JP2013209636A - Liquid-repellent treatment agent, liquid-repellent film, member having water-repellent region and hydrophilic region, method for producing the same, and method for producing member having pattern of functional material formed thereon - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a water-repellent treatment agent that can form a liquid-repellent film having excellent liquid repellency, and that, by having excellent base resistance, can form a pattern having high contrast even when a basic functional material is used.SOLUTION: A liquid-repellent treatment agent includes a fluorine-containing compound represented by general formula (1) and a fluorine-containing compound represented by general formula (12) or (13).

Description

  The present invention relates to a liquid repellent treatment agent, a liquid repellent film formed using the liquid repellent treatment agent, a member having a water repellent region and a hydrophilic region, a method for producing the member, and a pattern of a functional material. The present invention relates to a method for manufacturing the formed member.

The water repellent agent is used in various applications. For example, in the field of semiconductor elements, displays, light emitting elements, etc., a water repellent agent is applied on a hydrophilic base material to form a hydrophilic region and a water repellent agent. A functional material having a desired characteristic is formed at a desired position using a difference in properties between the hydrophilic region and the water-repellent region (for example, a hydrophilic region). There is known a method of forming a functional member having a pattern (having a functional material on the top and no functional material on the water-repellent region).
The functional member is used as, for example, a wiring, an electrode, an insulating layer, a light emitting layer, and an optical thin film.

  In recent years, such a water-repellent region may require hardness and friction resistance. For example, in the case of aiming to improve the productivity of functional members, more specifically, for example, a usage form in which a liquid in which inorganic fine particles are dispersed as a functional material is applied to a hydrophilic region at high speed by an inkjet method, for example. And a usage form in which a functional material is transferred to a hydrophilic region by a roll-to-roll method (Roll to Roll method). For this reason, there is a high demand for a water-repellent treatment agent that can be suitably used in a usage pattern that requires hardness and friction resistance in the water-repellent region. In order to improve the hardness and friction resistance of the water repellent region, it is effective to add a bifunctional or higher polymerizable compound to the water repellent treatment agent composition.

Patent Document 1 describes that a water-repellent region is formed by curing a composition containing a polymerizable fluorine-containing compound that is a polyhydric alcohol derivative.
Patent Document 2 describes that a water-repellent region is formed by curing a composition containing a polymerizable fluorine-containing compound having one or two epoxy groups.

  Regarding the polymerizable fluorine-containing compound, Patent Document 3 discloses a fluorine-containing polyfunctional monomer suitable for forming a polymer thin film suitable as an antireflection film.

International Publication No. 08/018599 JP 2007-248726 A JP 2006-028280 A

However, in a member having a water-repellent region and a hydrophilic region formed using the composition containing the polymerizable fluorine-containing compound described in Patent Document 1, a liquid containing a basic functional material in the hydrophilic region. When an attempt is made to form a functional material pattern by coating, the frictional resistance is excellent, but the water-repellent region is poor in base resistance, resulting in disturbance of the boundary between the hydrophilic region and the water-repellent region. There is a problem that the contrast at the boundary between the hydrophilic region and the water repellent region is lowered, and a functional member having a desired pattern cannot be obtained.
When the composition containing the polymerizable fluorine-containing compound described in Patent Document 2 is used as a water-repellent film, the fluorine content of the polymerizable fluorine-containing compound is low, so that the film has insufficient water repellency and high contrast. In addition, there is a problem that a member having the above cannot be obtained, and since the polymerizable group density is low, the friction resistance is inferior, so that it is not suitable for a usage form that requires hardness and friction resistance.
In addition, Patent Document 3 neither describes nor suggests that the fluorine-containing polyfunctional monomer can be used as a water-repellent film.

  Therefore, the problem of the present invention is high even when a basic functional material is used because a liquid-repellent film excellent in liquid repellency and friction resistance can be formed and the base resistance is excellent. It is an object of the present invention to provide a water repellent agent capable of forming a pattern having contrast.

  As a result of intensive studies in view of the above circumstances, the present inventors have found that in a liquid-repellent film using a liquid-repellent treatment agent having a specific compound having a fluorine-containing core part and another specific type of fluorine-containing compound. The inventors have found that the base resistance and the friction resistance are good and the liquid repellency is very high. Furthermore, even though the liquid repellency is very high, an unexpected effect was found that even when a liquid repellent treatment agent was applied to a hydrophilic surface, it was not repelled (a uniform coating film could be formed). The invention has been completed.

  That is, the present invention is as follows.

[1]
A liquid repellent treatment agent comprising a fluorine-containing compound represented by the following general formula (1) and a fluorine-containing compound represented by the following general formula (12) or (13).

In general formula (1), a represents an integer of 3 to 8, b represents an integer of 0 to 3, c represents an integer of 0 to 10, d and e each independently represents 0 or 1, r represents 0 or 1, Y represents a group represented by the following general formula (2), (3), (4) or (5), an allyl group, or a vinyl group, and L ₁ represents the following general formula ( 6) or a group represented by (7), L ₂ and L ₃ each independently represent a group represented by the following general formula (8), (9), (10) or (11) , Rf ₁ represents a (a + b) -valent, may contain an etheric oxygen atom, a linear, branched or cyclic saturated perfluoroalkyl group having 3 to 20 carbon atoms, Rf ₂ is etheric oxygen atoms may contain, represents a monovalent perfluoroalkyl group or a fluorine atom, linear or branched C1-5, Rf ₃ is It may contain ether oxygen atoms, a straight, branched or cyclic, monovalent perfluoroalkyl group of 3 to 100 carbon atoms.

In general formula (2), X represents a hydrogen atom, a fluorine atom, a chlorine atom, a methyl group, a trifluoromethyl group, or a hydroxyl group.
In general formulas (3), (4) and (5), R ₁ , R ₂ , R ₃ , R ₄ , R ₅ and R ₆ may each independently have a hydrogen atom or a substituent. It represents a good linear or branched monovalent alkyl group having 1 to 5 carbon atoms.
In general formula (5), k represents 1 or 2.
In general formulas (6) and (7), m represents an integer of 0 to 10.
In general formula (8), (9), (10), (11), n represents the integer of 0-10.
In the general formula (7), Y represents a group represented by the above general formula (2), (3), (4) or (5), an allyl group, or a vinyl group.

In general formula (12), f represents an integer of 1 to 5, g represents 0 or 1, and Y represents a group represented by the general formula (2), (3), (4) or (5). , An allyl group, or a vinyl group, L ₄ represents a group represented by the above general formula (6) or (7), or the following general formula (14) or (15), and Rf ₄ represents an etheric oxygen A linear, branched or cyclic monovalent perfluoroalkyl group having 1 to 100 carbon atoms which may contain an atom is represented.
In general formula (13), h and i each independently represent an integer of 1 to 5, Y is a group represented by the above general formula (2), (3), (4) or (5), or an allyl group Or a vinyl group, L ₄ each independently represents a group represented by the above general formula (6) or (7), or the following general formula (14) or (15), and Rf ₅ represents an etheric oxygen A linear, branched or cyclic divalent perfluoroalkyl group having 1 to 100 carbon atoms which may contain an atom is represented.

In general formula (14), m represents an integer of 0 to 10.
In general formula (15), Y represents a group represented by the above general formula (2), (3), (4) or (5), an allyl group, or a vinyl group.
[2]
The content ratio of the fluorine-containing compound represented by the general formula (1) is 5% by mass or more and 90% by mass or less, and the content ratio of the fluorine-containing compound represented by the general formula (12) or (13) is The liquid repellent treatment agent according to [1], which is 10% by mass or more and 95% by mass.
[3]
The liquid repellent treatment agent according to [1] or [2], wherein a fluorine atom content of the fluorine-containing compound represented by the general formula (12) or (13) is 30% by mass or more and 75% by mass or less.
[4]
Furthermore, the liquid-repellent processing agent of any one of [1]-[3] containing the non-fluorine compound represented by following General formula (16).

In general formula (16), j represents an integer of 1 to 6, and Y represents a group represented by the following general formula (21), (3), (4) or (5), an allyl group, or a vinyl group. L ₅ represents a group represented by the following general formula (6), (7), (14) or (15), and R ₇ is a hydrogen atom or a carbon number which may have a substituent. 1-20 linear, branched or cyclic j-valent organic groups are represented.

