon atoms or an alkynylene group having 2 to 20 carbon atoms.
The above R ^a is an alkyl group (preferably having 1 to 10 carbon atoms) or a phenyl group. The above R ^d is a hydrogen atom or an alkyl group (preferably having 1 to 10 carbon atoms).
Examples of groups combining two or more of the above include -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 )-alkylene group-, -N(R ^d )C(O) -alkylene group-, -(poly)oxyalkylene group-, -OC(O)-alkylene group-, -C(O)O-alkylene group-, -C(O)S-alkylene group-, -SO ₂ N (R ^d )-alkylene group-, -Si(R ^a ) ₂ -phenylene group-Si(R ^a ) ₂ , and the like.
In one embodiment, Q ^a is a single bond, -O-, -S-, -N(R ^d )-, -C(O)N(R ^d )-, -OC(O)N(R ^d ) -, -C(O)O-, -OC(O)-, and -C(O)S- are preferred, and single bonds, -C(O)N(R ^d )-, -OC(O)N( R ^d )-, -C(O)O-, and -OC(O)- are more preferred.

X ³¹ is a group having a single bond, an alkylene group, a carbon atom, a nitrogen atom, a silicon atom, a 2- to 8-valent organopolysiloxane residue, or a (h+i+1)-valent ring.
The alkylene group may have -O-, a silphenylene skeleton group, a divalent organopolysiloxane 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 organopolysiloxane residue, and a dialkylsilylene group.
The alkylene group represented by X ³¹ preferably has 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms.
Examples of the divalent to octavalent organopolysiloxane residues include divalent organopolysiloxane residues and (2w+1)-valent organopolysiloxane residues described below.

When X ³¹ is a group having a (h+i+1)-valent ring, Q ^a , (-Q ^b -Si(R ¹ ) _n L ² _3-n ), and -R ³¹ (when i=1 or more) are It is directly bonded to the atoms constituting the ring. However, the ring is a ring other than an organopolysiloxane ring. Hereinafter, unless otherwise specified, the ring in X ³¹ means a ring other than an organopolysiloxane ring.
The ring in X ³¹ may be a monocyclic ring, a fused polycyclic ring, a bridged ring, a spiro ring, or an assembled polycyclic ring, and the atoms constituting the ring may be a carbocyclic ring consisting only of carbon atoms, or a divalent ring. A heterocycle consisting of a heteroatom having the above valence and a carbon atom may also be used. Further, the bond between 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.
The monocyclic ring is preferably a 4- to 8-membered ring, more preferably a 5-membered ring or a 6-membered ring. The fused polycyclic ring is preferably a fused polycyclic ring in which two or more 4- to 8-membered rings are fused together, and fused polycyclic rings in which 2 or 3 rings selected from 5-membered rings and 6-membered rings are bonded together; A fused polycyclic ring in which one or two rings selected from membered rings and six-membered rings and one four-membered ring are bonded is more preferred. The bridged ring is preferably a bridged ring whose largest ring is a 5- or 6-membered ring, and the spiro ring is preferably a spiro ring consisting of two 4- to 6-membered rings. As a collective polycyclic ring, two or three rings selected from 5-membered rings and 6-membered rings are bonded via a single bond, 1 to 3 carbon atoms, or 1 heteroatom with a valence of 2 or 3. A set of polycyclic rings is preferred. In addition, in a set polycycle, either Q ^a , (-Q ^b -Si(R ¹ ) _n L ² _3-n ), or R ³¹ (when i=1 or more) is bonded to each ring. It is preferable.
The hetero atoms constituting the ring are preferably nitrogen atoms, oxygen atoms, and sulfur atoms, and more preferably nitrogen atoms and oxygen atoms. The number of heteroatoms constituting the ring is preferably 3 or less. Furthermore, when the number of heteroatoms constituting the ring is two or more, these heteroatoms may be the same or different.

As the ^ring in A heterocycle of a membered ring, a condensed ring in which two or three of these rings are fused together, a bridged ring in which the largest ring is a 5- or 6-membered ring, and two or more of these rings One type selected from the group consisting of a single bond, an alkylene group having 3 or less carbon atoms, an oxygen atom, or a sulfur atom as a linking group is preferable.
Preferred rings include a benzene ring, a 5- or 6-membered aliphatic ring, a 5- or 6-membered heterocycle having a nitrogen atom or an oxygen atom, and a 5- or 6-membered carbon ring and a 4- to 6-membered heterocycle. It is a fused ring with a ring.
Specific rings include the rings shown below, 1,3-cyclohexadiene ring, 1,4-cyclohexadiene ring, anthracene ring, cyclopropane ring, decahydronaphthalene ring, norbornene ring, norbornadiene ring, furan ring, Examples include 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. In addition, below, a ring having an oxo group (=O) is also shown.

 

^The bond ^{that does} _not constitute a ring of ^the atom that _constitutes the ^{ring in} The remaining bonds, if any, are bonded to hydrogen atoms or substituents. 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). etc.
In addition, a bond in which one of the carbon atoms constituting the ring can be bonded to Q ^a , (-Q ^b -Si(R ¹ ) _n L ² _3-n ), or -R ³¹ (when i = 1 or more) , even if any two of Q ^a , (-Q ^b -Si(R ¹ ) _n L ² _3-n ), and -R ³¹ are bonded to that one carbon atom. good. It is preferable that Q ^a and Q ^b are bonded to different ring constituent atoms. Each of the i R ^31s may be bonded to a separate ring atom, or two of the i R ^31s may be bonded to one ring carbon atom. There may be two or more ring-constituting carbon atoms to which two R ^31s are bonded.

Among these, X ³¹ is a group having a carbon atom, a nitrogen atom, a silicon atom, a 4- to 8-valent organopolysiloxane residue, or a (h+i+1)-valent ring, from the viewpoint of improving the abrasion resistance of the surface treatment layer. is preferable, and carbon atom is more preferable.

Q ^b is a single bond or a divalent linking group.
Examples of divalent linking groups include divalent hydrocarbon groups, divalent heterocyclic groups, -O-, -S-, -SO ₂ -, -N(R ^d )-, -C(O) -, -Si(R ^a ) ₂ -, and a combination of two or more thereof.
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 includes, for example, an alkylene group. The number of carbon atoms in the divalent saturated hydrocarbon group is preferably 1 to 30, more preferably 1 to 20, even more preferably 2 to 20, and examples thereof include 2, 3, 8, 9, and 11. Furthermore, the divalent aromatic hydrocarbon group preferably has 5 to 20 carbon atoms, such as a phenylene group. In addition, the divalent hydrocarbon group may be an alkenylene group having 2 to 20 carbon atoms or an alkynylene group having 2 to 20 carbon atoms.
The above R ^a is an alkyl group (preferably having 1 to 10 carbon atoms) or a phenyl group. The above R ^d is a hydrogen atom or an alkyl group (preferably having 1 to 10 carbon atoms).
Examples of groups combining two or more of the above include -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 )-, -N(R ^d )C(O )-, an alkylene group having an etheric oxygen atom, an alkylene group having -OC(O)-, an alkylene group having -C(O)O-, a -C(O)S-alkylene group, - Examples include an alkylene group having SO ₂ N(R ^d )-, an alkylene group -Si(R ^a ) ₂ -phenylene group -Si(R ^a ) ₂ , and the like.
In one embodiment, Q ^c is a single bond, -O-, -S-, -N(R ^d )-, -C(O)N(R ^d )-, -OC(O)N(R ^d ) -, -C(O)O-, -OC(O)-, and -C(O)S- are preferred, and single bonds, -OC(O)N(R ^d )-, and -OC(O)- is more preferable.

R ³¹ is a hydrogen atom, a hydroxyl group or an alkyl group.
The number of carbon atoms in the alkyl group is preferably 1 to 5, more preferably 1 to 3, and even more preferably 1.

h is an integer greater than or equal to 1, and i is an integer greater than or equal to 0.
When X ³¹ is a single bond or an alkylene group, h is 1 and i is 0.
When X 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.
When X ³¹ 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.
When X ³¹ is a divalent to octavalent organopolysiloxane residue, h is an integer of 1 to 7, i is an integer of 0 to 6, and h+i=1 to 7 is satisfied.
When X 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.
If there are two or more (-Q ^b -Si(R ¹ ) _n L ² _3-n ), two or more (-Q ^b -Si(R ¹ ) _n L ² _3-n ) are the same. It may be different or different. When there are two or more R ³¹ s, two or more (-R ³¹ )s may be the same or different.

Among these, i is preferably 0 from the viewpoint of improving the wear resistance of the surface treatment layer.

Q ^c is a single bond or a divalent linking group.
The definition and details of the divalent linking group are the same as those explained in Q ^a above.

R ³² is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and is preferably a hydrogen atom from the viewpoint of easy production of the compound.
As the alkyl group, a methyl group is preferred.

Q ^d is a single bond or an alkylene group. The alkylene group preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms. From the viewpoint of easy production of the compound, Q ^d is preferably a single bond or -CH ₂ -.

R ³³ is a hydrogen atom or a halogen atom, and is preferably a hydrogen atom from the viewpoint of easy production of the compound.

y is an integer from 1 to 10, preferably from 1 to 6.
Two or more [CH ₂ C(R ³² )(-Q ^d -Si(R ¹ ) _n L ² _3-n )] may be the same or different.

As the group (3-1A), groups (3-1A-1) to (3-1A-8) are preferable.
-(X ³² ) _s1 -Q ^b1 -Si(R ¹ ) _n L ² _3-n ...(3-1A-1)
-(X ³³ ) _s2 -Q ^a2 -N [-Q ^b2 -Si(R ¹ ) _n L ² _3-n ] ₂ ...(3-1A-2)
-Q ^a3 -Si(R ^g ) [-Q ^b3 -Si(R ¹ ) _n L ² _3-n ] ₂ ...(3-1A-3)
-[Q ^e ] _s4 -Q ^a4 -(O) _t4 -C[-(O) _u4 -Q ^b4 -Si(R ¹ ) _n L ² _3-n ] _3-w1 (-R ³¹ ) _w1 ...(3 -1A-4)
-Q ^a5 -Si[-Q ^b5 -Si(R ¹ ) _n L ² _3-n ] ₃ ...(3-1A-5)
-[Q ^e ] _v -Q ^a6 -Z ^a [-Q ^b6 -Si(R ¹ ) _n L ² _3-n ] _w2 ...(3-1A-6)
-[Q ^e ] _s4 -Q ^a4 -(O) _t4 -Z ^c [-(O-Q ^b4 ) _u4 -Si(R ¹ ) _n L ² _3-n ] _w3 (-OH) _w4 ...(3-1A -7)
-X ³⁴ -Q ^a7 -Z ^d [-Q ^b7 -Si(R ¹ ) _n L ² _3-n ] _h3 ...(3-1A-8)

Note that in formulas (3-1A-1) to (3-1A-8), the definitions of R ¹ , L ² , and n are as described above.
Further, among formulas (3-1A-1) to (3-1A-8), the terminal bonded to L ⁶ - in formula (3-1) is not -CH ₂ -.

In the group (3-1A-1), X ³² is -O-, -C(O)-, -C(O)O-, -SO ₂ N(R ^d )-, -N(R ^d )SO ₂ -, -N(R ^d )C(O)-, -C(O)N(R ^d )-, -OC(O)-, -OC(O)N(R ^d )-, -S-, -C(O)S-, or -N(R ^d )- (however, N in the formula is bonded to Q ^b1 ).
The definition of R ^d is as described above.
s1 is 0 or 1.

Q ^b1 is a single bond, or -O-, a silphenylene skeleton group, a divalent organopolysiloxane residue or a dialkylsilylene group, -O-, a silphenylene skeleton group, a divalent organopolysiloxane residue, A group in which an alkylene group which may have a dialkylsilylene group is bonded, a phenylene group, or a group in which an alkylene group is bonded to a phenylene group.

Q ^b1 is a single bond, -OCH ₂ CH ₂ CH ₂ -, -OCH ₂ CH ₂ OCH ₂ CH ₂ CH ₂ -, and -OCH ₂ CH ₂ CH ₂ Si (CH ₃ ) when s1 is 0. ₂ OSi(CH ₃ ) ₂ CH ₂ CH ₂ - is preferred.
When (X ³² ) _s1 is -O-, -CH ₂ CH ₂ CH ₂ - and -CH ₂ CH ₂ OCH ₂ CH ₂ CH ₂ - are preferred. When (X ³² ) _s1 is -C(O)N(R ^d )-, it is preferably an alkylene group having 2 to 6 carbon atoms (however, N in the formula is bonded to Q ^b1 ). When (X ³² ) _s1 is -C(O)O-, it is preferably an alkylene group having 2 to 6 carbon atoms. When (X ³² ) _s1 is -C(O)-, it is preferably an alkylene group having 2 to 6 carbon atoms. When Q ^b1 is one of these groups, the compound can be easily produced.

Specific examples of the group (3-1A-1) include the following groups. In the following formula, * represents the bonding position with L ⁶ in formula (3-1).

