JP-7856100-B2 - Fluorine-containing ether compounds, fluorine-containing ether mixtures, coating agents, articles, and methods for manufacturing articles

JP7856100B2JP 7856100 B2JP7856100 B2JP 7856100B2JP-7856100-B2

Inventors

高下隆太
長谷川剛
齊藤祥一
富澤英樹

Assignees

ＡＧＣ株式会社

Dates

Publication Date: 20260511
Application Date: 20220608
Priority Date: 20210621

Claims (16)

A fluorine-containing ether compound represented by the following formula (A). Formula (A): X 1 -Si(R 1 ) n L 2-n -O-X 2 -O-Si(R 1 ) n L 2-n -X 1 In formula (A), Each X1 independently represents a monovalent organic group having a poly(oxyfluoroalkylene) chain, X2 represents a divalent organic group containing a poly(oxyperfluoroalkylene) group , where the atoms at both ends of X2 bonded to the two oxygen atoms in formula (A) are carbon atoms. Each R1 independently represents a monovalent hydrocarbon group. Each L independently represents a hydrolyzable group or a hydroxyl group. Each n represents an independent integer between 0 and 2.
The fluorine-containing ether compound according to claim 1, wherein in formula (A), X2 comprises an alkylene group, a fluoroalkylene group, or an etheric oxygen atom-containing group having an etheric oxygen atom between carbon atoms of the alkylene group or fluoroalkylene group.
The fluorine-containing ether compound according to claim 1 , wherein formula (A) includes a structure represented by {(OCF 2 ) m21 (OCF 2 CF 2 ) m22 }, where m21 is an integer of 1 or more, m22 is an integer of 1 or more, and m21 + m22 is an integer from 2 to 500.
The fluorine-containing ether compound according to claim 3 , wherein in the above {(OCF 2 ) m21 (OCF 2 CF 2 ) m22 }, m21 > m22.
In equation (A), X² is Poly(oxyperfluoroalkylene) group and A divalent organic group selected from the group consisting of an alkylene group, an etheric oxygen atom-containing group having an etheric oxygen atom between carbon atoms of the alkylene group, a perfluoroalkylene group, and combinations thereof, which links a poly(oxyperfluoroalkylene) group to at least one of the two oxygen atoms in formula (A), A fluorine-containing ether compound according to claim 1 , wherein the group has a group having the same properties.
A method for producing a fluorine-containing ether compound according to any one of claims 1 to 5 , comprising transesterifying a compound represented by the following formula (Cs) with a compound represented by the following formula (Cd) in the presence of a catalyst. Formula (Cs): X 1 -Si(R 1 ) n L 3-n Formula (Cd): HO-X 2 -OH In the formula (Cs), X1 represents a monovalent organic group having a poly(oxyfluoroalkylene) chain, Each R1 independently represents a monovalent hydrocarbon group. Each L independently represents a hydrolyzable group or a hydroxyl group. n represents an integer between 0 and 2. In equation (Cd), X2 represents a divalent organic group, where the atoms at both ends of X2 that are bonded to the two hydroxyl groups in formula (Cd) are carbon atoms.
The method for producing a fluorine-containing ether compound according to claim 6, wherein in the transesterification, the molar ratio (M Cs / M Cd ) of the amount of the compound represented by formula ( Cs ) to the amount of the compound represented by formula (Cd ) is 1.5 to 4.0.
The method for producing a fluorine-containing ether compound according to claim 6, wherein the catalyst comprises at least one selected from the group consisting of carboxylic acids, Lewis acids, substituted or unsubstituted pyridines, substituted or unsubstituted imidazoles , tertiary phosphines, amine compounds, and solid catalysts.
A fluorine-containing ether mixture comprising two or more fluorine-containing ether compounds described in any one of claims 1 to 5 , or one or more fluorine-containing ether compounds described in any one of claims 1 to 5 and a fluorine-containing ether compound other than the fluorine-containing ether compounds described in any one of claims 1 to 5 .
A coating agent comprising a fluorine-containing ether compound according to any one of claims 1 to 5 .
The coating agent according to claim 10 , further comprising a liquid medium.
An article having a base material and a surface layer formed on the base material by the coating agent described in claim 10 .
The article according to claim 12 , wherein the article is a touch panel, and the surface layer is formed on the surface of a member that constitutes the surface of the touch panel that is touched by a finger.
A method for manufacturing an article, comprising applying the coating agent described in claim 10 to the surface of a substrate by a dry coating method to form a surface layer on the substrate.
A method for manufacturing an article, comprising applying the coating agent described in claim 11 to the surface of a substrate by a dry coating method to form a surface layer on the substrate.
The coating agent described in claim 11 is applied to the surface of the substrate by a wet coating method, The substrate to which the coating agent has been applied is dried to form a surface layer on the substrate, A method for manufacturing articles, including