In General Formula (21), X ¹ represents a hydrogen atom, a chlorine atom, a methyl group, or a hydroxyl group.
In general formulas (3), (4) and (5), R ₁ , R ₂ , R ₃ , R ₄ , R ₅ and R ₆ may each independently have a hydrogen atom or a substituent. It represents a good linear or branched monovalent alkyl group having 1 to 5 carbon atoms.
In general formula (5), k represents 1 or 2.
In general formulas (6), (7), and (14), m represents an integer of 0 to 10.
In general formulas (7) and (15), Y represents a group represented by the above general formula (21), (3), (4) or (5), an allyl group, or a vinyl group.
[5]
The liquid repellent treatment agent according to any one of [1] to [4], wherein (a + b) in the general formula (1) is an integer of 3 to 8.
[6]
The liquid repellent treatment agent according to any one of [1] to [5], wherein d and e in the general formula (1) are 1.
[7]
The fluorine-containing compound represented by the general formula (1) is a fluorine-containing compound represented by the following general formula (17), and the fluorine-containing compound represented by the general formula (12) or (13) is The liquid repellent treatment agent according to any one of [1] to [6], which is a fluorine-containing compound represented by the general formula (18) or (19).

In general formula (17), a represents an integer of 3 to 8, b represents an integer of 0 to 3, c represents an integer of 0 to 10, Y represents the following formulas (2), (3), ( 4) or a group represented by (5), an allyl group, or a vinyl group, L ₁ represents a group represented by the following formula (6) or (7), and Rf ₁ is an (a + b) -valent group. may contain an etheric oxygen atom, a linear, branched or cyclic saturated perfluoroalkyl group having 3 to 20 carbon atoms, Rf ₂ may contain an etheric oxygen atom, 1 to carbon atoms 5 represents a linear or branched monovalent perfluoroalkyl group or a fluorine atom, and Rf ₆ may contain an etheric oxygen atom having at least one trifluoromethyl group, having 3 to 3 carbon atoms 100 linear, branched or cyclic monovalent perfluoroalkyl groups are represented.

In general formula (2), X represents a hydrogen atom, a fluorine atom, a chlorine atom, a methyl group, a trifluoromethyl group, or a hydroxyl group.
In general formulas (3), (4) and (5), R ₁ , R ₂ , R ₃ , R ₄ , R ₅ and R ₆ may each independently have a hydrogen atom or a substituent. It represents a good linear or branched monovalent alkyl group having 1 to 5 carbon atoms.
In general formula (5), k represents 1 or 2.
In general formulas (6) and (7), m represents an integer of 0 to 10.
In general formula (8), (9), (10), (11), n represents the integer of 0-10.
In the general formula (7), Y represents a group represented by the above general formula (2), (3), (4) or (5), an allyl group, or a vinyl group.

In general formula (18), f represents an integer of 1 to 5, and Y represents a group represented by the above general formula (2), (3), (4) or (5), an allyl group, or a vinyl group. Rf ₇ represents a linear, branched or cyclic monovalent perfluoroalkyl group having 1 to 100 carbon atoms, which may contain an etheric oxygen atom, and has at least one trifluoromethyl group. .
In general formula (19), h and i each independently represent an integer of 1 to 5, Y is a group represented by the above general formula (2), (3), (4) or (5), an allyl group Or Rf ₈ represents a linear or branched divalent perfluoroalkyl group having 1 to 100 carbon atoms, which may contain an etheric oxygen atom.
[8]
The liquid repellent treatment agent according to any one of [1] to [7], wherein Rf1 in the general formula (1) is a group selected from the following f- ₁ to f-14.

Wherein * _{Y-L 1 -O-CH 2} - (CF 2) c - [CF (Rf 2)] r - (O) d -L 2 - or _{Rf 3 - (O) e -L} 3 - Represents the position to be combined.
[9]
A liquid repellent film obtained by curing the liquid repellent treatment agent according to any one of [1] to [8].
[10]
A member having a water-repellent region and a hydrophilic region on the surface of a substrate, wherein the water-repellent region is obtained by curing the liquid-repellent treatment agent according to any one of [1] to [8]. A member made of a liquid film.
[11]
The member according to [10], wherein the water-repellent region and the hydrophilic region form a pattern.
[12]
A step of forming a coating film containing the liquid repellent treatment agent according to any one of [1] to [8] on the surface of a substrate having a hydrophilic surface, and then irradiating a part of the coating film with light A step of curing the coating film containing the liquid repellent treatment agent, and then a step of removing the uncured liquid repellent treatment agent on the substrate surface to expose the hydrophilic surface, [10] or [11] The manufacturing method of the member as described in any one of.
[13]
The step of applying a liquid containing a functional material to the hydrophilic region of the member according to [10] or [11] or the member manufactured by the manufacturing method according to [12], and then a member to which the liquid is applied The manufacturing method of the member in which the pattern of the functional material was formed including the process of drying.

  According to the present invention, a liquid-repellent treatment agent that has good base resistance and friction resistance, has very high liquid repellency, and does not repel even when applied to a hydrophilic surface at the same time, the liquid repellency Provided are a liquid repellent film and a treated substrate using a treating agent, a method for producing a treated substrate, and a method for producing a member provided with a functional material.

Cross-sectional schematic diagram showing one embodiment of a method for producing a treated substrate of the present invention Cross-sectional schematic diagram showing one embodiment of a method for producing a member of the present invention

The liquid repellent treatment agent of the present invention contains a fluorine-containing compound represented by the following general formula (1) and a fluorine-containing compound represented by the following general formula (12) or (13).
The compounds represented by general formula (1), general formula (12), and general formula (13) are described in detail below.

<Compound represented by the general formula (1)>
The compound represented by the general formula (1) used in the present invention is mainly composed of a plurality of fluorine atoms and carbon atoms (however, oxygen atoms may be partly included), and does not substantially participate in polymerization. 3 groups having radical polymerizability, cationic polymerizability, or condensation polymerizability via an atomic group (hereinafter also referred to as “fluorine-containing core”) and a linking group such as an ester bond or an ether bond. This is a fluorine-containing compound having the above polymerizable group.

In general formula (1), a represents an integer of 3 to 8, b represents an integer of 0 to 3, c represents an integer of 0 to 10, d and e each independently represents 0 or 1, r represents 0 or 1, Y represents a group represented by the following general formula (2), (3), (4) or (5), an allyl group, or a vinyl group, and L ₁ represents the following general formula ( 6) or a group represented by (7), L ₂ and L ₃ each independently represent a group represented by the following general formula (8), (9), (10) or (11) , Rf ₁ represents a (a + b) -valent, may contain an etheric oxygen atom, a linear, branched or cyclic saturated perfluoroalkyl group having 3 to 20 carbon atoms, Rf ₂ is etheric oxygen atoms may contain, represents a monovalent perfluoroalkyl group or a fluorine atom, linear or branched C1-5, Rf ₃ is It may contain ether oxygen atoms, a straight, branched or cyclic, monovalent perfluoroalkyl group of 3 to 100 carbon atoms.

In general formula (2), X represents a hydrogen atom, a fluorine atom, a chlorine atom, a methyl group, a trifluoromethyl group, or a hydroxyl group.
In general formulas (3), (4) and (5), R ₁ , R ₂ , R ₃ , R ₄ , R ₅ and R ₆ may each independently have a hydrogen atom or a substituent. It represents a good linear or branched monovalent alkyl group having 1 to 5 carbon atoms.
In general formula (5), k represents 1 or 2.
In general formulas (6) and (7), m represents an integer of 0 to 10.
In general formula (8), (9), (10), (11), n represents the integer of 0-10.
In the general formula (7), Y represents a group represented by the above general formula (2), (3), (4) or (5), an allyl group, or a vinyl group.

  In general formula (1), a represents an integer of 3 to 8. a is preferably an integer of 3 to 6, more preferably an integer of 3 to 5, and even more preferably 3 or 4 from the viewpoint of availability of raw materials and ease of production.

  In general formula (1), b represents an integer of 0 to 3. From the viewpoint of ease of production, b is preferably an integer of 0 to 2, and more preferably 0 or 1.

  In general formula (1), a + b represents an integer of 3 to 11. a + b is preferably an integer of 3 to 8, more preferably an integer of 3 to 6, and further preferably 3 or 4, from the viewpoint of the balance between liquid repellency and friction resistance.

  In general formula (1), c represents an integer of 0 to 10. c is preferably an integer of 0 to 6, more preferably an integer of 0 to 3, further preferably 0 or 1, and still more preferably 1.

  In general formula (1), d represents 0 or 1. d is preferably 1 from the viewpoint of ease of production.

  In general formula (1), e represents 0 or 1. e is preferably 1.

  In general formula (1), r represents 0 or 1. r is preferably 1.

In general formula (1), Y is a group represented by the following general formula (2), (3), (4) or (5) (where X is a hydrogen atom, a fluorine atom, a chlorine atom, a methyl group, Represents a fluoromethyl group or a hydroxyl group, and R ₁ , R ₂ , R ₃ , R ₄ , R ₅ and R ₆ each independently have 1 to 5 carbon atoms which may have a hydrogen atom or a substituent. Represents a linear or branched monovalent alkyl group, and k represents 1 or 2.), an allyl group, or a vinyl group.

  In general formula (2), X is preferably a hydrogen atom, a fluorine atom or a methyl group, and more preferably a hydrogen atom.