 

 

 

In the group (3-1A-2), X ³³ is -O-, -NH-, -C(O)O-, -SO ₂ N(R ^d )-, -N(R ^d )SO ₂ -, -N(R ^d )C(O)- or -C(O)N(R ^d )-.
The definition of R ^d is as described above.

Q ^a2 is a single bond, an alkylene group, -C(O)-, or an etheric oxygen atom, -C(O)-, -C(O) between carbon atoms of an alkylene group having 2 or more carbon atoms. )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) A group having N(R ^d )- or -NH-.
The alkylene group represented by Q ^a2 preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms.
Ether oxygen atom, -C(O)-, -C(O)O-, -OC(O)-, -C between the carbon atoms of the alkylene group having 2 or more carbon atoms represented by Q ^a2 (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- The number of carbon atoms in the group having is preferably 2 to 10, more preferably 2 to 6.

Q ^a2 is -CH ₂ -, -CH 2 CH 2 -, -CH ₂ CH 2 CH ₂ -, -CH _{2 OCH 2 CH 2 -} , -CH _{2 NHCH 2 CH 2} - from the viewpoint of easy production of the compound. , -CH ₂ OC(O)CH ₂ CH ₂ -, or -C(O)- are preferred.

s2 is 0 or 1 (however, when Q ^a2 is a single bond, it is 0). From the viewpoint of easy production of the compound, 0 is preferable.

Q ^b2 is an alkylene group or a group having a divalent organopolysiloxane residue, an ether oxygen atom, or -NH- between carbon atoms of an alkylene group having 2 or more carbon atoms.
The number of carbon atoms in the alkylene group represented by Q ^b2 is preferably 1 to 30, more preferably 1 to 20, even more preferably 2 to 20, may be 2 to 10, or may be 2 to 6. . Examples include 2, 3, 8, 9, and 11. Further, the number of carbon atoms may be 1 to 10.
The number of carbon atoms in the group having a divalent organopolysiloxane residue, ether oxygen atom or -NH- between carbon atoms of the alkylene group having 2 or more carbon atoms represented by Q ^b2 is 2 to 10. is preferable, and 2 to 6 are more preferable.

As Q ^b2 , -CH ₂ CH ₂ CH ₂ -, -CH ₂ CH ₂ OCH ₂ CH ₂ CH ₂ - are preferable from the viewpoint of easy production of the compound (provided that the right side is bonded to Si).

The two [-Q ^b2 -Si(R ¹ ) _n L ² _3-n ] may be the same or different.

Specific examples of the group (3-1A-2) include the following groups. In the following formula, * represents the bonding position with L ⁶ in formula (3-1). Further, in the formula, α in (CH ₂ ) _α bonded to the reactive silyl group is an integer representing the number of methylene groups, preferably 1 to 30, more preferably 1 to 20, even more preferably 2 to 20, It may be from 2 to 10, or from 2 to 6. Examples include 2, 3, 8, 9, and 11. Further, the number of carbon atoms may be 1 to 10. A plurality of α's contained in the same compound may be the same or different, but are preferably the same. For example, all of the plurality of αs contained in the same compound are 2, 3, 8, 9, and 11. The same applies below.

 

 

In the group (3-1A-3), Q ^a3 is a single bond or a (poly)oxyalkylene group, and a single bond is preferable from the viewpoint of easy production of the compound.
The number of carbon atoms in the (poly)oxyalkylene group is preferably 1 to 10, more preferably 2 to 6.

R ^g is a hydrogen atom, a hydroxyl group, or an alkyl group.
From the viewpoint of easy production of the compound, R ^g is preferably a hydrogen atom or an alkyl group. The alkyl group preferably has 1 to 10 carbon atoms, more preferably 1 to 4 carbon atoms, and even more preferably a methyl group.

Q ^b3 is an alkylene group or a group having an ether oxygen atom or a divalent organopolysiloxane residue between carbon atoms of an alkylene group having 2 or more carbon atoms.
The number of carbon atoms in the alkylene group represented by Q ^b3 is preferably 1 to 30, more preferably 1 to 20, even more preferably 2 to 20, may be 2 to 10, or may be 2 to 6. . Examples include 2, 3, 8, 9, and 11. Further, the number of carbon atoms may be 1 to 10.
The carbon number of the group having an ether oxygen atom or a divalent organopolysiloxane residue between the carbon atoms of the alkylene group having 2 or more carbon atoms, represented by Q ^b3 , is preferably 2 to 20, and 2 to 20. 10 is more preferable, and 2 to 6 is even more preferable.
Q ^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 -} from the viewpoint of easy production of the compound.

The two [-Q ^b3 -Si(R ¹ ) _n L ² _3-n ] may be the same or different.

Specific examples of the group (3-1A-3) include the following groups. In the following formula, * represents the bonding position with L ⁶ in formula (3-1).

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 )-.
The definition of R ³¹ is as described above.
s4 is 0 or 1.
Q ^a4 is a single bond, an alkylene group which may have an etheric oxygen atom (when s4 is 1), or a (poly)oxyalkylene group (when s4 is 0).
The alkylene group or (poly)oxyalkylene group which may have an etheric oxygen atom preferably has 1 to 10 carbon atoms, more preferably 2 to 6 carbon atoms.
t4 is 0 or 1 (however, when Q ^a4 is a single bond, it is 0).
From the viewpoint of easy production of the compound, -Q ^a4 -(O) _t4 - is a single bond, -O-, -OCH ₂ -, -OCH ₂ CH ₂ O-, -OCH ₂ CH ₂ OCH ₂ -, -OCH ₂ CH ₂ CH ₂ CH ₂ OCH ₂ - is preferable (however, the left side is bonded to CH ₃ (CH ₂ ) _m1 - or -(CH ₂ ) _m2 -), and s4 is 1 In the case of , a single bond, -CH ₂ -, and -CH ₂ CH ₂ - are preferable.

Q ^b4 is an alkylene group, and the alkylene group is -O-, -C(O)N(R ^d )- (the definition of R ^d is as described above), a silphenylene skeleton group, a divalent It may or may not have an organopolysiloxane residue or a dialkylsilylene group.
In addition, when the alkylene group has -O- or a silphenylene skeleton group, it is preferable to have -O- or a silphenylene skeleton group between carbon atoms. In addition, when the alkylene group has -C(O)N(R ^d )-, a dialkylsilylene group, or a divalent organopolysiloxane residue, the terminal between carbon atoms or the side bonded to (O) _u4 preferably has these groups.
The number of carbon atoms in the alkylene group represented by Q ^b4 is preferably 1 to 30, more preferably 1 to 20, even more preferably 2 to 20, may be 2 to 10, or may be 2 to 6. . Examples include 2, 3, 8, 9, and 11. Further, the range may be from 1 to 10.

u4 is 0 or 1.
-(O) _u4 -Q ^b4 - includes -CH 2 CH ₂ -, -CH ₂ CH 2 CH ₂ -, -CH _{2 OCH 2} CH _{2 CH 2} -, -CH ₂ from the viewpoint of easy production of the compound. 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 -- and --CH ₂ CH ₂ CH ₂ Si(CH ₃ ) ₂ PhSi(CH ₃ ) ₂ CH ₂ CH ₂ -- are preferred (however, the right side is bonded to Si).

w1 is an integer from 0 to 2, preferably 0 or 1, and more preferably 0.
If there are two or more [-(O) _u4 -Q ^b4 -Si(R ¹ ) _n L ² _3-n ], two or more [-(O) _u4 -Q ^b4 -Si(R ¹ ) _n L ² _3-n ] may be the same or different.
When there are two or more R ³¹ s, two or more (-R ³¹ )s may be the same or different.

Specific examples of the group (3-1A-4) include the following groups. In the following formula, * represents the bonding position with L ⁶ in formula (3-1).

 

 

 

In the group (3-1A-5), Q ^a5 is a single bond, a carbonyloxyalkylene group, a carbonylaminoalkylene group, or a (poly)oxyalkylene group.
The carbon number of the carbonyloxyalkylene group, carbonylaminoalkylene group, and (poly)oxyalkylene group is preferably 1 to 10, more preferably 2 to 6.
Q ^a5 is a single bond, -C(O)OCH ₂ CH ₂ CH ₂ -, -C(O)NHCH ₂ CH ₂ CH ₂ -, -OCH ₂ CH ₂ CH ₂ - from the viewpoint of easy production of the compound. , and -OCH ₂ CH ₂ OCH ₂ CH ₂ CH ₂ - are preferred (however, the left side is bonded to L ⁶ - in formula (3-1)).

Q ^b5 is an alkylene group or a group having an ether oxygen atom or a divalent organopolysiloxane residue between carbon atoms of an alkylene group having 2 or more carbon atoms.
The number of carbon atoms in the alkylene group represented by Q ^b5 is preferably 1 to 30, more preferably 1 to 20, even more preferably 2 to 20, may be 2 to 10, or may be 2 to 6. . Examples include 2, 3, 8, 9, and 11. Further, the number of carbon atoms may be 1 to 10.
The number of carbon atoms in the group having an ether oxygen atom or a divalent organopolysiloxane residue between carbon atoms of the alkylene group having 2 or more carbon atoms represented by Q ^b5 is preferably 2 to 20, and 2 to 20. 10 is more preferable, and 2 to 6 is even more preferable.
Q ^b5 is preferably -CH ₂ CH ₂ CH ₂ - and -CH ₂ CH ₂ OCH ₂ CH ₂ CH ₂ - (provided that the right side is Si(R ¹ ) _n L ² _3-n .).

The three [-Q ^b5 -Si(R ¹ ) _n L ² _3-n ] may be the same or different.

Specific examples of the group (3-1A-5) include the following groups. In the following formula, * represents the bonding position with L ⁶ in formula (3-1).

 

 

The definition of Q ^e in group (3-1A-6) is as defined in group (3-1A-4) above.
v is 0 or 1.

Q ^a6 is a single bond, an alkylene group which may have an etheric oxygen atom (when v is 1), or a (poly)oxyalkylene group.
The alkylene group or (poly)oxyalkylene group which may have an etheric oxygen atom preferably has 1 to 10 carbon atoms, more preferably 2 to 6 carbon atoms.
When v is 1, Q ^a6 is -CH ₂ OCH 2 CH ₂ CH ₂ -, -CH ₂ OCH ₂ CH _{2 OCH 2} CH ₂ CH ₂ -, -CH ₂ CH ₂ from the viewpoint of easy production of the compound _. -, -CH ₂ CH ₂ CH ₂ - are preferred (provided that the right side is bonded to Z ^a ).
When v is 0, Q ^a6 is preferably -OCH ₂ CH ₂ CH ₂ - or -OCH ₂ CH ₂ OCH ₂ CH ₂ CH ₂ - (provided that Z ^a on the right side ).

Z ^a is a (w2+1)-valent organopolysiloxane residue or a (w2+1)-valent group having an alkylene group between the organopolysiloxane residues.
w2 is an integer from 2 to 7.
Examples of (w2+1)-valent organopolysiloxane residues and (w2+1)-valent groups having an alkylene group between organopolysiloxane residues include the following groups: . However, R ^a in the following formula is as described above.

 

Q ^b6 is an alkylene group or a group having an ether oxygen atom or a divalent organopolysiloxane residue between carbon atoms of an alkylene group having 2 or more carbon atoms.
The number of carbon atoms in the alkylene group represented by Q ^b6 is preferably 1 to 30, more preferably 1 to 20, even more preferably 2 to 20, may be 2 to 10, or may be 2 to 6. . Examples include 2, 3, 8, 9, and 11. Further, the number of carbon atoms may be 1 to 10.
The carbon number of the group having an ether oxygen atom or a divalent organopolysiloxane residue between the carbon atoms of the alkylene group having 2 or more carbon atoms represented by Q ^b6 is preferably 2 to 20, and 2 to 20. 10 is more preferable, and 2 to 6 is even more preferable.
As Q ^b6 , -CH ₂ CH ₂ - and -CH ₂ CH ₂ CH ₂ - are preferable from the viewpoint of easy production of the compound.
w2 [-Q ^b6 -Si(R ¹ ) _n3 L ² _3-n ] may be the same or different.

Specific examples of the group (3-1A-6) include the following groups. In the following formula, * represents the bonding position with L ⁶ in formula (3-1).

 

In group (3-1A-7), Z ^c is a (w3+w4+1)-valent hydrocarbon group.
w3 is an integer of 4 or more.
w4 is an integer greater than or equal to 0.
The definitions and preferred ranges of Q ^e , s4, Q ^a4 , t4, Q ^b4 , and u4 are the same as the definitions of each symbol in group (3-1A-4).