Description

This disclosure relates to fluorine-containing ether compounds, fluorine-containing ether mixtures, coatings, articles, and methods for producing articles. Fluorine-containing compounds are suitable for use as surface treatment agents because they exhibit high lubricity, water-repellent and oil-repellent properties. By imparting water-repellent and oil-repellent properties to the surface of a substrate using a surface treatment agent, dirt on the substrate surface becomes easier to wipe away, improving dirt removal efficiency. Among fluorine-containing compounds, fluorine-containing ether compounds having poly(oxyfluoroalkylene) chains with ether bonds in the fluoroalkylene chain are compounds with excellent flexibility and are particularly excellent at removing oils and greases. As fluorine-containing ether compounds, compounds having a poly(oxyperfluoroalkylene) chain and a hydrolyzable silyl group at the terminal are widely used. For example, Patent Document 1 describes that a surface treatment layer having water-repellent, oil-repellent, stain-resistant, and waterproof properties, as well as excellent abrasion resistance, can be formed using a mixture of a poly(oxyperfluoroalkylene) group-containing silane compound and a fluorine-containing compound. Patent Document 2 describes a fluorine-containing ether composition for vapor deposition that comprises a compound having a poly(oxyperfluoroalkylene) chain and a hydrolyzable silyl group, and a partial condensate of the said compound, and capable of forming a vapor-deposited film with excellent friction resistance. Japanese Patent Publication No. 2016-132719International Publication No. 2018/221520 The embodiments for carrying out the embodiments of this disclosure will be described in detail below. However, the embodiments of this disclosure are not limited to the embodiments described below. In the embodiments described below, the components (including elemental steps, etc.) are not essential unless otherwise specified. The same applies to numerical values and their ranges, and do not limit the embodiments of this disclosure. In this disclosure, the term "process" includes not only processes that are independent of other processes, but also processes that cannot be clearly distinguished from other processes, provided that the purpose of such process is achieved. In this disclosure, the numerical range indicated using "~" includes the numbers before and after "~" as the minimum and maximum values, respectively. In this disclosure, each component may contain multiple types of the corresponding substance. If multiple types of the substance corresponding to each component are present in the composition, the content or amount of each component means the total content or amount of the multiple types of substances present in the composition, unless otherwise specified. In this disclosure, the terms “alkyl group” and “alkylene group” mean an unsubstituted alkyl group and an unsubstituted alkylene group, respectively, unless otherwise specified. <Fluorine-containing ether compounds> The fluorine ether compounds of this disclosure are represented by the following formula (A). Formula (A): X 1 -Si(R 1 ) n L 2-n -O-X 2 -O-Si(R 1 ) n L 2-n -X 1 In formula (A), Each X1 independently represents a monovalent organic group having a poly(oxyfluoroalkylene) chain, X2 represents a divalent organic group, where the atoms at both ends of X2 bonded to the two oxygen atoms in formula (A) are carbon atoms. Each R1 independently represents a monovalent hydrocarbon group. Each L independently represents a hydrolyzable group or a hydroxyl group. Each n represents an independent integer between 0 and 2. In this disclosure, the fluorine-containing ether compound is also referred to as a "specific fluorine-containing ether compound." In this disclosure, each group of a specific fluorine-containing ether compound may be referred to as follows: (S) group: A monovalent organic group represented by X 1 -Si(R 1 ) nL 2-n -O- in formula (A) above. (D) group: A divalent group represented by -X 2- in formula (A) above. The specific fluorine ether compound has a structure represented by (S) group-(D) group-(S) group. The two (S) groups may be the same or different. From the viewpoint of ease of manufacture, it is preferable that the two (S) groups are the same. The inventors discovered that using a specific fluorine-containing ether compound allows for the formation of a surface layer with excellent abrasion resistance. While the reason for this is not entirely clear, it is speculated to be as follows: For example, Patent Document 1 describes a composition obtained by mixing a poly(oxyperfluoroalkylene) group-containing silane compound with a monovalent poly(oxyperfluoroalkylene) group-containing alcohol compound. On the other hand, since specific fluorine-containing ether compounds have a structure in which multiple (S) groups having poly(oxyfluoroalkylene) chains are linked via (D) groups, it