In the general formulas (3) to (5), R ₁ , R ₂ , R ₃ , R ₄ , R ₅ and R ₆ are each independently a hydrogen atom or a carbon atom which may have a substituent 1 Represents a linear or branched monovalent alkyl group of ˜5. Examples of the substituent when the alkyl group has a substituent include a fluorine atom, an alkoxyl group, and a hydroxyl group.
R ₁ , R ₂ , R ₃ , R ₄ , R ₅ and R ₆ are each independently preferably a hydrogen atom, a methyl group or an ethyl group, more preferably a hydrogen atom.

  In general formula (5), k represents 1 or 2. k is preferably 1.

  Y in the general formula (1) may be the same or different from each other, but is preferably the same from the viewpoint of production suitability. When mutually different, it is preferable at the point which can produce harder hardened | cured material by combining two or more types of hardening processes.

  Y in the general formula (1) is preferably a group represented by the general formula (2) or the general formula (3) from the viewpoint of a balance between liquid repellency and friction resistance.

In General Formula (1), L ₁ represents a group represented by the following General Formula (6) or (7) (where m represents an integer of 0 to 10).

In general formulas (6) and (7), m is preferably 0 to 4, more preferably 0 or 1, and still more preferably 0. When m is 0, L ₁ is a single bond.

In general formula (1), L ₂ and L ₃ are each independently a group represented by the following general formula (8), (9), (10) or (11) (where n is 0 to 10). Represents an integer).

In general formulas (8), (9), (10), and (11), n is preferably 0 to 4, more preferably 0 or 1, and still more preferably 0. When n is 0, it represents that L ₂ and L ₃ are single bonds.

In the general formula (1), Rf ₁ constitutes a “fluorine-containing core part” and has a (a + b) -valent, C3-C20 linear, branched or cyclic group which may contain an etheric oxygen atom. Represents a saturated perfluoroalkyl group. The perfluoroalkyl group is an alkyl group in which substantially all hydrogen atoms are substituted with fluorine atoms, and is a group having no substituent such as a hydroxyl group, a carboxyl group, or a nitro group.
Rf ₁ is preferably a (a + b) -valent branched or cyclic saturated perfluoroalkyl group having 3 to 16 carbon atoms which may contain an etheric oxygen atom, more preferably an (a + b) -valent. A branched or cyclic saturated perfluoroalkyl group having 4 to 12 carbon atoms, which may contain an etheric oxygen atom.

Preferable examples of the “fluorinated core portion” represented by Rf ₁ include the following structures.

Wherein * _{Y-L 1 -O-CH 2} - (CF 2) c - [CF (Rf 2)] r - (O) d -L 2 - or _{Rf 3 - (O) e -L} 3 - Represents the position to be combined.

Rf ₁ is the above f-1, f-2, f-4, f-5, f-6, f-8, f-10, f-11 or f-12 from the viewpoint of availability of raw material. Preferably, it is f-5, f-8, or f-11 from the viewpoint of the balance between liquid repellency and friction resistance, and most preferably f-8.

In the general formula (1), Rf ₂ represents an etheric oxygen atom may include, monovalent perfluoroalkyl group or a fluorine atom, linear or branched C1-5. Examples of perfluoroalkyl groups include CF _3- , CF ₃ CF _2- , CF ₃ (CF ₂ ) _3- , (CF ₃ ) ₂ CF-, CF ₃ CF ₂ OCF ₂ CF _2- , CF ₃ CF _{2 OCF 2 CF 2 OCF 2 -,} 2 (CF 3) 2 CFO (CF 2) - and the like are.
Rf ₂ is preferably CF ₃ — or a fluorine atom, and more preferably a fluorine atom.

In the general formula (1), Rf ₃ may contain an etheric oxygen atom, a straight, branched or cyclic, monovalent perfluoroalkyl group of 3 to 100 carbon atoms.
Rf ₃ is preferably a perfluoroalkyl group having 3 to 60 carbon atoms which may contain an etheric oxygen atom, and is a perfluoroalkyl group having 4 to 40 carbon atoms which may contain an etheric oxygen atom. More preferred is a perfluoroalkyl group having 6 to 20 carbon atoms which may contain an etheric oxygen atom.
Specific examples of Rf ₃ are shown below.
In the following examples, x and y represent an integer combination such that the number of carbon atoms in Rf ₃ satisfies ₃ to 100. x is preferably 1 to 40, and more preferably 3 to 20. y is preferably 1 to 40, and more preferably 3 to 20.

CF ₃ (CF ₂ ) _5- ,
(CF ₃ ) ₂ CFOCF ₂ CF _2- ,
CF ₃ OCF ₂ CF _2- ,
CF ₃ (OCF ₂ CF ₂ ) ₄ −,
_{CF 3 CF 2 (OCF 2 CF} 2) x -,
_{CF 3 (OCF 2) x (} OCF 2 CF 2) y -,
_{CF 3 (OCF 2 CF 2 CF} 2) x -,
_{CF 3 CF 2 CF 2 (OCF} (CF 3) CF 2) 4 -,
CF ₃ CF ₂ OCF ₂ CF _2- ,
_{CF 3 CF 2 (OCF 2 CF} 2) 4 -,
CF ₃ CF ₂ (OCF ₂ CF ₂ ) _6- ,
CF ₃ OCF ₂ CF ₂ CF ₂ CF _2- ,
_{((CF 3) 2 CF)} 2 CFCF (CF 3) -,
(CF ₃ ) ₃ COCF ₂ CF _2- ,
(CF ₃ CF ₂ OCF ₂ ) ₂ CFOCF ₂ CF _2- ,
(CF ₃ ) ₃ CCF ₂ CF (CF ₃ ) CF ₂ CF _2- ,
(CF ₃ ) ₂ CFCF ₂ CF ₂ CF ₂ CF (CF ₃ ) CF ₂ CF _2- ,

CF ₃ (CF ₂ ) ₃ −,
_{CF 3 (CF 2) 7 -} ,
CF ₃ (CF ₂ ) ₉ −,
CF ₃ CF ₂ CF ₂ OCF _2- ,
CF ₃ CF ₂ CF ₂ OCF ₂ CF _2- ,
_{CF 3 CF 2 CF 2 OCF (} CF 3) -,
_{CF 3 CF 2 CF 2 OCF (} CF 3) CF 2 -,
_{CF 3 CF 2 CF 2 OCF (} CF 3) CF 2 OCF 2 CF 2 -,
_{CF 3 CF 2 CF 2 OCF (} CF 3) CF 2 OCF (CF 3) -,
_{CF 3 CF 2 CF 2 OCF (} CF 3) CF 2 OCF (CF 3) CF 2 -

  From the viewpoint of liquid repellency, the compound represented by the general formula (1) preferably has a fluorine atom content of 32% by mass or more of the compound, more preferably 35% by mass or more, and still more preferably 40% by mass. % Or more.

  The fluorine-containing compound represented by the general formula (1) is preferably a fluorine-containing compound represented by the following general formula (17).

In general formula (17), a represents an integer of 3 to 8, b represents an integer of 0 to 3, c represents an integer of 0 to 10, Y represents the general formulas (2), (3), (4) or (5) represents a group, an allyl group, or a vinyl group, L ₁ represents a group represented by the general formula (6) or (7), and Rf ₁ represents an (a + b) value. Represents a linear, branched or cyclic saturated perfluoroalkyl group having 3 to 20 carbon atoms which may contain an etheric oxygen atom, and Rf ₂ may contain an etheric oxygen atom. 1 to 5 linear or branched monovalent perfluoroalkyl group or fluorine atom, Rf ₆ having at least one trifluoromethyl group, which may contain an etheric oxygen atom, carbon number 3 to 100 linear, branched or cyclic monovalent perfluoroalkyl groups are represented.

In the general formula (17), specific examples and preferred ranges of a, b, c, Y, L ₁ , Rf ₁ , Rf ₂ are a, b, c, Y, L ₁ in the general formula (1), The same as Rf ₁ and Rf ₂ .

In the general formula (17), Rf ₆ is a linear, branched or cyclic monovalent peroxy group having 3 to 100 carbon atoms, which may contain an etheric oxygen atom, having at least one trifluoromethyl group. Represents a fluoroalkyl group.
Rf ₆ is preferably a C 3-60 perfluoroalkyl group having at least one trifluoromethyl group, which may contain an etheric oxygen atom, and an ether having at least one trifluoromethyl group It is more preferably a perfluoroalkyl group having 4 to 40 carbon atoms which may contain a functional oxygen atom, and may contain an etheric oxygen atom having at least one trifluoromethyl group and having 6 to 20 carbon atoms. More preferred is a perfluoroalkyl group.
Specific examples and preferred ranges of Rf ₆ are the same as the specific examples and preferred ranges of Rf ₃ in the general formula (1).