Z ^c may consist of a hydrocarbon chain, may have an ether oxygen atom between carbon atoms of the hydrocarbon chain, and is preferably composed of a hydrocarbon chain.
The valence of Z ^c is preferably 5 to 20, more preferably 5 to 10, even more preferably 5 to 8, particularly preferably penta or hexavalent.
The number of carbon atoms in Z ^c is preferably 3 to 50, more preferably 4 to 40, even more preferably 5 to 30.
w3 is preferably 4 to 20, more preferably 4 to 16, even more preferably 4 to 8, and particularly preferably 4 or 5.
w4 is preferably 0 to 10, more preferably 0 to 8, even more preferably 0 to 6, particularly preferably 0 to 3, and most preferably 0 or 1.
If there are two or more [-(O-Q ^b4 ) _u4 -Si(R ¹ ) _n L ² _3-n ], two or more [-(O-Q ^b4 ) _u4 -Si(R ¹ ) _n L ² _3-n ] may be the same or different.

Specific examples of the group (3-1A-7) include the following groups. In the following formula, * represents the bonding position with L ⁶ in formula (3-1).

 

In group (3-1A-8), X ³⁴ is a single bond, -C(O)NR ⁶ -, -C(O)-, -OC(O)O-, -NHC(O)O-, - NHC(O)NR ⁶ -, -O-, or SO ₂ NR ⁶ -.
When the atom in Z ^d to which Q ^a7 is bonded is a carbon atom, Q ^a7 is a single bond, an alkylene group, or a carbon-carbon atom of an alkylene group having 2 or more carbon atoms -C(O)NR ⁶ -, -C A group having (O)-, -NR ⁶ - or O-, or a group having -C(O)- at the N-side end of an alkylene group. When the atom in Z ^d to which Q ^a7 is bonded is a nitrogen atom, Q ^a7 is a single bond, an alkylene group, or a bond between the carbon and carbon atoms of an alkylene group having 2 or more carbon atoms -C(O)NR ⁶ -, -C A group having (O)-, -NR ⁶ - or O-, or a group having -C(O)- at the N-side end of an alkylene group. Note that R ⁶ is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group.
-X ³⁴ -Q ^a7 - is preferably a single bond or -OCH ₂ - from the viewpoint of easy production of the compound (provided that the left side is bonded to L ⁶ - in formula (3-1)).

Z ^d is a group having a (h3+1)-valent ring structure in which Q ^a7 has a carbon atom or a nitrogen atom to which Q b7 directly bonds, and Q ^b7 has a carbon atom or nitrogen atom to which it directly bonds.
Examples of the ring structure in Z ^d include the ring structures described above, and preferred forms are also the same.

When the atom in Z ^d to which Q ^b7 is bonded is a carbon atom, Q b7 is an alkylene group, -C(O) ^{NR 6} -, -C(O) between carbon atoms of an alkylene group having 2 or more carbon atoms. A group having -, -NR ⁶ - or O-, a group having -C(O)NR ⁶ -, -C(O)-, -NR ⁶ - or O- at the end of the side not bonded to Si of an alkylene group , or the end of an alkylene group having 2 or more carbon atoms that has -C(O)NR ⁶ -, -C(O)-, -NR ⁶ - or O- between the carbon atoms and is not bonded to Si. It is a group having -C(O)NR ⁶ -, -C(O)-, -NR ⁶ -, or O-. When the atom in Z ^d to which Q ^b7 is bonded is a nitrogen atom, -C(O) ^{NR 6} -, -C(O )-, -NR ⁶ - or O-. R ⁶ is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group. When Y ¹¹ has two or more Q ^b7s , the two or more Q ^b7s may be the same or different.
Q ^b7 is preferably -CH ₂ CH ₂ CH ₂ - and -CH ₂ CH ₂ OCH ₂ CH ₂ CH ₂ - (provided that the right side is Si(R ¹ ) _n L ² ₃ -bonds to _n ).

h3 is an integer of 1 or more, preferably 2 or 3.
h3 [-Q ^b7 -Si(R ¹ ) _n L ² _3-n ] may be the same or different.

Specific examples of the group (3-1A-8) include the following groups. In the following formula, * represents the bonding position with L ⁶ in formula (3-1).

 

^Y12 in formula (3-2) is a group (g2-1) (however, d1+d3=p+q, d2+d4=g), a group (g2-2) (however, e1=p+q, e2=g) ), group (g2-3) (however, g=1), group (g2-4) (however, h1=p+q, h2=g), or group (g2-5) (however, , i1=p+q, i2=g).

 

(-A ¹ -Q ¹² -) _e1 C(R ^e2 ) _4-e1-e2 (-Q ²² -) _e2 ...(g2-2)
(-A ¹ -Q ¹³ -) ₂ N-Q ²³ - ... (g2-3)
(-A ¹ -Q ¹⁴ -) _h1 Z ¹ (-Q ²⁴ -) _h2 ... (g2-4)
(-A ¹ -Q ¹⁵ -) _i1 Si(R ^e3 ) _4-i1-i2 (-Q ²⁵ -) _i2 ...(g2-5)

However, in formulas (g2-1) to (g2-5), the A ¹ side is bonded to (T ¹ -Z-L ³ ) or (T ² -A-L ⁴ ) in formula (3-2), The Q ²² , Q ²³ , Q ²⁴ , or Q ²⁵ side is bonded to (-Si(R ¹ ) _n L ² _3-n ).
A ¹ is a single bond, -C(O)NR ⁶ -, -C(O)-, -OC(O)O-, -NHC(O)O-, -NHC(O)NR ⁶ -, -O -, NR ⁶ -, or SO ₂ NR ⁶ -.
Q ¹¹ is a single bond, -O-, an alkylene group, or a bond between carbon atoms of an alkylene group having 2 or more carbon atoms -C(O)NR ⁶ -, -C(O)-, -NR ⁶ -, or It is a group having O-.
Q ¹² has -C(O)NR ⁶ -, -C(O)-, -NR ⁶ - or O- between carbon atoms of a single bond, an alkylene group, or an alkylene group having 2 or more carbon atoms. group, and when Y ¹ has two or more Q ^{12 s} , two or more Q ^12s may be the same or different.
Q ¹³ is a single bond, an alkylene group, a group having -C(O)NR ⁶ -, -C(O)-, -NR ⁶ - or O- between carbon atoms of an alkylene group having 2 or more carbon atoms; , or a group having -C(O)- at the N-side end of the alkylene group, and the two Q ^13s of Y ¹² may be the same or different.
Q ¹⁴ is Q ¹² when the atom in Z ¹ to ^{which Q 14 is bonded is a carbon atom, and is Q 13 when} the atom ^{in Z 1 to which Q 14 is bonded} is a nitrogen ^atom ; When there are two or more, two or more ^Q14 may be the same or different.
Q ¹⁵ has -C(O)NR ⁶ -, -C(O)-, -NR ⁶ - or O- between carbon atoms of a single bond, an alkylene group, or an alkylene group having 2 or more carbon atoms. group, and when Y ¹² has two or more Q ^{15 s} , the two or more Q ^15s may be the same or different.
Q ²² is an alkylene group, a group having -C(O)NR ⁶ -, -C(O)-, -NR ⁶ - or O- between carbon atoms of an alkylene group having 2 or more carbon atoms, an alkylene group A group having -C(O)NR ⁶ -, -C(O)-, -NR ⁶ - or O- at the end not bonded to Si, or between carbon atoms of an alkylene group having 2 or more carbon atoms -C(O)NR ⁶ -, -C(O)-, -NR ⁶ - or O- and -C(O)NR ⁶ -, -C(O) at the end that does not bond to Si It is a group having -, -NR ⁶ - or O-, and when Y ¹² has two or more Q ^22s , the two or more Q ^22s may be the same or different.
Q ²³ is an alkylene group or a group having -C(O)NR ⁶ -, -C(O)-, -NR ⁶ - or O- between carbon atoms of an alkylene group having 2 or more carbon atoms; , two ^Q23s may be the same or different.
Q ²⁴ is Q ²² when the atom in Z ¹ to ^which Q 24 is bonded is a carbon atom, and Q ²³ when the atom ⁱⁿ Z ¹ to which Q ²⁴ is bonded is a nitrogen ^atom ; When there are two or more, two or more ^Q24 may be the same or different.
Q ²⁵ is an alkylene group or a group having -C(O)NR ⁶ -, -C(O)-, -NR ⁶ - or O- between carbon atoms of an alkylene group having 2 or more carbon atoms; , Y ¹² has two or more Q ^25s , the two or more Q ^25s may be the same or different.
Z ¹ is a group having an h1+h2 valent ring structure in which Q ¹⁴ has a carbon atom or nitrogen atom to which Q 14 is directly bonded, and Q ²⁴ has a carbon atom or nitrogen atom to which Q 24 is directly bonded.
R ^e1 is a hydrogen atom or an alkyl group, and when Y ¹² has two or more R ^e1s , the two or more R ^e1s may be the same or different.
R ^e2 is a hydrogen atom, a hydroxyl group, an alkyl group, or an acyloxy group.
R ^e3 is an alkyl group.
R ⁶ is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group.

d1 is an integer from 0 to 3, preferably 1 or 2. d2 is an integer from 0 to 3, preferably 1 or 2. d1+d2 is an integer from 1 to 3.
d3 is an integer from 0 to 3, preferably 1 or 2. d4 is an integer from 0 to 3, preferably 2 or 3. d3+d4 is an integer from 1 to 3.
d1+d3 is an integer from 2 to 5, preferably 2.
d2+d4 is an integer from 1 to 5, preferably 4 or 5.
e1+e2 is 3 or 4. e1 is 2 or 3, preferably 2. e2 is 1 or 2, preferably 2.
h1 is an integer of 2 or more, preferably 2. h2 is an integer of 1 or more, preferably 1 or 2.
i1+i2 is 3 or 4. i1 is 2 or 3, preferably 2. i2 is 1 or 2, preferably 2.

The number of carbon atoms in the alkylene groups of Q ¹¹ , Q ¹² , Q ¹³ , Q ¹⁴ , Q ¹⁵ , Q ²² , Q ²³ , Q ²⁴ , and Q ²⁵ is determined from the viewpoint of easy production of compound (3-2) and surface treatment. From the viewpoint of further improving the abrasion resistance of the layer, the number is preferably 1 to 30, more preferably 1 to 20, even more preferably 2 to 20, may be 2 to 10, or may be 2 to 6. Examples include 2, 3, 8, 9, and 11. Further, the number of carbon atoms may be 1 to 10, 1 to 6, or 1 to 4. However, when the alkylene group has a specific bond between carbon atoms, the lower limit of the number of carbon atoms is 2.

-A ¹ -Q ¹² -, -A ¹ -Q ¹³ , -A ¹ -Q ¹⁴ -, and -A ¹ -Q ¹⁵ - are preferably single bonds from the viewpoint of easy production of compound (3-2). .
-Q ²² -, -Q ²³ -, -Q ²⁴ -, and -Q ²⁵ - are preferably alkylene groups, more preferably alkylene groups having 1 to 10 carbon atoms, from the viewpoint of easy production of compound (3-2). Preferably, an alkylene group having 1 to 4 carbon atoms is more preferable, and an alkylene group having 3 to 4 carbon atoms is particularly preferable.

Examples of the ring structure in Z ¹ include the ring structures described above, and preferred forms are also the same. In addition, since Q ¹⁴ and Q ²⁴ are directly bonded to the ring structure in Z ¹ , for example, an alkylene group is not connected to the ring structure and Q ¹⁴ or Q ²⁴ is not connected to the alkylene group.

The number of carbon atoms in the alkyl group of R ^e1 , R ^e2 or R ^e3 is preferably 1 to 6, more preferably 1 to 3, and even more preferably 1 to 2 from the viewpoint of ease of producing compound (3-2).
The number of carbon atoms in the alkyl group portion of the acyloxy group of R ^e2 is preferably 1 to 6, more preferably 1 to 3, and even more preferably 1 to 2, from the viewpoint of ease of producing compound (3-2).
h1 is preferably from 2 to 6, more preferably from 2 to 4, and even more preferably from 2 to 4, from the viewpoint of facilitating the production of compound (3-2) and from the viewpoint of further improving the abrasion resistance of the surface treatment layer.
h2 is preferably 2 to 6, more preferably 2 to 4, even more preferably 2 or 3, from the viewpoint of easy production of compound (3-2) and from the viewpoint of further excellent wear resistance of the surface treatment layer. .

Other forms of Y ¹ include the group (g2-8) (however, d1+d3=p+q, d2×k3+d4×k3=g), the group (g2-9) (however, e1=p+q, e2×k3 = g), group (g2-10) (however, g=k3), group (g2-11) (however, h1=p+q, h2×k3=g), or group ( g2-12) (where i1=p+q, i2×k3=g).