  Although the specific example of a compound represented by General formula (1) below is given, this invention is not limited by these. As a specific example, only structures in which all Y in the same molecule are the same are listed. However, when Y is different from each other as described above, a favorable effect may be obtained, and this does not exclude any structure with different Y in the same molecule. In the following specific example compounds, x and y each independently represents an integer of 1 to 40. n1, n2, n3, and n4 each independently represents an integer of 0 to 10.

  Among the above specific examples, MA1, MA2, MA3, MA4, MA5, MA6, MA7, MA9, MA12, MA13, MA14, MA17, MA23, MA24, MA30, MA31, MA32, MA33, MA35, MA37, MA38, ME1 , ME2, ME3, ME4, ME5, ME6, ME7, ME12, ME13, ME14, ME17, ME23, ME24, ME29, ME31, ME32, ME33, ME35, ME37, ME39, ME40 are preferred, MA1, MA3, MA6, MA17 MA30, MA31, MA33, ME1, ME6, ME17, ME29, ME33, ME39 are more preferable, MA30, MA31, MA33, ME29, ME33, ME39 are more preferable, and MA31, ME29 are most preferable. .

  As a method for producing these fluorine-containing polyfunctional monomers, a compound having an ester bond, a dialkoxy group and / or a halogen atom, preferably a compound having an ester bond, is preferably substantially liquid-phase fluorinated. A method in which three or more polymerizable groups are introduced after all hydrogen atoms have been replaced with fluorine atoms is preferred. Liquid phase fluorination is described, for example, in US Pat. No. 5,093,432.

The compound subjected to liquid phase fluorination is required to be dissolved in a fluorine-based solvent used for liquid phase fluorination or to be liquid, but there is no particular limitation other than that. From the viewpoint of such solubility and reactivity, a compound containing fluorine in advance may be used. A compound having an ester bond, a dialkoxy group, and / or a halogen atom is preferable because it can serve as a reaction point when a polymerizable group is introduced after liquid phase fluorination.
By introducing fluorine atoms by liquid phase fluorination, it is possible to extremely increase the fluorine content of the portion other than the polymerizable group introduced later.

  The water repellent agent of the present invention may contain only one type of fluorine-containing compound represented by the general formula (1), or may contain two or more types.

<Compound represented by formula (12) or (13)>
The compound represented by formula (12) or (13) contained in the liquid repellent treatment agent of the present invention will be described.

In general formula (12), f represents an integer of 1 to 5, g represents 0 or 1, and Y represents a group represented by the following general formula (2), (3), (4) or (5). , An allyl group, or a vinyl group, L ₄ represents a group represented by the following general formula (6), (7), (14), or (15), and Rf ₄ contains an etheric oxygen atom. Alternatively, it represents a linear, branched or cyclic monovalent perfluoroalkyl group having 1 to 100 carbon atoms.
In General Formula (13), h and i each independently represent an integer of 1 to 5, Y is a group represented by the following General Formula (2), (3), (4) or (5), or an allyl group Or a vinyl group, L ₄ each independently represents a group represented by the following general formula (6), (7), (14), or (15), and Rf ₅ contains an etheric oxygen atom. Alternatively, it represents a linear, branched or cyclic divalent perfluoroalkyl having 1 to 100 carbon atoms.

In general formula (2), X represents a hydrogen atom, a fluorine atom, a chlorine atom, a methyl group, a trifluoromethyl group, or a hydroxyl group.
In general formulas (3), (4) and (5), R ₁ , R ₂ , R ₃ , R ₄ , R ₅ and R ₆ may each independently have a hydrogen atom or a substituent. It represents a good linear or branched monovalent alkyl group having 1 to 5 carbon atoms.
In general formula (5), k represents 1 or 2.
In general formulas (6), (7), and (14), m represents an integer of 0 to 10.
In the general formulas (7) and (15), Y represents a group represented by the general formula (2), (3), (4) or (5), an allyl group, or a vinyl group.

  In general formula (12), f represents the integer of 1-5. f is preferably an integer of 1 to 3, and more preferably 1 or 2.

  In general formula (12), g represents 0 or 1. g is preferably 1.

In general formula (12), Y represents a group represented by the above general formula (2), (3), (4) or (5), an allyl group, or a vinyl group.
Y in general formula (12) is synonymous with Y in general formula (1). Y in the general formula (12) is preferably a group represented by the above formula (2) or formula (3) from the viewpoint of the balance between liquid repellency and friction resistance.

In General Formula (12), L ₄ represents a group represented by the above General Formula (6), (7), (14) or (15) (where m represents an integer of 0 to 10). Y in the general formula (15) has the same meaning as Y in the general formula (12), and preferred groups are also the same. m is preferably 0 to 4, more preferably 0 or 1, and still more preferably 0. That is, L ₄ is preferably a single bond.

In General Formula (12), Rf ₄ represents a linear, branched or cyclic monovalent perfluoroalkyl group having 1 to 100 carbon atoms which may contain an etheric oxygen atom.
Rf ₄ is preferably a perfluoroalkyl group having 2 to 75 carbon atoms which may contain an etheric oxygen atom, and is a perfluoroalkyl group having 4 to 60 carbon atoms which may contain an etheric oxygen atom. More preferred is a perfluoroalkyl group having 6 to 50 carbon atoms which may contain an etheric oxygen atom.
Rf ₄ is preferably a linear perfluoroalkyl group which may contain an etheric oxygen atom, or which has a trifluoromethyl group as a branched chain.
Specific examples of Rf ₄ are shown below.
Incidentally, z in the following examples, the number of carbons in Rf ₄ represents an integer of combinations satisfying 1-100. z is preferably 1 to 40, and more preferably 3 to 20.

C ₄ F _9- ,
C ₆ F _13- ,
_{CF 3 (CF 2) 7 -} ,
CF ₃ (CF ₂ ) ₉ −,
CF ₃ OCF ₂ CF _2- ,
CF ₃ CF ₂ OCF ₂ CF _2- ,
CF ₃ OCF ₂ CF ₂ CF ₂ CF _2- ,
(CF ₃ ) ₂ CFOCF ₂ −,
_{((CF 3) 2 CF)} 2 CFCF (CF 3) -,
_{CF 3 O (CF 2 CF 2} O) z CF 2 -,
(CF ₃ CF ₂ OCF ₂ ) ₂ CFOCF ₂ CF _2- ,
(CF ₃ ) ₃ CCF ₂ CF (CF ₃ ) CF ₂ CF _2- ,
(CF ₃ ) ₂ CFCF ₂ CF ₂ CF ₂ CF (CF ₃ ) CF ₂ CF _2- ,
_{CF 3 CF 2 O (CF 2} CF 2 O) z CF 2 -,
(CF ₃ ) ₃ COCF ₂ CF _2- ,
_{(CF 3) 3 CO (CF} 2 CF 2 O) z CF 2 -,
_{(CF 3) 2 CFO (CF} 2 CF 2 CF 2 O) z CF 2 CF 2 -,
_{CF 3 O (CF 2 CF 2} CF 2 O) z CF 2 CF 2 -,
_{CF 3 CF 2 CF 2 O (} CF (CF 3) CF 2 O) z CF (CF 3) -,
CF ₃ CF ₂ OCF ₂ CF ₂ OCF ₂ CF _2- ,
_{CF 3 CF 2 OCF 2 CF 2} OCF 2 CF 2 OCF 2 CF 2 OCF 2 CF 2 -,
CF ₃ CF ₂ CF ₂ OCF _2- ,
CF ₃ CF ₂ CF ₂ OCF ₂ CF _2- ,
_{CF 3 CF 2 CF 2 OCF (} CF 3) -,
_{CF 3 CF 2 CF 2 OCF (} CF 3) CF 2 -,
_{CF 3 CF 2 CF 2 OCF (} CF 3) CF 2 OCF 2 CF 2 -,
_{CF 3 CF 2 CF 2 OCF (} CF 3) CF 2 OCF (CF 3) CF 2 -

  In general formula (13), h and i each independently represent an integer of 1 to 5. h and i are each independently preferably an integer of 1 to 3, more preferably 1 or 2, and still more preferably 1.

  Y in the general formula (13) has the same meaning as Y in the general formula (12), and preferred groups are also the same.

_{L 4} in the general formula (13) has the same meaning as _{L 4} in the formula (12), which is also the same preferable groups.

In General Formula (13), Rf ₅ represents a linear, branched or cyclic divalent perfluoroalkylene group having 1 to 100 carbon atoms which may contain an etheric oxygen atom.
Rf ₅ is preferably a linear divalent perfluoroalkylene group having 2 to 90 carbon atoms which may contain an etheric oxygen atom, and may be a linear carbon which may contain an etheric oxygen atom. A divalent perfluoroalkylene group having a number of 6 to 80 is more preferable.
Rf ₅ is preferably a linear perfluoroalkylene group which may contain an etheric oxygen atom, or which has a trifluoromethyl group as a branched chain.
Specific examples of Rf ₅ are shown below.
In addition, p and q in the following example represent the combination of integers in which the carbon number in Rf ₅ satisfies 1 to 100. p is preferably 1 to 40, and more preferably 3 to 20. q is preferably 1 to 40, more preferably 3 to 20.

_{-CF 2 O- (CF 2 CF 2} O) p -CF 2 -,
_{-CF 2 O- (CF 2 CF 2} CF 2 O) p -CF 2 -,
_{-CF 2 O- (CF 2 CF 2} CF 2 CF 2 O) p -CF 2 -,
_{-CF 2 O- (CF 2 CF 2} O) p (CF 2 O) q -CF 2 -,
- _{(CF 2) 2} -,
- _{(CF 2)} 4 -,
- _{(CF 2)} 6 -,
- _{(CF 2)} 8 -,
- _{(CF 2) 10} -,
_{- (CF 3) CF [OCF} 2 CF (CF 3)] p OCF 2 (CF 2) 4 CF 2 O [CF (CF 3) CF 2 O] q CF (CF 3) -,
_{-CF 2 [OCF 2 CF (CF} 3)] p OCF 2 -,
_{- (CF 2) 4 CF 2} O [CF (CF 3) CF 2 O] p CF (CF 3) CF 2 OCF 2 CF 2 -

  The fluorine-containing compound represented by the general formula (12) or (13) is preferably a fluorine-containing compound represented by the following general formula (18) or (19).

In general formula (18), f represents an integer of 1 to 5, and Y represents a group represented by the general formula (2), (3), (4) or (5), an allyl group, or a vinyl group. Rf ₇ represents a linear or branched monovalent perfluoroalkyl group having 1 to 100 carbon atoms, which may contain an etheric oxygen atom, and has at least one trifluoromethyl group.
In general formula (19), h and i each independently represent an integer of 1 to 5, Y is a group represented by the general formula (2), (3), (4) or (5), or an allyl group Or Rf ₈ represents a linear or branched divalent perfluoroalkyl group having 1 to 100 carbon atoms, which may contain an etheric oxygen atom.

  In general formulas (18) and (19), specific examples and preferred ranges of f, Y, h and i are the same as those in f, Y, h and i in general formula (12) or (13).

In General Formula (18), Rf ₇ is a linear or branched monovalent perfluoroalkyl having 1 to 100 carbon atoms, which may contain an etheric oxygen atom, having at least one trifluoromethyl group. Represents a group.
Rf ₇ has at least one trifluoromethyl group, may contain an etheric oxygen atom, has 2 to 75 carbon atoms, is linear, or is linear perfluoro having a trifluoromethyl group as a branched chain It is preferably an alkyl group, has at least one trifluoromethyl group, may contain an etheric oxygen atom, has 4 to 60 carbon atoms, is linear, or has a trifluoromethyl group as a branched chain The perfluoroalkyl group is more preferably a perfluoroalkyl group having 6 to 50 carbon atoms and having at least one trifluoromethyl group, which may contain an etheric oxygen atom.
Specific examples and preferred ranges of Rf ₇ are the same as those of Rf ₄ in the general formula (12).
Specific examples of Rf ₇ are shown below.
In addition, z1 in the following example represents the combination of the integers in which the carbon number in Rf ₇ satisfies 1 to 100. z1 becomes like this. Preferably it is 0-20, More preferably, it is 1-10.

C ₄ F _9- ,
C ₆ F _13- ,
_{CF 3 (CF 2) 7 -} ,
CF ₃ (CF ₂ ) ₉ −,
CF ₃ OCF ₂ CF _2- ,
CF ₃ CF ₂ OCF ₂ CF _2- ,
CF ₃ OCF ₂ CF ₂ CF ₂ CF _2- ,
(CF ₃ ) ₂ CFOCF ₂ −,
_{((CF 3) 2 CF)} 2 CFCF (CF 3) -,
_{CF 3 O (CF 2 CF 2} O) z CF 2 -,
(CF ₃ ) ₃ CCF ₂ CF (CF ₃ ) CF ₂ CF _2- ,
(CF ₃ ) ₂ CFCF ₂ CF ₂ CF ₂ CF (CF ₃ ) CF ₂ CF _2- ,
_{CF 3 CF 2 O (CF 2} CF 2 O) z1 CF 2 -,
(CF ₃ ) ₃ COCF ₂ CF _2- ,
_{(CF 3) 3 CO (CF} 2 CF 2 O) z1 CF 2 -,
_{(CF 3) 2 CFO (CF} 2 CF 2 CF 2 O) z1 CF 2 CF 2 -,
_{CF 3 O (CF 2 CF 2} CF 2 O) z1 CF 2 CF 2 -,
_{CF 3 CF 2 CF 2 O (} CF (CF 3) CF 2 O) z1 CF (CF 3) -,
CF ₃ CF ₂ OCF ₂ CF ₂ OCF ₂ CF _2- ,
_{CF 3 CF 2 OCF 2 CF 2} OCF 2 CF 2 OCF 2 CF 2 OCF 2 CF 2 -,
CF ₃ CF ₂ CF ₂ OCF _2- ,
CF ₃ CF ₂ CF ₂ OCF ₂ CF _2- ,
_{CF 3 CF 2 CF 2 OCF (} CF 3) -,
_{CF 3 CF 2 CF 2 OCF (} CF 3) CF 2 -,
_{CF 3 CF 2 CF 2 OCF (} CF 3) CF 2 OCF 2 CF 2 -,
_{CF 3 CF 2 CF 2 OCF (} CF 3) CF 2 OCF (CF 3) CF 2 -

In General Formula (19), Rf ₈ represents a linear or branched divalent perfluoroalkyl group having 1 to 100 carbon atoms which may contain an etheric oxygen atom.
Specific examples and preferred ranges of Rf ₉ are the same as those of Rf ₅ in the general formula (13).

  From the viewpoint of liquid repellency, the compound represented by the general formula (12) or (13) preferably has a fluorine atom content of 30% by mass to 75% by mass, more preferably 32% by mass to 37%. It is not more than mass%, more preferably not less than 33 mass% and not more than 60 mass%.

  Although the specific example of a compound represented by General formula (12) or (13) below is given, this invention is not limited by these. Z in the following specific example compounds represents an integer of 1 to 40, and p and q each independently represents an integer of 1 to 40.

  Among the above specific examples, AA-2, AA-3, AA-9, AA-12, AA-13, AA-14, AA-15, AA-17, AE-2, AE-5, AE-9 AE-12, AE-13, AE-15, AE-17 are preferred, and AA-2, AA-3, AA-9, AA-13, AA-14, AA-15, AE-2, AE-5. AE-9, AE-13, and AE-15 are more preferable, and AA-2, AA-13, AA-15, AE-2, AE-13, and AE-15 are most preferable.

  The compound represented by the general formula (12) or (13) may be obtained commercially or may be produced by synthesis. In the case of synthesis, there is no particular limitation on the synthesis method, and it is known by a known method, for example, a method by dehydration condensation of a commercially available fluorinated alcohol compound and acrylic acid, or a substitution reaction with epichlorohydrin. Can be synthesized.

  The water repellent agent of the present invention may contain only one type of fluorine-containing compound represented by the general formula (12) or (13), or may contain two or more types.

<Liquid repellent treatment agent>
The liquid repellent treatment agent of the present invention contains at least one fluorine-containing compound represented by the above general formula (1) and the fluorine-containing compound represented by the above general formula (12) or (13). To do.
The fluorine-containing compound represented by the general formula (1), for example, the compound MA31, has a liquid repellent part having a high fluorine content at the center of the molecule, and a polymerizable group Y having a low liquid repellent property around it. It has a dispersed molecular structure. Therefore, despite the high fluorine content, the free energy on the molecular surface is relatively high and the affinity for the hydrophilic surface of the substrate is relatively high.
On the other hand, the fluorine-containing compounds represented by the general formula (12) or (13), for example, the compounds AA-2 and AA-15 have a molecular structure in which the high fluorine content portion and the polymerizable group Y are unevenly distributed. Therefore, the free energy on the molecular surface is very low, and the affinity with the hydrophilic surface of the substrate is very low. Since it has such a molecular structure, when the fluorine-containing compound represented by the general formula (12) or (13) is applied to the hydrophilic surface of the substrate, it is rebounded to form a uniform coating film. Can not.