 

(-A ¹ -Q ¹² -) _e1 C(R ^e2 ) _4-e1-e2 (-Q ²² -G ¹ ) _e2 ...(g2-9)
(-A ¹ -Q ¹³ ) ₂ -N-Q ²³ -G ¹ ... (g2-10)
(-A ¹ -Q ¹⁴ -) _h1 Z ¹ (-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)

However, in formulas (g2-8) to (g2-12), the A ¹ side is bonded to (T ¹ -Z-L ³ ) or (T ² -A-L ⁴ ) in formula (3-2), The G ¹ side is bonded to (-Si(R ¹ ) _n L ² _3-n ). G ¹ is a group (g3), and two or more G ^1s included in Y ¹² may be the same or different. The symbols other than G ¹ are the same as those in equations (g2-1) to (g2-5).
-Si(R ⁸ ) _3-k3 (-Q ³ -) _k3 ...(g3)
However, in formula (g3), the Si side is bonded to Q ²² , Q ²³ , Q ²⁴ , and Q ²⁵ , and the Q ³ side is bonded to (-Si(R ¹ ) _n L ² _3-n ). R ⁸ is an alkyl group. Q ³ is an alkylene group, a group having -C(O)NR ⁶ -, -C(O)-, -NR ⁶ - or -O- between carbon atoms of an alkylene group having 2 or more carbon atoms, 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. R ⁹ is an alkyl group, a phenyl group, or an alkoxy group, and two R ^9s may be the same or different. p is an integer from 0 to 5, and when p is 2 or more, two or more (OSi(R ⁹ ) ₂ ) may be the same or different.

The number of carbon atoms in the alkylene group of ^Q3 is preferably 1 to 30, more preferably 1 to 20, from the viewpoint of easy production of compound (3-2) and the viewpoint of further excellent wear resistance of the surface treatment layer. It is more preferably from 2 to 20, may be from 2 to 10, or may be from 2 to 6. Examples include 2, 3, 8, 9, and 11. Further, the number of carbon atoms may be 1 to 10, 1 to 6, or 1 to 4. However, when the alkylene group has a specific bond between carbon atoms, the lower limit of the number of carbon atoms is 2.
The number of carbon atoms in the alkyl group of R ⁸ is preferably 1 to 6, more preferably 1 to 3, and even more preferably 1 to 2 from the viewpoint of easy production of compound (3-2).
The number of carbon atoms in the alkyl group of R ⁹ is preferably 1 to 6, more preferably 1 to 3, and even more preferably 1 to 2 from the viewpoint of ease of producing compound (3-2).
The number of carbon atoms in the alkoxy group of R ⁹ is preferably 1 to 6, more preferably 1 to 3, and even more preferably 1 to 2 from the viewpoint of excellent storage stability of compound (3-2).
p is preferably 0 or 1.

Examples of the compound (3-2) include compounds of the following formula. The compound of the following formula is preferred from the viewpoints of easy industrial production, ease of handling, and superior abrasion resistance of the surface treatment layer. R ^t in the compound of the following formula is (T ¹ -Z-L ³ ) or (T ² -AL ⁴ ) in the above-mentioned formula (3-2), and at least one of the two or more R ^t One is (T ¹ -Z-L ³ ), and at least one other is (T ² -A-L ⁴ ).

Examples of the compound (3-2) in which Y ¹² is a group (g2-1) include compounds of the following formula.

 

Examples of the compound (3-2) in which Y ¹² is a group (g2-2) include compounds of the following formula.

 

Examples of the compound (3-2) in which Y ¹² is a group (g2-3) include compounds of the following formula.

 

Examples of the compound (3-2) in which Y ¹² is a group (g2-4) include compounds of the following formula.

 

Examples of the compound (3-2) in which Y ¹² is a group (g2-5) include compounds of the following formula.

 

Examples of the compound (3-2) in which Y ¹² is a group (g2-8) include compounds of the following formula.

 

Examples of the compound (3-2) in which Y ¹² is a group (g2-9) include compounds of the following formula.

 

Examples of the compound (3-2) in which Y ¹² is a group (g2-10) include compounds of the following formula.

 

Examples of the compound (3-2) in which Y ¹² is a group (g2-11) include compounds of the following formula.

 

Examples of the compound (3-2) in which Y ¹² is a group (g2-12) include compounds of the following formula.

 

Specific examples of the linking group represented by Y ¹ include organic groups having the following structure. The linking group represented by Y ¹ is not limited to the specific examples below. However, in the following formula, a is each independently an integer of 1 to 5, preferably an integer of 1 to 3. In the following formula, b is each independently an integer of 1 to 5, preferably an integer of 1 to 3. In the following formula, ^Z * is a bond bonded to chain Z, ^A * is a bond bonded to chain A, and * ^Si is a bond bonded to a reactive silyl group.

 

 

 

 

 

 

Examples of the compounds of the present disclosure include the following compounds. However, in the following formula, X2 is an integer of 1 to 200, preferably an integer of 10 to 80.

 

 

 

 

 

 

The number average molecular weight (Mn) of the compound of the present disclosure is preferably 400 to 20,000, more preferably 500 to 18,000, and even more preferably 600 to 15,000. When Mn is 400 or more, water repellency and abrasion resistance are excellent. When Mn is 20,000 or less, the viscosity can be easily controlled within an appropriate range, and solubility is improved, resulting in excellent handling properties during film formation.

[Method for producing compound]
The method for producing the compound of the present disclosure is not particularly limited. Examples of synthetic schemes for compounds of the present disclosure are shown below.

 

 

[Composition]
The composition of the present disclosure only needs to contain the compound of the present disclosure, and components other than the compound of the present disclosure are not particularly limited. Compositions of the present disclosure preferably include a compound of the present disclosure and a liquid medium. When the composition of the present disclosure includes a liquid medium, the composition of the present disclosure may be in a liquid state, and may be a solution or a dispersion.
The composition of the present disclosure only needs to contain the compound of the present disclosure, and may contain impurities such as by-products generated in the manufacturing process of the compound of the present disclosure.
The composition of the present disclosure may contain one type of compound of the present disclosure, or may contain two or more types of compounds of the present disclosure.

The content of the compound of the present disclosure is preferably 0.001 to 40% by mass, more preferably 0.01 to 20% by mass, and further preferably 0.1 to 10% by mass, based on the total amount of the composition of the present disclosure. preferable. In the case of the composition of the present disclosure used in the wet coating method, the content of the compound of the present disclosure may be 0.01 to 10% by mass, based on the total amount of the composition of the present disclosure, and 0. It may be 0.02 to 5% by weight, 0.03 to 3% by weight, or 0.05 to 2% by weight.

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. Specifically, examples include hydrocarbon-based organic solvents, ketone-based organic solvents, and ethers. Examples include organic solvents based on organic solvents, organic solvents based on esters, organic solvents based on glycol, and organic solvents based on alcohol.
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, Examples include p-xylene, o-diethylbenzene, m-diethylbenzene, p-diethylbenzene, n-butylbenzene, sec-butylbenzene, and tert-butylbenzene.
Specific examples of ketone organic solvents include acetone, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, cyclohexanone, 2-heptanone, 4-heptanone, 3,5,5-trimethyl-2-cyclohexen-1-one, and 3,5,5-trimethyl-2-cyclohexen-1-one. Examples include 3,5-trimethylcyclohexanone and isophorone.
Specific examples of ether organic solvents include diethyl ether, cyclopentyl methyl ether, tetrahydrofuran, and 1,4-dioxane.
Specific examples of ester organic solvents include methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, isobutyl acetate, tert-butyl acetate, amyl acetate, isoamyl acetate, ethyl 3-ethoxypropionate, ethyl ethylene glycol lactate. 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 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 mono Butyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol diacetate, 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, and ethylene glycol mono-2. -Ethylhexyl ether, diethylene glycol mono-2-ethylhexyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, propylene glycol monopropyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monoethyl ether, ethylene glycol monotert -Butyl ether, ethylene glycol monopropyl ether, ethylene glycol monomethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monobutyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monomethyl ether, Propylene 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, Propylene 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 alcoholic organic solvents include methanol, ethanol, 1-propanol, isopropyl alcohol, n-butanol, diacetone alcohol, isobutanol, sec-butanol, tert-butanol, pentanol, 3-methyl-1,3 -Butanediol, 1,3-butanediol, 1,3-butylene glycol, octanediol, 2,4-diethylpentanediol, butylethylpropanediol, 2-methyl-1,3-propanediol, 4-hydroxy-4 -Methyl-2-pentanone, 2-ethyl-1-hexanol, 3,5,5-trimethyl-1-hexanol, isodecanol, isotridecanol, 3-methoxy-3-methyl-1-butanol, 2-methoxybutanol , 3-methoxybutanol, cyclohexanol, furfuryl alcohol, tetrahydrofurfuryl alcohol, benzyl alcohol, and methylcyclohexanol.

Further, examples of the organic solvent include halogenated organic solvents, nitrogen-containing compounds, sulfur-containing compounds, and siloxane compounds.
Specific examples of halogenated organic solvents include dichloromethane, chloroform, carbon tetrachloride, dichloroethane, chlorobenzene, o-chlorotoluene, m-chlorotoluene, p-chlorotoluene, m-dichlorobenzene, 1,2,3-trichloropropane. can be mentioned.
Examples of nitrogen-containing compounds include nitrobenzene, acetonitrile, benzonitrile, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, and 1,3-dimethyl-2-imidazolidinone.
Examples of sulfur-containing compounds include carbon disulfide and dimethyl sulfoxide.
Examples of the siloxane compound include hexamethyldisiloxane, octamethyltrisiloxane, and decamethyltetrasiloxane.

The content of the liquid medium is preferably 60 to 99.999% by mass, more preferably 80 to 99.99% by mass, and even more preferably 90 to 99.9% by mass, based on the total amount of the composition of the present disclosure. In the case of the composition of the present disclosure used in a wet coating method, the content of the liquid medium may be 90-99.99% by weight, 95-99% by weight, based on the total amount of the composition of the present disclosure. It may be .98% by mass, 97 to 99.97% by mass, or 98 to 99.95% by mass.
The composition of the present disclosure may contain only one type of liquid medium, or may contain two or more types.

The composition of the present disclosure may contain other components in addition to the compound of the present disclosure and 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 hydrolysis and condensation reactions of reactive silyl groups.

In addition, other components include a metal compound having a hydrolyzable group (hereinafter, a metal compound having a hydrolyzable group is also referred to as a "specific metal compound"). When the composition of the present disclosure contains a specific metal compound, the slipperiness and antifouling properties of the surface treatment layer can be further improved. Specific metal compounds include the following formulas (M1) to (M3).

M(X ^b1 ) _m1 (X ^b2 ) _m2 (X ^b3 ) _m3 ...(M1)
Si(X ^b4 )(X ^b5 ) ₃ ...(M2)
(X ^b6 ) ₃ Si-(Y ^b1 )-Si(X ^b7 ) ₃ ...(M3)

In formula (M1),
M represents a trivalent or tetravalent metal atom.
Each of X ^b1 independently represents a hydrolyzable group.
Each of X ^b2 independently represents a siloxane skeleton-containing group.
Each of X ^b3 independently represents a hydrocarbon chain-containing group.
m1 is an integer from 2 to 4,
m2 and m3 are each independently an integer of 0 to 2,
When M is a trivalent metal atom, m1+m2+m3 is 3, and when M is a tetravalent metal atom, m1+m2+m3 is 4.

In formula (M2),
X ^b4 represents a hydrolyzable silane oligomer residue.
Each of X ^b5 independently represents a hydrolyzable group or an alkyl group having 1 to 4 carbon atoms.
In formula (M3),
X ^b6 and X ^b7 each independently represent a hydrolyzable group or a hydroxyl group.
Y ^b1 represents a divalent organic group.

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, and Zr, even more preferably Al, Si, Ti, and Zr, and particularly preferably Si. .

In formula (M1), the hydrolyzable group represented by X ^b1 is the same as the hydrolyzable group represented by L in (-Si(R ¹ ) _n L _3-n ) in the above reactive silyl group. Examples include:

The siloxane skeleton-containing group represented by X ^b2 has a siloxane unit (-Si-O-) and may be linear or branched. The siloxane unit is preferably 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 include a divalent hydrocarbon group in a part of the siloxane skeleton. Specifically, some oxygen atoms in the siloxane skeleton may be replaced with divalent hydrocarbon groups. Examples of the divalent hydrocarbon group include alkylene groups such as a methylene group, an ethylene group, a propylene group, and a butylene group.
A hydrolyzable group, a hydrocarbon group (preferably an alkyl group), etc. 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.
The siloxane skeleton-containing group is preferably a group represented by ^* -(O-Si(CH ₃ ) ₂ ) _n CH ₃ , where n is an integer from 1 to 5, and * represents a bond with an adjacent atom. Represents a part.

The hydrocarbon chain-containing group represented by X ^b3 may be a group consisting only of a hydrocarbon chain, or may be a group having an etheric oxygen atom between carbon atoms of the hydrocarbon chain. The hydrocarbon chain may be straight or branched, preferably straight. 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, more preferably a methyl group, an ethyl group, or a propyl group.

It is preferable that m1 is 3 or 4.

Compounds represented by formula (M1) include the following formulas (M1-1) to (M1-
Compounds represented by formula (M1-1) are preferred, and compounds represented by formula (M1-1) are more preferred. As the compound represented by formula (M1-1), tetraethoxysilane, tetramethoxysilane, and triethoxymethylsilane are preferred.

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)

In formula (M2), the number of silicon atoms contained in the hydrolyzable silane oligomer residue represented by X ^b4 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 methoxy group, ethoxy group, propoxy group, butoxy group, and methoxy group and ethoxy group are preferred. The hydrolyzable silane oligomer residue may have one or more types 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- ^* and the like. Here, * represents a bonding site with an adjacent atom.

In formula (M2), the hydrolyzable group represented by X ^b5 is the same as the hydrolyzable group represented by L in (-Si(R ¹ ) _n L _3-n ) in the above reactive silyl group Examples include a cyano group, a hydrogen atom, and an allyl group, with an alkoxy group or an isocyanato group being preferred. The alkoxy group is preferably an alkoxy group having 1 to 4 carbon atoms.
As X ^b5 , a hydrolyzable group is preferable.

Examples of the compound represented by formula (M2) include (H ₅ C ₂ O) ₃ -Si-(OSi(OC ₂ H ₅ ) ₂ ) ₄ OC ₂ H ₅ and the like.

The compound represented by formula (M3) is a compound having a reactive silyl group at both ends of a divalent organic group, that is, bissilane.
In formula (M3), the hydrolyzable groups represented by X ^b6 and X ^b7 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. an alkoxy group and an isocyanato group are preferred. The alkoxy group is preferably an alkoxy group having 1 to 4 carbon atoms, more preferably a methoxy group or an ethoxy group.
In formula (M3), X ^b6 and X ^b7 may be the same group or different groups. From the viewpoint of availability, it is preferable that X ^b6 and X ^b7 are the same group.

In formula (M3), Y ^b1 is a divalent organic group that connects the reactive silyl groups at both ends. The number of carbon atoms in Y ^b1 of the divalent organic group is preferably 1 to 8, more preferably 1 to 3.
Examples of Y ^b1 include an alkylene group, a phenylene group, and an alkylene group having an etheric oxygen atom between carbon atoms. For example, -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 -, -CH ₂ C(CH ₃ ) ₂ CH ₂ -, -C(CH ₃ ) ₂ CH ₂ CH ₂ C(CH ₃ ) ₂ -, -CH ₂ CH ₂ OCH ₂ CH ₂ -, -CH ₂ CH ₂ CH ₂ OCH ₂ CH ₂ CH ₂ -, -CH(CH ₃ )CH ₂ OCH ₂ CH(CH ₃ )-, and -C ₆ H ₄ -.

Examples of the compound represented by formula (M3) include (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) _3Si ( _CH2 ) _2Si ( _NCO ) ₃ , Cl3Si( _CH2 ) _{2SiCl3 ,} ( _CH3O ) _3Si ( _CH2 ) _6Si ( _OCH3 ) ₃ , ( _C2H5O ) _{3Si ( CH2} ) _6Si ( _OC2H5 ) _{3 is} mentioned.

The content of other components that may be included in the composition of the present disclosure is preferably 10% by mass or less, more preferably 1% by mass or less, based on the total amount of the composition of the present disclosure. When the composition of the present disclosure includes 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 based on the total amount of the composition of the present disclosure. , more preferably 0.02 to 8% by weight, particularly preferably 0.05 to 5% by weight.

The total content of the compound of the present disclosure and other components (hereinafter also referred to as "solid content concentration") is preferably 0.001 to 40% by mass, and 0.01% by mass, based on the total amount of the composition of the present disclosure. The amount is more preferably 20% by weight, and even more preferably 0.01% to 10% by weight. The solid content concentration of the composition of the present disclosure is a value calculated from the mass of the composition before heating and the mass after heating in a convection dryer at 120° C. for 4 hours.

Since the composition of the present disclosure contains a liquid medium, it is useful for coating purposes and can be used as a coating liquid.

[Surface treatment agent]
In one aspect, the surface treatment agent of the present disclosure comprises a compound of the present disclosure. Furthermore, the surface treatment agent of the present disclosure may include the compound of the present disclosure and a liquid medium. The surface treating agent of the present disclosure may be a composition of the present disclosure. Preferred embodiments of the liquid medium contained in the surface treatment agent are the same as those of the liquid medium contained in the composition of the present disclosure.

Since the compound of the present disclosure has the above-mentioned structure, a surface treatment layer with excellent water repellency and abrasion resistance can be formed by using a surface treatment agent containing the compound of the present disclosure.

[Goods]
In one aspect, the article of the present disclosure includes a base material and a surface treatment layer surface treated with the surface treatment agent.

The surface treatment layer may be formed on a part of the surface of the base material, or may be formed on the entire surface of the base material. The surface treatment layer may be spread over the surface of the base material in the form of a film, 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 proceeded, and a dehydration condensation reaction of the silanol groups has proceeded.

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 sufficiently obtained. 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 is determined by using an X-ray diffractometer for thin film analysis (product name "ATX-G", manufactured by RIGAKU) to obtain an interference pattern of reflected X-rays by the X-ray reflectance method. It can be calculated from the vibration period of

The type of base material is not particularly limited, and includes, for example, base materials that are required to have water repellency. As a base material, for example, a base material that may be used in contact with another article (e.g., a stylus) or a person's fingers; a base material that may be held by a person's fingers during operation; , a mounting table).
Examples of the base material include metal, resin, glass, sapphire, ceramic, stone, fiber, nonwoven fabric, paper, wood, natural leather, artificial leather, and composite materials thereof. The glass may be chemically strengthened.

Base materials include building materials, decorative building materials, interior goods, transportation equipment (e.g. automobiles), signboards/bulletin boards, drinking vessels/tableware, aquariums, ornamental equipment (e.g. frames, boxes), laboratory equipment, furniture, textile products. , Packaging containers; Glass or resin used for art, sports, games, etc.; 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. Examples include glass or resin. The shape of the base material may be plate-like or film-like.

As the base material, touch panel base materials, display base materials, and eyeglass lenses are suitable, and touch panel base materials are particularly suitable. As the material for the touch panel base material, glass or transparent resin is preferable.

The base material may be a base material that has been subjected to surface treatment such as corona discharge treatment, plasma treatment, plasma graft polymerization treatment, etc. on one surface or both surfaces. A surface-treated base material has better adhesion with the surface-treated layer, and the abrasion resistance of the surface-treated layer is further improved. Therefore, it is preferable to perform surface treatment on the surface of the base material that is in contact with the surface treatment layer. Furthermore, when the surface-treated base material is provided with a base layer, which will be described later, the adhesion with the base layer is better, and the wear resistance of the surface-treated layer is further improved. Therefore, when a base layer is provided, it is preferable to perform a surface treatment on the surface of the base material that is in contact with the base layer.

The surface treatment layer may be provided directly on the surface of the base material, or a base layer may be provided between the base material and the surface treatment layer. From the perspective of further improving the water repellency and abrasion resistance of the surface treatment layer, the article of the present disclosure includes a base material, a base layer disposed on the base material, and a surface treatment of the present disclosure disposed on the base layer. It is preferable to include a surface treatment layer whose surface is treated with an agent.

The base layer includes silicon and at least one selected from the group consisting of a group 1 element, a group 2 element, a group 4 element, a group 5 element, a group 13 element, and a group 15 element of the periodic table. A layer containing an oxide containing a specific element is preferable.

Group 1 elements of the periodic table (hereinafter also referred to as "Group 1 elements") mean lithium, sodium, potassium, rubidium, and cesium. As Group 1 elements, lithium, sodium, and potassium are used because they enable the surface treatment layer to be formed more uniformly on the underlayer without defects, and from the viewpoint of suppressing variations in the composition of the underlayer between samples. Preferably, sodium and potassium are more preferable. The underlayer may contain two or more types of Group 1 elements.

Group 2 elements of the periodic table (hereinafter also referred to as "Group 2 elements") mean beryllium, magnesium, calcium, strontium, and barium. As Group 2 elements, magnesium, calcium, and barium are used because they enable the surface treatment layer to be formed more uniformly on the underlayer without defects, and from the viewpoint of suppressing variations in the composition of the underlayer between samples. Preferably, magnesium and calcium are more preferable. The underlayer may contain two or more types of Group 2 elements.

Group 4 elements of the periodic table (hereinafter also referred to as "Group 4 elements") mean titanium, zirconium, and hafnium. As the Group 4 element, titanium and zirconium are preferable from the viewpoint of being able to form a surface treatment layer on the underlayer more uniformly without defects or from the viewpoint of suppressing variations in the composition of the underlayer between samples. Titanium is more preferred. The base layer may contain two or more types of Group 4 elements.

Group 5 elements of the periodic table (hereinafter also referred to as "Group 5 elements") mean vanadium, niobium, and tantalum. As the Group 5 element, vanadium is particularly preferable from the viewpoint of providing better wear resistance of the surface treatment layer. The underlayer may contain two or more types of Group 5 elements.

Group 13 elements of the periodic table (hereinafter also referred to as "Group 13 elements") mean boron, aluminum, gallium, and indium. As Group 13 elements, boron, aluminum, and gallium are selected from the viewpoint of forming a surface treatment layer on the underlayer more uniformly without defects, or from the viewpoint of suppressing variations in the composition of the underlayer between samples. Preferably, boron and aluminum are more preferable. The base layer may contain two or more types of Group 13 elements.

Group 15 elements of the periodic table (hereinafter also referred to as "Group 15 elements") mean nitrogen, phosphorus, arsenic, antimony, and bismuth. As Group 15 elements, phosphorus, antimony, and bismuth are used from the viewpoint of forming a surface treatment layer on the underlayer more uniformly without defects or from the viewpoint of suppressing variations in the composition of the underlayer between samples. Preferably, phosphorus and bismuth are more preferable. The base layer may contain two or more types of Group 15 elements.

As the specific elements contained in the underlayer, Group 1 elements, Group 2 elements, and Group 13 elements are preferable because the wear resistance of the surface treatment layer is better, and Group 1 elements and Group 2 elements are more preferable. , Group 1 elements are more preferred.
As the specific element, only one type of element may be included, or two or more types of elements may be included.

The oxide contained in the base layer may be a mixture of oxides of the above elements (silicon and specific elements) alone (for example, a mixture of silicon oxide and an oxide of a specific element), or a mixture of the above elements (silicon and specific elements). It may be a composite oxide containing two or more types, or a mixture of an oxide of the above element alone and a composite oxide.

The ratio of the total molar concentration of the specific element in the underlayer to the molar concentration of silicon in the underlayer (specific element/silicon) is 0.02 to 2.90 from the viewpoint of better wear resistance of the surface treatment layer. It is preferably 0.10 to 2.00, even more preferably 0.20 to 1.80.
The molar concentration (mol %) of each element in the underlayer can be measured, for example, by depth direction analysis using X-ray photoelectron spectroscopy (XPS) using ion sputtering.

The base layer may be a single layer or a multilayer. The base layer 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. If the thickness of the base layer is equal to or greater than the above lower limit, the adhesion of the surface treatment layer to the base layer will be further improved, and the wear resistance of the surface treatment layer will be more excellent. If the thickness of the base layer is below the above upper limit, the base layer itself will have excellent wear resistance.
The thickness of the base layer is measured by observing a cross section of the base layer using a transmission electron microscope (TEM).

The base layer can be formed, for example, by a vapor deposition method using a vapor deposition material or a wet coating method.

The vapor deposition material used in the vapor deposition method preferably contains an oxide containing silicon and a specific element.
Specific examples of the form of the vapor deposition material include powder, molten body, sintered body, granulated body, and crushed body, and from the viewpoint of ease of handling, molten body, sintered body, and granulated body are preferable.
Here, the melt means a solid obtained by melting the powder of the vapor deposition material at a high temperature and then cooling and solidifying the powder. A sintered body means a solid obtained by firing a powder of a vapor deposition material, and if necessary, a molded body obtained by press-molding the powder may be used instead of a powder of a vapor deposition material. Good too. The granule refers to a solid material obtained by kneading a powder of a vapor deposition material and a liquid medium (for example, water, an organic solvent) to obtain particles, and then drying the particles.

The vapor deposition material can be manufactured, for example, by the following method.
・A method of obtaining a vapor deposition material powder by mixing silicon oxide powder and oxide powder of a specific element.
- A method of kneading the powder of the vapor deposition material and water to obtain particles, and then drying the particles to obtain granules of the vapor deposition material.
・Powders containing silicon (e.g. powder of silicon oxide, silica sand, silica gel) and powders containing specific elements (e.g. powder of oxides of specific elements, carbonates, sulfates, nitrates, oxalic acid) A method of obtaining a sintered body by drying a mixture of salt, hydroxide) and water, and then firing the dried mixture or a press-molded body of the dried mixture.
・Powders containing silicon (e.g. powder of silicon oxide, silica sand, silica gel) and powders containing specific elements (e.g. powder of oxides of specific elements, carbonates, sulfates, nitrates, oxalic acid) (salt, hydroxide) at high temperature, and then cooled and solidified to obtain a molten product.