Surprisingly, the liquid repellent treatment agent containing the fluorine-containing compound represented by the general formula (1) and the fluorine-containing compound represented by the general formula (12) or (13) has a high fluorine content. However, even when applied to a hydrophilic surface, a uniform coating film can be formed without being repelled. This is presumed to be due to the following phenomenon.
That is, in the coating after coating, the fluorine-containing compound represented by the general formula (12) or (13) having a very low molecular surface free energy is unevenly distributed at the interface with air and has a relatively high molecular surface free energy. It is presumed that the fluorine-containing compound represented by the general formula (1) having the above is unevenly distributed at the interface with the hydrophilic surface.
In this way, it is possible to obtain a liquid-repellent treatment agent having an excellent characteristic that it has very high liquid repellency and is not repelled even when applied to a hydrophilic surface.
Moreover, since the fluorine-containing compound represented by the general formula (1) and the fluorine-containing compound represented by the general formula (12) or (13) are highly compatible, the fluorine-containing compound represented by the general formula (1) A coating film formed by applying a liquid repellent treatment agent containing a compound and a fluorine-containing compound represented by the general formula (12) or (13) is also excellent in transparency.

In the liquid repellent treatment agent, the fluorine-containing compound represented by the general formula (1) is 5 to 90% by mass with respect to the total solid content of the liquid repellent treatment agent from the viewpoint of improving the friction resistance. It is preferably 7 to 70% by mass, more preferably 10 to 50% by mass.
In addition, the fluorine-containing compound represented by the general formula (12) or (13) is 10 to 95% by mass with respect to the total solid content of the liquid repellent treatment agent from the viewpoint of liquid repellency. Is preferable, it is more preferable that it is 30-93 mass%, and it is further more preferable that it is 50-90 mass%.

In the liquid repellent treatment agent of the present invention, the content ratio of the fluorine-containing compound represented by the general formula (1) and the fluorine-containing compound represented by the general formula (12) or (13) is a mass ratio (general The fluorine-containing compound represented by the formula (1) / (the fluorine-containing compound represented by the general formula (12) or (13)) is preferably 0.05 to 9, and preferably 0.07 to 2. More preferably, it is 33, and it is still more preferable that it is 0.1-1. When the ratio of (fluorinated compound represented by general formula (1)) / (fluorinated compound represented by general formula (12) or (13)) is 0.05 or more, the friction resistance is improved after curing. It is preferable from the reason that an effect can be obtained, and is preferably 9 or less from the reason that a sufficient liquid repellency effect can be obtained after curing.
The content of the “fluorinated compound represented by the general formula (12) or (13)” is the same as that of the fluorinated compound represented by the general formula (12) and the general formula (13) in the liquid repellent agent. When both of the fluorine-containing compounds represented by general formula (12) are included, the total content of the fluorine-containing compound represented by general formula (12) and the fluorine-containing compound represented by general formula (13).

  The water repellent treatment agent of the present invention has the above-mentioned MA1, MA2, MA3, MA4, MA5, MA6, MA7, MA9, MA12, MA13, MA14, MA17, MA23, MA24, as the compound represented by the general formula (1). MA30, MA31, MA32, MA33, MA35, MA37, MA38, ME1, ME2, ME3, ME4, ME5, ME6, ME7, ME12, ME13, ME14, ME17, ME23, ME24, ME29, ME31, ME32, ME33, ME35, As compounds having ME37, ME39, or ME40 and represented by the general formula (12) or (13), AA-2, AA-3, AA-9, AA-12, AA-13, AA-14 , AA-15, AA-17, AE-2, AE-5, AE-9, AE-12, AE-13, AE- 5, or preferably has a AE-17.

<Non-fluorine compound>
The liquid repellent treatment agent of the present invention preferably further contains a non-fluorine compound represented by the following general formula (16) from the viewpoint of promoting the curing of the liquid repellent treatment agent.

In General Formula (16), j represents an integer of 1 to 6, Y is a group represented by the following General Formula (21), (3), (4) or (5) (where X ¹ is a hydrogen atom) Represents a chlorine atom, a methyl group, or a hydroxyl group, and R ₁ , R ₂ , R ₃ , R ₄ , R _5, and R ₆ are each independently a hydrogen atom or a carbon number that may have a substituent. 1 to 5 represents a linear or branched monovalent alkyl group, k represents 1 or 2, and an allyl group or a vinyl group, and L ₅ represents the following general formula (6), ( 7) represents a group represented by (14) or (15) (where m represents an integer of 0 to 10), and R ₇ represents a hydrogen atom or a carbon which may have a substituent. A linear, branched or cyclic j-valent organic group represented by formulas 1 to 20 is represented. In general formulas (7) and (15), Y represents a group represented by general formula (21), (3), (4) or (5), an allyl group, or a vinyl group.

  In general formula (16), j represents the integer of 1-6. j is preferably an integer of 4-6.

  In the general formula (16), Y represents a group represented by the above general formula (21), (3), (4) or (5), an allyl group, or a vinyl group.

In general formula (21), X ¹ is preferably a hydrogen atom.

  General formula (3)-(5) is synonymous with formula (3)-(5) which Y in General formula (1) can take.

  Y in the general formula (16) is preferably a group represented by the above formula (21) or formula (3) from the viewpoint of a curing acceleration effect.

In General Formula (16), L ₅ has the same meaning as L ₄ in General Formula (12), and preferred groups are also the same.

In General Formula (16), R ₇ represents a hydrogen atom or a linear, branched, or cyclic j-valent organic group having 1 to 20 carbon atoms that may have a substituent. The organic group is not particularly limited, and examples thereof include a skeleton obtained by removing a hydroxyl group from dipentaerythritol, pentaerythritol, and ditrimethylolpropane. Examples of the substituent when the organic group has a substituent include a hydroxyl group, a carboxyl group, and an amino group.

  Specific examples of the non-fluorine compound represented by the general formula (16) include pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, ditrimethylolpropane tetra (meth). ) Acrylate, pentaerythritol tetraglycidyl ether and the like.

  The non-fluorine compound represented by the general formula (16) is preferably included in an amount of 1 to 25% by mass with respect to the fluorine-containing compound represented by the general formula (1) from the viewpoint of liquid repellency. .

<Polymerization initiator>
The liquid repellent treatment agent of the present invention preferably further contains a polymerization initiator. Examples of the polymerization initiator include a thermal polymerization initiator that initiates polymerization by heat and a photopolymerization initiator that initiates polymerization by light. The polymerization initiator to be used is not particularly limited, but for the purpose of obtaining a member having a desired pattern in the hydrophilic region and the water repellent region described later, a photopolymerization initiator is used so as to be suitable for pattern formation using a photomask. It is preferable.

Photoinitiators include photoradical polymerization initiators that initiate light polymerization by generating radicals by absorbing light, and photocationic polymerization initiators that initiate polymerization reaction by absorbing light and generating cations. There is an agent.
Examples of the radical photopolymerization initiator include 2-hydroxy-2-methyl-1-phenylpropan-1-one (manufactured by BASF Japan Ltd., Darocur 1173), 1-hydroxycyclohexyl phenyl ketone (BASF Japan Ltd.). Irgacure 184), benzyl dimethyl ketal (Irgacure 651, manufactured by BASF Japan Ltd.), 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one (BASF Japan) (Irgacure 907), 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 (BASF Japan, Irgacure 369), 2,4-diethyl As a preferred example, thioxanthone (manufactured by Nippon Kayaku Co., Ltd., Kayacure DETX) It can gel.
The cationic photopolymerization initiator, for example, ^{_{[CH 3 -ph-I + -ph}} -CH- (CH 3) 2] [PF 6 -] ( although, ph represents a 1,4-phenylene group) is preferred, ^{_{[CH 3 -ph-I + -ph}} -CH- (CH 3) 2] [PF 6 -] ( although, ph is a 1,4-phenylene group show a) 3 propylene carbonate: a mixture of 1 (BASF Japan An example is Irgacure 250 manufactured by Co., Ltd. Other preferred examples include dimethyl-4-methylphenylsulfonium trifluoromethanesulfonate (manufactured by Wako Pure Chemical Industries, Ltd., WPAG-336).
As a photocationic polymerization initiator, a sulfonium salt compound or an iodonium salt compound is preferable.
These may be used alone or in combination of two or more. 0.1-50 mass% is preferable with respect to the total amount of the polymeric compound in a liquid-repellent processing agent, and, as for the quantity of a photoinitiator, 1-10 mass% is more preferable.

<Solvent>
The liquid repellent treatment agent of the present invention may contain a solvent in order to improve applicability. Solvents include ketones such as acetone and 2-butanone, alcohols such as methanol, ethanol and isopropanol, esters such as ethyl acetate and butyl acetate, hydrocarbons such as hexane, nonafluorobutyl methyl ether (Sumitomo 3M ( Fluorine-containing compounds such as Nobec HFE-7100), dichloropentafluoropropane (Asahi Glass Co., Ltd., Asahi Clin AK-225; a mixture of CF ₃ CF ₂ CHCl ₂ and CClF ₂ CF ₂ CHClF) Is preferred. These may be used alone or in combination of two or more. The solid content concentration in the solution is preferably 0.01 to 50% by mass, more preferably 0.1 to 10% by mass.