A specific example of a vapor deposition method using a vapor deposition material includes a vacuum vapor deposition method. The vacuum deposition method is a method in which a deposition material is evaporated in a vacuum chamber and adhered to the surface of a base material.
The temperature during vapor deposition (for example, the temperature of the boat in which the vapor deposition material is placed when using a vacuum vapor deposition apparatus) is preferably 100 to 3,000°C, more preferably 500 to 3,000°C.
The pressure during vapor deposition (for example, when using a vacuum vapor deposition apparatus, the pressure in the tank in which the vapor deposition material is placed) is preferably 1 Pa or less, more preferably 0.1 Pa or less.
When forming the base layer 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.

Specific examples of evaporation methods include resistance heating, in which the evaporation material is melted and evaporated on a resistance heating boat made of high-melting-point metal, and irradiation of an electron beam onto the evaporation material to directly heat the evaporation material on the surface. An example is the electron gun method, which melts and evaporates. The method of evaporating the deposition material is that it can evaporate high-melting point substances because it can be heated locally, and that there is no risk of reaction with the container or contamination with impurities because the area that is not hit by the electron beam is at a low temperature. Gun law is preferred.
As a method for evaporating the evaporation materials, a plurality of boats may be used, or all the evaporation materials may be placed in a single boat. The vapor deposition method may be codeposition, alternate vapor deposition, or the like. Specifically, examples include mixing silica and a specific element source in the same boat, co-evaporating silica and a specific element source in separate boats, and alternately depositing silica and a specific element source in separate boats. can be mentioned. The conditions, order, etc. of vapor deposition are appropriately selected depending on the structure of the underlying layer.

In the wet coating method, it is preferable to form the base layer on the base material by a wet coating method using a coating liquid containing a compound containing silicon, a compound containing a specific element, and a liquid medium.

Specific examples of silicon compounds include silicon oxide, silicic acid, partial condensates of silicic acid, alkoxysilanes, and partially hydrolyzed condensates of alkoxysilanes.

Specific examples of compounds containing specific elements include oxides of specific elements, alkoxides of specific elements, carbonates of specific elements, sulfates of specific elements, nitrates of specific elements, oxalates of specific elements, and water of specific elements. Examples include oxides.

Examples of the liquid medium include those similar to the liquid medium contained in the composition of the present disclosure described above.

The content of the liquid medium is preferably 0.01 to 20% by mass, more preferably 0.1 to 10% by mass, based on the total amount of the coating liquid used to form the base layer.

Specific examples of wet coating methods for forming the base layer include spin coating, wipe coating, spray coating, squeegee coating, dip coating, die coating, inkjet, flow coating, roll coating, Examples include the cast method, Langmuir-Blodgett method, and gravure coating method.

After wet coating the coating liquid, it is preferable to dry the coating film. The drying temperature of the coating film is preferably 20 to 200°C, more preferably 80 to 160°C.

The article of the present disclosure is preferably an optical member. Examples of optical components include medical devices such as car navigation systems, mobile phones, smartphones, digital cameras, digital video cameras, PDAs, portable audio players, car audio, game devices, eyeglass lenses, camera lenses, lens filters, sunglasses, and gastrocameras. Examples include personal appliances, copying machines, PCs, displays (eg, liquid crystal displays, organic EL displays, plasma displays, touch panel displays), touch panels, protective films, and antireflection films. In particular, the article is preferably a display or a touch panel.

[Method for manufacturing articles]
A method for producing an article of the present disclosure is, for example, a method of surface-treating a base material using the surface treatment agent of the present disclosure to produce an article in which a surface-treated layer is formed on the base material. . Surface treatments include dry coating methods and wet coating methods.

Examples of dry coating methods include vacuum deposition, CVD, and sputtering. As the dry coating method, a vacuum evaporation method is preferable from the viewpoint of suppressing decomposition of the compound and the simplicity of the apparatus. At the time of vacuum deposition, a pellet-like substance obtained by impregnating a porous metal body such as iron or steel with the compound of the present disclosure may be used. A pellet-like material impregnated with the compound of the present disclosure may be used by impregnating a porous metal body such as iron or steel with a composition containing the compound of the present disclosure and a liquid medium, and drying the liquid medium.

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, and Langmuir-Blodgett methods. , gravure coating method.

In order to improve the abrasion resistance of the surface treatment layer, an operation may be performed to accelerate the reaction between the compound of the present disclosure and the base material, if necessary. Such operations include heating, humidification, light irradiation, and the like.
For example, by heating a base material on which a surface treatment layer is formed in a moist atmosphere, a hydrolysis reaction of hydrolyzable groups, a reaction between hydroxyl groups, etc. on the surface of the base material and silanol groups, and a condensation reaction of silanol groups. can promote reactions such as the formation of siloxane bonds.
After the surface treatment, compounds in the surface treatment layer that are not chemically bonded to other compounds or the base material may be removed as necessary. Examples of the removal method include a method of pouring a solvent onto the surface treatment layer, a method of wiping with a cloth impregnated with a solvent, and the like.

Next, embodiments of the present disclosure will be specifically described using Examples, but the embodiments of the present disclosure are not limited to these Examples.

[Synthesis Example 1: Synthesis of compound (1-1)]
1,3-bistrifluoromethylbenzene (100 g), pyridine (12 g), and p-toluenesulfonyl chloride (25 g) were added to hexaethylene glycol monomethyl ether (30 g), and the mixture was stirred at 25° C. for 24 hours. After the reaction was completed, the solvent was distilled off under reduced pressure and flash column chromatography using silica gel (developing solvent: ethyl acetate/hexane) was performed to obtain 25 g of compound (1-1).

 

The structure of compound (1-1) was confirmed from the following NMR data.
¹ H NMR (500 MHz, Chloroform-d) δ 7.82 - 7.58 (m, 2H), 7.55 - 7.33 (m, 2H), 4.28 (t, J = 7.1 Hz, 2H), 3.93 - 3.22 (m, 25H) , 2.41 (d, J = 1.0 Hz, 3H).

[Synthesis Example 2: Synthesis of compound (1-2)]
Tetrahydrofuran (THF, 100 g) was added to acetonitrile (2.0 g), and the mixture was cooled to -15°C. Subsequently, 2M diisopropylamide lithium solution (25 mL) was added and stirred at -15°C for 10 minutes. Then, compound (1-1) (23 g) was added and stirred at 25° C. for 1 hour. After cooling the reaction solution to -15°C again, 2M diisopropylamide lithium solution (25 mL) was added and stirred at -15°C for 10 minutes. Thereafter, 17 g of 1-bromooctadecane was added and stirred at 25° C. for 1 hour. After the reaction was completed, hydrochloric acid and dichloromethane were added for extraction, and the solvent was distilled off.
By performing flash column chromatography using silica gel (developing solvent: ethyl acetate/hexane), 18 g of compound (1-2) was obtained.

 

The structure of compound (1-2) was confirmed from the following NMR data.
¹ H NMR (500 MHz, Chloroform-d) δ 3.99 - 3.13 (m, 25H), 2.56 (p, J = 7.0 Hz, 1H), 2.04 - 1.47 (m, 4H), 1.41 - 0.72 (m, 35H) .

[Synthesis Example 3: Synthesis of compound (1-3)]
Water (5 g) and concentrated sulfuric acid (15 g) were added to compound (1-2) (10 g), and the mixture was stirred at 100° C. for 24 hours. After the reaction was completed, water (100 g) and dichloromethane (100 g) were added for extraction, and the solvent was distilled off. By performing flash column chromatography using silica gel (developing solvent: methanol/dichloromethane), 6.7 g of compound (1-3) was obtained.

 

The structure of compound (1-3) was confirmed from the following NMR data.
¹ H NMR (500 MHz, Chloroform-d) δ 3.97 - 3.17 (m, 25H), 2.55 (p, J = 7.0 Hz, 1H), 1.84 - 1.51 (m, 4H), 1.51 - 0.82 (m, 35H) .

[Synthesis Example 4: Synthesis of compound (1-4)]
Compound (1-3) (5.9 g), 4-(4,6-dimethoxy-1,3,5-triazin-2-yl)-4-methylmorpholinium chloride (4.0 g), allylamine (1 .2g) and methanol (20g) were added, and the mixture was stirred at 25°C for 24 hours. After the reaction was completed, the solvent was distilled off under reduced pressure and flash column chromatography using silica gel (developing solvent: methanol/dichloromethane) was performed to obtain 4.7 g of compound (1-4).

 

The structure of compound (1-4) was confirmed from the following NMR data.
¹ H NMR (500 MHz, Chloroform-d) δ 5.80 (tt, J = 13.5, 6.1 Hz, 1H), 5.29 - 5.07 (m, 2H), 4.46 - 4.08 (m, 2H), 3.92 - 3.26 (m, 25H), 2.38 (p, J = 7.0 Hz, 1H), 1.80 - 0.78 (m, 39H).

[Synthesis Example 5: Synthesis of compound (1-5)]
After adding 1,3-bistrifluoromethylbenzene (10 g) to compound (1-4) (3.0 g) and stirring, platinum/1,3-divinyl-1,1,3,3-tetramethyldisiloxane A toluene solution of the complex (platinum content: 3% by mass, 0.1 g), aniline (0.1 g), and trimethoxysilane (1.0 g) were added, and after stirring at 40°C for 24 hours, the solvent was distilled off under reduced pressure. In this way, 3.3 g of compound (1-5) was obtained.

 

The structure of compound (1-5) was confirmed from the following NMR data.
¹ H NMR (500 MHz, Chloroform-d) δ 3.86 - 3.29 (m, 34H), 3.25 - 3.02 (m, 2H), 2.38 (p, J = 7.0 Hz, 1H), 1.80 - 1.08 (m, 38H) , 0.98 - 0.53 (m, 5H).

[Synthesis Example 6: Synthesis of compound (2-1)]
1,3-bistrifluoromethylbenzene (100 g), pyridine (12 g), and p-toluenesulfonyl chloride (19 g) were added to hexaethylene glycol (28 g), and the mixture was stirred at 25° C. for 24 hours. After the reaction was completed, the solvent was distilled off under reduced pressure and flash column chromatography using silica gel (developing solvent: ethyl acetate/hexane) was performed to obtain 12 g of compound (2-1).

 

The structure of compound (2-1) was confirmed from the following NMR data.
¹ H NMR (500 MHz, Chloroform-d) δ 7.80 - 7.55 (m, 2H), 7.55 - 7.32 (m, 2H), 4.28 (t, J = 7.1 Hz, 2H), 3.96 - 3.45 (m, 22H) , 2.41 (d, J = 1.0 Hz, 3H).

[Synthesis Example 7: Synthesis of compound (2-2)]
THF (100 g) was added to acetonitrile (1.0 g) and cooled to -15°C. Subsequently, 2M diisopropylamide lithium solution (50 mL) was added and stirred at -15°C for 10 minutes. Then, compound (2-1) (11 g) was added and stirred at 25° C. for 1 hour. After cooling the reaction solution to -15°C again, 2M diisopropylamide lithium solution (25 mL) was added and stirred at -15°C for 10 minutes. Thereafter, 9 g of 1-bromooctadecane was added and stirred at 25° C. for 1 hour. After the reaction was completed, hydrochloric acid and dichloromethane were added for extraction, and the solvent was distilled off.
By performing flash column chromatography using silica gel (developing solvent: ethyl acetate/hexane), 8.2 g of compound (2-2) was obtained.

 

The structure of compound (2-2) was confirmed from the following NMR data.
¹ H NMR (500 MHz, Chloroform-d) δ 3.92 - 3.29 (m, 22H), 2.56 (p, J = 7.0 Hz, 1H), 2.11 - 1.47 (m, 4H), 1.47 - 1.02 (m, 32H) , 1.03 - 0.77 (m, 3H).

[Synthesis Example 8: Synthesis of compound (2-3)]
Water (5 g) and concentrated sulfuric acid (15 g) were added to compound (2-2) (8.0 g), and the mixture was stirred at 100° C. for 24 hours. After the reaction was completed, water (100 g) and dichloromethane (100 g) were added for extraction, and the solvent was distilled off. By performing flash column chromatography using silica gel (developing solvent: methanol/dichloromethane), 6.2 g of compound (2-3) was obtained.

 

The structure of compound (2-3) was confirmed from the following NMR data.
¹ H NMR (500 MHz, Chloroform-d) δ 3.88 - 3.31 (m, 22H), 2.55 (p, J = 7.0 Hz, 1H), 2.03 - 1.05 (m, 36H), 1.00 - 0.78 (m, 3H) .

[Synthesis Example 9: Synthesis of compound (2-4)]
Compound (2-3) (5.9 g), 4-(4,6-dimethoxy-1,3,5-triazin-2-yl)-4-methylmorpholinium chloride (4.0 g), allylamine (1 .2g) and methanol (20g) were added, and the mixture was stirred at 25°C for 24 hours. After the reaction was completed, the solvent was distilled off under reduced pressure and flash column chromatography using silica gel (developing solvent: methanol/dichloromethane) was performed to obtain 4.2 g of compound (2-4).

 

The structure of compound (2-4) was confirmed from the following NMR data.
¹ H NMR (500 MHz, Chloroform-d) δ 5.80 (tt, J = 13.5, 6.1 Hz, 1H), 5.19 (ddq, J = 25.8, 13.4, 1.1 Hz, 2H), 4.48 - 4.15 (m, 2H) , 3.95 - 3.32 (m, 22H), 2.38 (p, J = 7.0 Hz, 1H), 1.75 - 1.10 (m, 36H), 1.04 - 0.75 (m, 3H).

[Synthesis Example 10: Synthesis of compound (2-5)]
Compound (2-4) (4.0 g), dichloromethane (40 g), and trichloroacetyl isocyanate (1.5 g) were added, and the mixture was stirred at 25° C. for 24 hours. After evaporating the solvent under reduced pressure, methanol (30 g), water (3 g), and potassium carbonate (3 g) were added, and the mixture was stirred at 25° C. for 24 hours. After the reaction was completed, the solvent was distilled off and flash column chromatography using silica gel (developing solvent: methanol/dichloromethane) was performed to obtain 3.2 g of compound (2-5).

 

The structure of compound (2-5) was confirmed from the following NMR data.
¹ H NMR (500 MHz, Chloroform-d) δ 6.00 - 5.59 (m, 3H), 5.19 (ddq, J = 25.7, 13.4, 1.1 Hz, 2H), 4.57 - 4.13 (m, 4H), 3.93 - 3.27 ( m, 20H), 2.38 (p, J = 7.0 Hz, 1H), 1.78 - 1.04 (m, 36H), 1.01 - 0.72 (m, 3H).

[Synthesis Example 11: Synthesis of compound (2-6)]
After adding 1,3-bistrifluoromethylbenzene (10 g) to compound (2-5) (3.0 g) and stirring, platinum/1,3-divinyl-1,1,3,3-tetramethyldisiloxane A toluene solution of the complex (platinum content: 3% by mass, 0.1 g), aniline (0.1 g), and trimethoxysilane (1.0 g) were added, and after stirring at 40°C for 24 hours, the solvent was distilled off under reduced pressure. In this way, 3.3 g of compound (2-6) was obtained.

 

The structure of compound (2-6) was confirmed from the following NMR data.
¹ H NMR (500 MHz, Chloroform-d) δ 5.86 (s, 2H), 4.50 - 4.10 (m, 2H), 3.92 - 2.88 (m, 31H), 2.38 (p, J = 7.0 Hz, 1H), 1.88 - 1.06 (m, 38H), 0.98 - 0.84 (m, 3H), 0.82 - 0.49 (m, 2H).

[Synthesis Example 12: Synthesis of compound (3-1)]
1,3-bistrifluoromethylbenzene (100 g), potassium carbonate (12.5 g), and phenol (5.0 g) were added to 1,18-dibromooctadecane (20 g), and the mixture was stirred at 80° C. for 24 hours. The solvent was distilled off under reduced pressure and flash column chromatography using silica gel (developing solvent: ethyl acetate/hexane) was performed to obtain 8.4 g of compound (3-1).

 

The structure of compound (3-1) was confirmed from the following NMR data.
¹ H NMR (500 MHz, Chloroform-d) δ 7.41 - 7.14 (m, 2H), 7.01 (tt, J = 7.5, 1.5 Hz, 1H), 6.97 - 6.79 (m, 2H), 3.99 (t, J = 7.1 Hz, 2H), 3.42 (t, J= 7.1 Hz, 2H), 1.79 (dp, J = 38.9, 7.1 Hz, 4H), 1.60 - 1.07 (m, 28H).

[Synthesis Example 13: Synthesis of compound (3-2)]
THF (100 g) was added to acetonitrile (0.8 g) and cooled to -15°C. Subsequently, 2M diisopropylamide lithium solution (10 mL) was added, and the mixture was stirred at -15°C for 10 minutes. Thereafter, compound (3-1) (8.4 g) was added and stirred at 25° C. for 1 hour. After cooling the reaction solution to -15°C again, 2M diisopropylamide lithium solution (10 mL) was added and stirred at -15°C for 10 minutes. Then, compound (1-1) (10 g) was added and stirred at 25° C. for 1 hour. After the reaction was completed, hydrochloric acid and dichloromethane were added for extraction, and the solvent was distilled off.
By performing flash column chromatography using silica gel (developing solvent: ethyl acetate/hexane), 11.4 g of compound (3-2) was obtained.

 

The structure of compound (3-2) was confirmed from the following NMR data.
¹ H NMR (500 MHz, Chloroform-d) δ 7.37 - 6.82 (m, 5H), 4.22 - 3.18 (m, 27H), 2.56 (p, J = 7.0 Hz, 1H), 2.11 - 0.91 (m, 36H) .

[Synthesis Example 14: Synthesis of compound (3-3)]
Water (5 g) and concentrated sulfuric acid (15 g) were added to compound (3-2) (8.0 g), and the mixture was stirred at 100° C. for 24 hours. After the reaction was completed, water (100 g) and dichloromethane (100 g) were added for extraction, and the solvent was distilled off. By performing flash column chromatography using silica gel (developing solvent: methanol/dichloromethane), 5.9 g of compound (3-3) was obtained.

 

The structure of compound (3-3) was confirmed from the following NMR data.
¹ H NMR (500 MHz, Chloroform-d) δ 7.44 - 6.77 (m, 5H), 4.12 - 3.20 (m, 27H), 2.55 (p, J = 7.0 Hz, 1H), 2.08 - 1.06 (m, 36H) .

[Synthesis Example 15: Synthesis of compound (3-4)]
Compound (3-3) (5.9 g), 4-(4,6-dimethoxy-1,3,5-triazin-2-yl)-4-methylmorpholinium chloride (4.0 g), allylamine (1 .2g) and methanol (20g) were added, and the mixture was stirred at 25°C for 24 hours. After the reaction was completed, the solvent was distilled off under reduced pressure and flash column chromatography using silica gel (developing solvent: methanol/dichloromethane) was performed to obtain 4.0 g of compound (3-4).

 

The structure of compound (3-4) was confirmed from the following NMR data.
¹ H NMR (500 MHz, Chloroform-d) δ 7.39 - 6.73 (m, 5H), 5.80 (tt, J = 13.6, 6.1 Hz, 1H), 5.19 (ddq, J= 25.6, 13.4, 0.9 Hz, 2H) , 4.51 - 3.20 (m, 29H), 2.38 (p, J = 7.0 Hz, 1H), 1.93 - 0.94 (m, 36H).

[Synthesis Example 16: Synthesis of compound (3-5)]
After adding 1,3-bistrifluoromethylbenzene (10 g) to compound (3-4) (3.0 g) and stirring, platinum/1,3-divinyl-1,1,3,3-tetramethyldisiloxane A toluene solution of the complex (platinum content: 3% by mass, 0.1 g), aniline (0.1 g), and trimethoxysilane (1.0 g) were added, and after stirring at 40°C for 24 hours, the solvent was distilled off under reduced pressure. In this way, 3.3 g of compound (3-5) was obtained.

 

The structure of compound (3-5) was confirmed from the following NMR data.
¹ H NMR (500 MHz, Chloroform-d) δ 7.39 - 6.82 (m, 5H), 4.18 - 3.30 (m, 36H), 3.27 - 2.94 (m, 2H), 2.38 (p, J = 7.0 Hz, 1H) , 1.88 - 0.98 (m, 38H), 0.68 (ddt, J = 46.9, 12.2, 7.1 Hz, 2H).

[Synthesis Example 17: Synthesis of compound (4-1)]
THF (100 g) and sodium hydride (2.3 g) were added to 1,18-octadecanediol (25 g), and the mixture was stirred at 0° C. for 15 minutes. Thereafter, 4-fluorophenylsulfur pentafluoride (20 g) was added and stirred at 25° C. for 24 hours. After the reaction was completed, hydrochloric acid and dichloromethane were added for extraction, and the solvent was distilled off. By performing flash column chromatography using silica gel (developing solvent: ethyl acetate/hexane), 12.5 g of compound (4-1) was obtained.

 

The structure of compound (4-1) was confirmed from the following NMR data.
¹ H NMR (500 MHz, Chloroform-d) δ 8.17 - 7.91 (m, 2H), 7.12 - 6.83 (m, 2H), 3.99 (t, J = 7.1 Hz, 2H), 3.55 (q, J= 7.0 Hz , 2H), 1.89 - 1.09 (m, 32H).

[Synthesis Example 18: Synthesis of compound (4-2)]
1,3-bistrifluoromethylbenzene (100 g), pyridine (12 g), and p-toluenesulfonyl chloride (10 g) were added to compound (4-1) (12.5 g), and the mixture was stirred at 25° C. for 24 hours. After the reaction was completed, the solvent was distilled off under reduced pressure and flash column chromatography using silica gel (developing solvent: ethyl acetate/hexane) was performed to obtain 12.3 g of compound (4-2).

 

The structure of compound (4-2) was confirmed from the following NMR data.
¹ H NMR (500 MHz, Chloroform-d) δ 8.14 - 7.92 (m, 2H), 7.80 - 7.61 (m, 2H), 7.54 - 7.28 (m, 2H), 7.12 - 6.83 (m, 2H), 3.99 ( td, J = 7.1, 1.1 Hz, 4H), 2.41 (d, J = 1.1 Hz, 3H), 1.97 - 0.98 (m, 32H).

[Synthesis Example 19: Synthesis of compound (4-3)]
THF (100 g) was added to acetonitrile (0.8 g) and cooled to -15°C. Subsequently, 2M diisopropylamide lithium solution (10 mL) was added, and the mixture was stirred at -15°C for 10 minutes. Thereafter, compound (4-2) (12.3 g) was added and stirred at 25° C. for 1 hour. After cooling the reaction solution to -15°C again, 2M diisopropylamide lithium solution (10 mL) was added and stirred at -15°C for 10 minutes. Then, compound (1-1) (10 g) was added and stirred at 25° C. for 1 hour. After the reaction was completed, hydrochloric acid and dichloromethane were added for extraction, and the solvent was distilled off.
By performing flash column chromatography using silica gel (developing solvent: ethyl acetate/hexane), 10.5 g of compound (4-3) was obtained.

 

The structure of compound (4-3) was confirmed from the following NMR data.
¹ H NMR (500 MHz, Chloroform-d) δ 8.15 - 7.90 (m, 2H), 7.10 - 6.79 (m, 2H), 4.32 - 3.14 (m, 27H), 2.56 (p, J = 7.0 Hz, 1H) , 2.13 - 0.91 (m, 36H).

[Synthesis Example 20: Synthesis of compound (4-4)]
Water (5 g) and concentrated sulfuric acid (15 g) were added to compound (4-3) (8.0 g), and the mixture was stirred at 100° C. for 24 hours. After the reaction was completed, water (100 g) and dichloromethane (100 g) were added for extraction, and the solvent was distilled off. By performing flash column chromatography using silica gel (developing solvent: methanol/dichloromethane), 6.5 g of compound (4-4) was obtained.

 

The structure of compound (4-4) was confirmed from the following NMR data.
¹ H NMR (500 MHz, Chloroform-d) δ 8.21 - 7.85 (m, 2H), 7.12 - 6.84 (m, 2H), 4.14 - 3.24 (m, 27H), 2.55 (p, J = 7.0 Hz, 1H) , 2.08 - 1.06 (m, 36H).

[Synthesis Example 21: Synthesis of compound (4-5)]
Compound (4-4) (6.0 g), 4-(4,6-dimethoxy-1,3,5-triazin-2-yl)-4-methylmorpholinium chloride (4.0 g), allylamine (1 .2g) and methanol (20g) were added, and the mixture was stirred at 25°C for 24 hours. After the reaction was completed, the solvent was distilled off under reduced pressure and flash column chromatography using silica gel (developing solvent: methanol/dichloromethane) was performed to obtain 5.2 g of compound (4-5).

 

The structure of compound (4-5) was confirmed from the following NMR data.
¹ H NMR (500 MHz, Chloroform-d) δ 8.17 - 7.90 (m, 2H), 7.11 - 6.84 (m, 2H), 5.80 (tt, J = 13.6, 6.1 Hz, 1H), 5.19 (ddq, J = 25.6, 13.4, 0.9 Hz, 2H), 4.54 - 3.17 (m, 29H), 2.38 (p, J = 7.0 Hz, 1H), 1.93 - 1.04 (m, 36H).

[Synthesis Example 22: Synthesis of compound (4-6)]
After adding 1,3-bistrifluoromethylbenzene (10 g) to compound (4-5) (3.0 g) and stirring, platinum/1,3-divinyl-1,1,3,3-tetramethyldisiloxane A toluene solution of the complex (platinum content: 3% by mass, 0.1 g), aniline (0.1 g), and trimethoxysilane (1.0 g) were added, and after stirring at 40°C for 24 hours, the solvent was distilled off under reduced pressure. In this way, 3.3 g of compound (4-6) was obtained.