  In addition, the liquid repellent treatment agent may contain a polymerization inhibitor, a phosphor, a resin, a monomer, an inorganic particle, a particulate organic polymer, a heat stabilizer and the like as long as it does not contradict the gist of the present invention.

<Liquid repellent film and member having hydrophilic region and water repellent region>
A liquid repellent film can be formed using the liquid repellent treatment agent of the present invention.
In addition, using the liquid repellent treatment agent of the present invention, a member having a hydrophilic region and a water repellent region on the surface of the substrate (also referred to as “treated substrate”) can be produced. The treatment substrate of the present invention is a step of forming a coating film containing the liquid repellent treatment agent of the present invention on the surface of the substrate having a hydrophilic surface, and then irradiates a part of the surface of the coating film with light. To form a liquid-repellent film by curing the liquid-repellent treatment agent, and then to remove the uncured liquid-repellent treatment agent present on the surface of the substrate to expose the hydrophilic surface. can do.

The treated substrate of the present invention can be produced, for example, by the following steps 1 to 4 as shown in FIG.
Step 1: A step of hydrophilizing the surface of the substrate 1 to make the surface a hydrophilic surface 2 (FIG. 1A).
Step 2: Next, a step of forming a coating film 3 containing the liquid repellent treatment agent of the present invention on the surface 2 (FIG. 1B).
Step 3: Next, a part of the surface of the coating film 3 is irradiated with light 6 to cure the liquid repellent treatment agent, thereby forming the liquid repellent film 4 (FIG. 1C).
Step 4: Next, a step of removing the uncured liquid repellent treatment agent present on the surface of the substrate to expose the hydrophilic surface 2 (FIG. 1D).

Step 1:
When the surface of the substrate exhibits hydrophilicity, step 1 can be omitted, but it is preferable that the surface of the substrate is hydrophilized.
As the base material in the present invention, glass; silicon wafer; metal such as Pd, Pt, Ru, Ag, Au, Ti, In, Cu, Cr, Fe, Zn, Sn, Ta, W, or Pb; PdO, SnO Metal oxides such as ₂ , In ₂ O ₃ , PbO, or Sb ₂ O ₃ ; borides such as HfB ₂ , ZrB ₂ , LaB ₆ , CeB ₆ , YB ₄ , or GdB ₄ ; TiC, ZrC, HfC, TaC Carbides such as TiN, ZrN, or HfN; semiconductors such as Si or Ge; carbon; resins such as polyimide, polystyrene, polyethylene terephthalate, triacetylcellulose, or polytetrafluoroethylene; etc. The substrate can be selected from the following materials. Glass, silicon wafer, metal oxide, or polyimide is preferred.

  The shape of the substrate is not particularly limited and is preferably a flat surface, a curved surface, or a partially curved surface, and more preferably a flat surface. Further, the area of the substrate is not particularly limited, and a substrate having a surface having a size as long as a conventional coating method can be applied can be employed. Moreover, it is preferable to perform the process in the surface of the base material in this invention by the single side | surface of the base material on a plane.

It is preferable to wash the surface of the substrate in advance in the production of the treated substrate. Moreover, it is also preferable to hydrophilize the substrate surface, and it is also preferable to use a substrate having a hydrophilic thin film on the surface. The treatment of these surfaces can be done in a common way, and it may be difficult to distinguish whether the treatment is any of these treatments. In the present specification, these are all regarded as a hydrophilic treatment of the base material and will be described below.
As a method for hydrophilizing the surface of the substrate, a general method for hydrophilizing the surface of plastic, metal, glass, ceramics, or the like is applicable. Examples of the method include a method of wet-cleaning the surface of the substrate, a method of wet-oxidizing the surface of the substrate, a method of photo-cleaning or photo-oxidizing the surface of the substrate, and a method of applying a hydrophilic compound to the surface of the substrate Or a combination of these. When the material of the substrate is hydrophilic, it can be used as it is, but such a substrate is usually easily soiled. Therefore, it is preferable to hydrophilize the substrate by wet cleaning, light cleaning, or a combination thereof before use. When the material of the substrate is hydrophobic, it is preferable that the surface of the substrate is hydrophilized by wet oxidation, photooxidation, or application of a hydrophilic compound.

For wet cleaning of the substrate, water, an aqueous cleaning agent, or a non-aqueous cleaning agent (organic solvent, fluorine-based solvent, etc.) can be used. In particular, the substrate is washed with water or an aqueous detergent containing a surfactant, and then dried using a low-boiling organic solvent such as isopropyl alcohol or ethyl alcohol while removing foreign substances or moisture on the surface. The method is preferred. Further, depending on the type of substrate and the type and degree of dirt, a process can be added or a part of the process can be omitted. In order to remove the soil, wet cleaning of the substrate with organic soil adhered is first performed with dichloropentafluoropropane (AK-225 manufactured by Asahi Glass Co., Ltd .; CF ₃ CF ₂ CHCl ₂ and CClF ₂ CF ₂ CHClF). It is preferable to wash in advance with a fluorinated solvent such as a mixture of the above, and then immerse and wash the substrate with an aqueous cleaner or an organic solvent. When performing immersion cleaning, ultrasonic cleaning may be used in combination. With respect to glass, instead of immersion cleaning or in combination with immersion cleaning, a method of polishing and cleaning with an abrasive containing cerium oxide fine particles, rinsing with pure water, and air drying may be employed.

  In the wet oxidation of the substrate, the surface is oxidized using an aqueous solution of an oxidizing agent such as a peroxide. It does not specifically limit as an oxidizing agent, A sulfuric acid, nitric acid, hydrogen peroxide, potassium persulfate, ammonium persulfate, potassium permanganate etc. are mentioned. The method for wet-oxidizing the substrate is not particularly limited as long as the aqueous solution can be applied to the surface of the substrate, and a spin coating method, a dip coating method, a spray method, a roll coating method and the like can be employed.

Examples of the method for photocleaning or photooxidizing the substrate include UV irradiation treatment, UV / O ₃ treatment, plasma treatment, corona discharge treatment, flame treatment and the like, and UV / O ₃ treatment is preferred.
Further, only wet cleaning tends to leave a slight amount of organic dirt (for example, residual detergent residue of neutral detergent, clean room floating substance, etc.). On the other hand, the above-mentioned optical cleaning does not have the fear. Therefore, a method of removing relatively large dirt first by wet cleaning and then cleaning by light cleaning is also preferable.

Examples of hydrophilic compounds that can be used for the hydrophilic treatment of the surface of the substrate include hydrophilic polymers such as poly (vinyl alcohol), poly (vinyl pyrrolidone), and poly (ethylene glycol); multivalents such as glycerin, pentaerythritol, and sorbitol. There is alcohol. Examples of the hydrophilic treatment compound that reacts with the surface of the substrate to form a hydrophilic residue such as a silanol group on the surface include Si (OCH ₃ ) ₄ , Si (OCH ₂ CH ₃ ) ₄ , [(CH ₃ ). Silane compound having a hydrolyzable group such as ₃ Si] ₂ NH, H—Si (OCH ₂ CH ₃ ) ₃ , NH ₂ CH ₂ CH ₂ CH ₂ —Si (OCH ₂ CH ₃ ) ₃ , or part of the compound Or the compound by which all were hydrolyzed, or the hydrolysis-condensation product of this compound is mentioned.

The hydrophilic compound is preferably applied as a solution dissolved in a solvent. The hydrophilic polymer and polyhydric alcohol are preferably dissolved in water, and the silane compound is preferably dissolved in an alcohol solvent such as isopropyl alcohol. The concentration of the hydrophilic compound in the solution is preferably 0.01 to 10% by mass, and more preferably 0.1 to 1% by mass.
The coating method on the substrate is not particularly limited, and spin coating, dip coating, spraying, roll coating, meniscus coating, screen printing, and the like can be employed.

  It is preferable to employ a method of applying a hydrophilic compound as the hydrophilization treatment when the surface of the base material is formed of different materials because the same hydrophilicity can be imparted to the surfaces of different materials.

Step 2:
In order to form a coating film containing the liquid repellent treatment agent of the present invention on the surface of a substrate having a hydrophilic surface, it is preferable that the liquid repellent treatment agent is applied to the substrate and then dried. The liquid repellent treatment agent is preferably applied as a solution containing the above-mentioned solvent.

  As a coating method, methods such as spin coating, dip coating, wire bar coating, blade coating, and roll coating can be employed. The application is preferably performed at room temperature or under heating. Moreover, it is preferable that the base material after application | coating is dried in air | atmosphere or nitrogen stream. The drying is preferably performed at room temperature. When drying is performed under heating, it is preferable to appropriately change the temperature and time depending on the heat resistance of the base material.