 

The structure of compound (4-6) was confirmed from the following NMR data.
¹ H NMR (500 MHz, Chloroform-d) δ 8.15 - 7.94 (m, 2H), 7.13 - 6.79 (m, 2H), 4.26 - 3.28 (m, 36H), 3.22 - 3.01 (m, 2H), 2.38 ( p, J = 7.0 Hz, 1H), 1.87 - 1.04 (m, 38H), 0.68 (ddt, J = 46.9, 12.2, 7.1 Hz, 2H).

[Synthesis Example 23: Synthesis of compound (5-1)]
Add 1,3-bistrifluoromethylbenzene (100 g), pyridine (12 g), and p-toluenesulfonyl chloride (5 g) to monocarbinol-terminated polydimethylsiloxane (40 g, Gelest, product number: MCR-C12), The mixture was stirred at 25°C for 24 hours. After the reaction was completed, the solvent was distilled off under reduced pressure and flash column chromatography using silica gel (developing solvent: ethyl acetate/hexane) was performed to obtain 33 g of compound (5-1).

 

The structure of compound (5-1) was confirmed from the following NMR data. Note that the average value of the number of repetitions X in the above formula is 11.
¹ H NMR (500 MHz, Chloroform-d) δ 7.81 - 7.61 (m, 2H), 7.53 - 7.23 (m, 2H), 4.28 (t, J = 7.2 Hz, 2H), 3.73 (t, J= 7.0 Hz , 2H), 3.33 (t, J = 7.1 Hz, 2H), 2.41 (d, J = 1.1 Hz, 3H), 1.69 - 1.11 (m, 6H), 1.04 - 0.89 (m, 3H), 0.75 (dt, J = 30.4, 7.0 Hz, 4H), 0.26 - -0.15 (m, 72H).

[Synthesis Example 24: Synthesis of compound (5-2)]
THF (100 g) was added to acetonitrile (0.8 g) and cooled to -15°C. Subsequently, 2M diisopropylamide lithium solution (10 mL) was added, and the mixture was stirred at -15°C for 10 minutes. Then, compound (1-1) (10 g) was added and stirred at 25° C. for 1 hour. After cooling the reaction solution to -15°C again, 2M diisopropylamide lithium solution (10 mL) was added and stirred at -15°C for 10 minutes. Then, compound (5-1) (22 g) was added and stirred at 25° C. for 1 hour. After the reaction was completed, hydrochloric acid and dichloromethane were added for extraction, and the solvent was distilled off.
By performing flash column chromatography using silica gel (developing solvent: ethyl acetate/hexane), 19 g of compound (5-2) was obtained.

 

The structure of compound (5-2) was confirmed from the following NMR data. Note that the average value of the number of repetitions X in the above formula is 11.
¹ H NMR (500 MHz, Chloroform-d) δ 3.90 - 3.13 (m, 29H), 2.60 (p, J = 7.0 Hz, 1H), 2.01 - 1.16 (m, 10H), 1.03 - 0.90 (m, 3H) , 0.87 - 0.58 (m, 4H), 0.24 - -0.25 (m, 72H).

[Synthesis Example 25: Synthesis of compound (5-3)]
Water (5 g) and concentrated sulfuric acid (15 g) were added to compound (5-2) (8.0 g), and the mixture was stirred at 100° C. for 24 hours. After the reaction was completed, water (100 g) and dichloromethane (100 g) were added for extraction, and the solvent was distilled off. By performing flash column chromatography using silica gel (developing solvent: methanol/dichloromethane), 7.1 g of compound (5-3) was obtained.

 

The structure of compound (5-3) was confirmed from the following NMR data. Note that the average value of the number of repetitions X in the above formula is 11.
¹ H NMR (500 MHz, Chloroform-d) δ 3.86 - 3.17 (m, 29H), 2.59 (p, J = 7.0 Hz, 1H), 2.01 - 1.11 (m, 10H), 1.06 - 0.90 (m, 3H) , 0.75 (dt, J = 30.4, 7.0 Hz, 4H), 0.22 - -0.16 (m, 72H).

[Synthesis Example 26: Synthesis of compound (5-4)]
Compound (5-3) (6.0 g), 4-(4,6-dimethoxy-1,3,5-triazin-2-yl)-4-methylmorpholinium chloride (4.0 g), allylamine (1 .2g) and methanol (20g) were added, and the mixture was stirred at 25°C for 24 hours. After the reaction was completed, the solvent was distilled off under reduced pressure and flash column chromatography using silica gel (developing solvent: methanol/dichloromethane) was performed to obtain 5.0 g of compound (5-4).

 

The structure of compound (5-4) was confirmed from the following NMR data. Note that the average value of the number of repetitions X in the above formula is 11.
¹ H NMR (500 MHz, Chloroform-d) δ 5.95 - 5.66 (m, 1H), 5.33 - 5.07 (m, 2H), 4.46 - 4.08 (m, 2H), 3.92 - 3.10 (m, 29H), 2.42 ( p, J = 7.0 Hz, 1H), 1.92 - 1.14 (m, 10H), 1.07 - 0.91 (m, 3H), 0.87 - 0.61 (m, 4H), 0.21 - -0.18 (m, 72H).

[Synthesis Example 27: Synthesis of compound (5-5)]
After adding 1,3-bistrifluoromethylbenzene (10 g) to compound (5-4) (3.0 g) and stirring, platinum/1,3-divinyl-1,1,3,3-tetramethyldisiloxane A toluene solution of the complex (platinum content: 3% by mass, 0.1 g), aniline (0.1 g), and trimethoxysilane (1.0 g) were added, and after stirring at 40°C for 24 hours, the solvent was distilled off under reduced pressure. In this way, 3.2 g of compound (5-5) was obtained.

 

The structure of compound (5-5) was confirmed from the following NMR data. Note that the average value of the number of repetitions X in the above formula is 11.
¹ H NMR (500 MHz, Chloroform-d) δ 4.00 - 2.94 (m, 40H), 2.42 (p, J = 7.0 Hz, 1H), 1.80 - 1.10 (m, 12H), 1.05 - 0.89 (m, 3H) , 0.87 - 0.54 (m, 6H), 0.26 - -0.19 (m, 72H).

[Synthesis Example 28: Synthesis of Compound (C-1) (Comparative Example 1)]
Compound (C-1) was obtained according to Examples of JP-A-2017-201010.

 

[Manufacture and evaluation of articles]
The base material was surface-treated using each compound obtained in Synthesis Examples 5, 11, 16, 22, 27, and 28, and octadecyltrimethoxysilane (manufactured by Tokyo Kasei Kogyo Co., Ltd., product code: O0256), and Examples 1- 7 items were obtained. As a surface treatment method, the following dry coating method was used for each example. Chemically strengthened glass was used as the base material. The obtained article was evaluated by the following method. The results are shown in Table 1.

(Dry coating method)
The dry coating was performed using a vacuum evaporation device (VTR350M, manufactured by ULVAC) (vacuum evaporation method). 0.5 g of a 20% by mass ethyl acetate solution of each compound was filled into a molybdenum boat in a vacuum evaporation apparatus, and the inside of the vacuum evaporation apparatus was evacuated to 1×10 ⁻³ Pa or less. The boat containing the compound solution is heated at a temperature increase rate of 10°C/min or less, and when the deposition rate exceeds 1 nm/sec using a crystal oscillation type film thickness meter, the shutter is opened to deposit the compound solution onto the surface of the substrate. The membrane was started. When the film thickness reached approximately 50 nm, the shutter was closed to complete the film formation on the surface of the substrate. The substrate on which the compound was deposited was heat-treated at 150° C. for 30 minutes to obtain an article having a surface layer on the surface of the substrate.

(Evaluation method)
<Method of measuring water contact angle>
The contact angle of about 2 μL of distilled water placed on the surface of the surface layer was measured using a contact angle measuring device (DM-500, manufactured by Kyowa Interface Science Co., Ltd.). Measurements were made at five different locations on the surface of the surface layer, and the average value was calculated. The 2θ method was used to calculate the contact angle.
The evaluation criteria are as follows.
AA: 105 degrees or more.
A: 100 degrees or more and less than 105 degrees.
B: Less than 100 degrees.

<Method for measuring contact angle of n-hexadecane>
The contact angle of about 2 μL of n-hexadecane placed on the surface of the surface layer was measured using a contact angle measuring device (DM-500, manufactured by Kyowa Interface Science Co., Ltd.). Measurements were made at five different locations on the surface of the surface layer, and the average value was calculated. The 2θ method was used to calculate the contact angle.
The evaluation criteria are as follows.
A: It is 35 degrees or more.
B: 30 degrees or more and less than 35 degrees.
C: Less than 30 degrees.

<Method for measuring the falling angle of n-hexadecane>
The falling angle was measured using an automatic contact angle meter DM-501. Specifically, about 15 μL of normal hexadecane was dropped onto the surface of the surface layer, and automatic measurement was performed.
The evaluation criteria are as follows.
A: Less than 10 degrees.
B: 10 degrees or more.

In the above examples, Examples 1 to 5 are examples, and Examples 6 to 7 are comparative examples. As shown in Table 1, Examples 1 to 5 have good initial water contact angles and initial n-hexadecane contact angles. That is, both the water repellency and oil repellency evaluations were good. On the other hand, Examples 6 and 7 cannot achieve both excellent water repellency and oil repellency.

The compounds of the present disclosure are useful as surface treatment agents. The surface treatment agent can be used, for example, for substrates in display devices such as touch panel displays, optical elements, semiconductor elements, building materials, automobile parts, nanoimprint technology, and the like. Furthermore, the surface treatment agent can be used for bodies, window glasses (windshields, side glasses, rear glasses), mirrors, bumpers, etc. of transportation equipment such as trains, automobiles, ships, and airplanes. Furthermore, the surface treatment agent can be used for outdoor articles such as building exterior walls, tents, solar power generation modules, sound insulation boards, and concrete; fishing nets, insect nets, and aquariums. Furthermore, the surface treatment agent can be used for various indoor equipment such as kitchens, bathrooms, washstands, mirrors, toilet peripheral parts; ceramics such as chandeliers and tiles; artificial marble, and air conditioners. Furthermore, the surface treatment agent can be used as an antifouling treatment for jigs, inner walls, piping, etc. in a factory. Furthermore, the surface treatment agent can be used for goggles, glasses, helmets, pachinko machines, textiles, umbrellas, play equipment, and soccer balls. Furthermore, the surface treatment agent can also be used as an adhesion prevention agent for various packaging materials such as food packaging materials, cosmetic packaging materials, and the inside of pots. In addition, surface treatment agents are used for medical applications such as car navigation systems, mobile phones, smartphones, digital cameras, digital video cameras, PDAs, portable audio players, car audio, game equipment, eyeglass lenses, camera lenses, lens filters, sunglasses, and gastrocameras. It can be used for optical members such as appliances, copying machines, PCs, displays (for example, liquid crystal displays, organic EL displays, plasma displays, touch panel displays), touch panels, protective films, and antireflection films.

The disclosure of Japanese Patent Application No. 2022-069031 filed on April 19, 2022 is incorporated herein by reference in its entirety. In addition, all documents, patent applications, and technical standards mentioned herein are incorporated by reference to the same extent as if each individual document, patent application, and technical standard were specifically and individually indicated to be incorporated by reference. , incorporated herein by reference.

Claims (11)

1. A compound containing at least one member selected from the group consisting of a polydialkylsiloxane residue and an alkylene chain having 10 or more carbon atoms, a polyoxyalkylene chain, and a reactive silyl group.
2. A compound represented by the following formula (1).
   
   
   In formula (1),
   T ¹ and T ² are each independently a hydrogen atom or a monovalent group,
   Z is each independently a polydialkylsiloxane residue or an alkylene chain having 10 or more carbon atoms,
   A is a polyoxyalkylene chain,
   Y ¹ is a (p+q+g)-valent linking group,
   R ¹ is each independently a monovalent hydrocarbon group,
   L ² is each independently a hydrolyzable group or a hydroxyl group,
   p is an integer from 1 to 3,
   q is an integer from 1 to 3,
   n is an integer from 0 to 2,
   g is an integer of 1 or more.
3. The compound according to claim 2, wherein p and q in the formula (1) are both 1.
4. A composition comprising the compound according to any one of claims 1 to 3 and a liquid medium.
5. A surface treatment agent comprising the compound according to any one of claims 1 to 3.
6. The surface treatment agent according to claim 5, further comprising a liquid medium.
7. A method for manufacturing an article, comprising performing a surface treatment on a base material using the surface treatment agent according to claim 5, and manufacturing an article in which a surface treatment layer is formed on the base material.
8. A method for manufacturing an article, comprising performing a surface treatment on a base material using the surface treatment agent according to claim 6, and manufacturing an article in which a surface treatment layer is formed on the base material.
9. An article comprising a base material and a surface treatment layer disposed on the base material and surface treated with the surface treatment agent according to claim 5.
10. The article according to claim 9, wherein the article is an optical member.
11. The article according to claim 9, wherein the article is a display or a touch panel.