Step 3:
After forming the coating film, a part of the surface of the coating film is irradiated with light. The light used for light irradiation is preferably light having a wavelength of 200 nm or more, and more preferably light having a wavelength of 300 nm or more. Moreover, light with a wavelength of 380 nm or less is preferable, and light with a wavelength of 365 nm or less is more preferable. Light having a wavelength of 200 nm or more has an advantage that there is little possibility of decomposing the substrate. Moreover, the photoinitiator which starts superposition | polymerization by light irradiation with a wavelength of 380 nm or less is easy to obtain, and a light source is also cheap. The irradiation time can be appropriately changed according to the wavelength of light, the intensity of light, the type of light source, the type of composition, and the like. In the case of an ultra high pressure mercury lamp, irradiation may be performed at ² to 100 mW / cm ² for 5 to 120 seconds. In general, in the case of a high-pressure mercury lamp, irradiation can be performed in a shorter time than an ultra-high pressure mercury lamp.

  Light sources include low-pressure mercury lamps, high-pressure mercury lamps, ultrahigh-pressure mercury lamps, xenon lamps, sodium lamps, gas lasers such as nitrogen, liquid lasers of organic dye solutions, solid-state lasers containing rare earth ions in inorganic single crystals, etc. Can be mentioned. Further, as a light source other than the laser from which monochromatic light is obtained, light having a specific wavelength obtained by extracting a broadband line spectrum or continuous spectrum using an optical filter such as a bandpass filter or a cutoff filter may be used. Since a large area can be irradiated at a time, a high pressure mercury lamp or an ultrahigh pressure mercury lamp is preferable as the light source.

  The light irradiation is preferably performed through a photomask. By this method, it is possible to cause a curing reaction only in a desired region on the surface of the film, and it is possible to obtain a treated substrate in which a hydrophilic region and a water-repellent region form a desired pattern. The desired pattern in the present invention is different depending on the application, but for example, a linear pattern, a dot pattern, a ring pattern, a lattice pattern, a honeycomb pattern, etc., a wiring, an electrode, an insulating layer according to the application, The pattern is a light emitting layer or the like, and the interval is, for example, 0.5 μm to 1 cm.

  The atmosphere for light irradiation can be arbitrarily selected. When forming a liquid-repellent film obtained by curing a liquid-repellent treatment agent with a film thickness of 100 nm or less, light irradiation may be performed under an inert gas atmosphere such as a nitrogen gas atmosphere because it may be inhibited by oxygen. It is preferable to do this. Examples of the inert gas include a gas selected from nitrogen, argon, helium, carbon dioxide, and the like, and nitrogen gas is most preferable because it can be obtained at a low cost.

  The film thickness of the liquid repellent film is not particularly limited because the optimum film thickness varies depending on the application form, but is preferably 1 nm or more and 10 mm or less, more preferably 5 nm or more and 1 mm or less, and further preferably 10 nm or more and 500 μm or less.

  Light irradiation may be performed from either side of the base material as long as the base material transmits light used for light irradiation, and usually the surface of the film containing the liquid repellent treatment agent of the base material. It is preferable to perform light irradiation from the side.

  When light irradiation is performed using light or laser light that has been removed from a photomask, a treated substrate in which a hydrophilic region and a water-repellent region form a desired pattern is obtained. Further, a pattern in which the line width between the hydrophilic region and the water repellent region is 10 μm or less can be formed.

Step 4:
After forming a liquid repellent film obtained by curing the liquid repellent treatment agent, the uncured liquid repellent treatment agent present on the surface of the substrate is removed. By removing the uncured liquid repellent treatment agent, the hydrophilic surface is exposed. As a method for removing the uncured liquid repellent treatment agent, it is preferable to wash the surface on which the polymerizable fluorine-containing compound remains with an organic solvent. As the organic solvent used for washing, a solvent that dissolves the polymerizable fluorine-containing compound is preferable. Examples of the organic solvent include ketones such as acetone and 2-butanone, alcohol solvents such as methanol, ethanol and isopropanol; ester solvents such as ethyl acetate and butyl acetate; hydrocarbon solvents such as hexane and nonafluorobutylmethyl. Ether (Sumitomo 3M Co., Ltd., Novec HFE-7100), dichloropentafluoropropane (Asahi Glass Co., Ltd., ASAHIKLIN AK-225; mixture of CF ₃ CF ₂ CHCl ₂ and CClF ₂ CF ₂ CHClF), etc. And the like.

  As described above, a treated substrate having a hydrophilic region and a water-repellent region on the surface of the substrate is provided. The hydrophilic region and the water repellent region can be distinguished by the contact angle with water.

The contact angle of the hydrophilic region with respect to water is preferably 50 degrees or less, more preferably 40 degrees or less, and particularly preferably 20 degrees or less. The contact angle of water in the water repellent region is preferably 80 degrees or more, more preferably 100 degrees or more, and particularly preferably 110 degrees or more.
The difference between the water contact angle of the hydrophilic region and the water contact angle of the water repellent region is preferably 50 ° or more, more preferably 70 ° or more, and particularly preferably 80 ° or more.

  Since the water-repellent region in the treated substrate of the present invention is composed of a liquid-repellent film obtained by curing the liquid-repellent treating agent containing the polymerizable fluorine-containing compound of the present invention, not only water but also an organic solvent is used. Provides liquid repellency. Since the water repellent region exhibits liquid repellency with respect to the organic solvent, the relatively hydrophilic region exhibits lyophilicity with respect to the organic solvent.

When a liquid containing a functional material, which will be described later, is applied, the larger the difference in the contact angle between the hydrophilic region and the water-repellent region, the more the liquid containing the functional material straddling the water-repellent region and the hydrophilic region enters the hydrophilic region. The pattern of the functional material obtained by allowing the liquid to easily flow and drying the liquid containing the functional material can more accurately reproduce the pattern of the water repellent region and the hydrophilic region.
In addition, the smaller the absolute value of the contact angle of the hydrophilic region, the better the liquid containing the functional material wets and spreads in the hydrophilic region, and the functional material pattern film obtained by drying the liquid containing the functional material The thickness can be made more uniform.

  In the present invention, when a flexible substrate such as a plastic substrate or ultra-thin glass is used as a base material, a plurality of rolls installed so that a roll-to-roll method (Roll to Roll method) can be performed, and a plurality of rolls A processing base material can be obtained with high throughput by installing an exposure machine between them and irradiating the substrate with light.

<Member on which functional material pattern is formed>
A member on which a pattern of a functional material is formed can be manufactured using a treatment substrate in which a hydrophilic region and a water-repellent region form a desired pattern. The member of the present invention is a process in which a liquid containing a functional material is applied to the surface of a treated substrate, and the liquid is attached to a hydrophilic region in which a pattern of the treated substrate is formed, and then dried to be a functional material. The pattern can be produced by a step of forming a pattern and, if necessary, a step of removing the liquid repellent film.

The member in which the pattern of the functional material of the present invention is formed can be manufactured by, for example, the following steps 5 and 6 and, if necessary, step 7 as shown in FIG.
Step 5: A step of applying a liquid 11 containing a functional material to the surface of the treated substrate 9 (FIG. 2E), and attaching the solution 11 to the hydrophilic region 7 in which the pattern of the treated substrate is formed ( FIG. 2 (f)).
Process 6: Next, the process of forming the pattern of the functional material 12 by making it dry (FIG.2 (g)).
Step 7: Next, a step of removing the water-repellent region 8 made of the liquid-repellent film 4 (FIG. 2 (h)).

Step 5:
Examples of the functional material include a metal particle dispersed paste for forming a metal wiring, a dye material for forming a color filter, a ceramic material for forming an electronic device / organic display, an organic semiconductor material, and the like.

  The liquid containing the functional material refers to a liquid or liquid material in which the functional material is dissolved or dispersed in water, an organic solvent, or a mixture thereof. Since the water-repellent region of the treated substrate of the present invention also exhibits oil repellency as described above, an organic solvent having a low polarity can also be used as the organic solvent. The organic solvent is not particularly limited, and alcohols such as methanol, ethanol, propanol and butanol; n-pentane, n-hexane, n-heptane, n-octane, decane, dodecane, tetradecane, hexadecane, octadecane, cyclohexane, Hydrocarbons such as toluene, xylene, tetrahydronaphthalene and decahydronaphthalene; ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol methyl ethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, tetrahydrofuran and dioxane Compound; propylene carbonate, γ-butyrolactone, N-methyl-2-pyrrolidone, Methylformamide, dimethylsulfoxide, polar compounds such as cyclohexanone and the like. Among these, it is preferable to select a suitable solvent in terms of solubility, dispersibility, and stability. These organic solvents may be used alone or in a mixture of two or more.

  Examples of the coating method of the liquid include a coating method such as spin coating, dip coating, wire bar coating, blade coating, and roll coating, and a printing method in a specific region such as screen printing and an inkjet method. Among these, screen printing and an ink jet method are preferable because they can be selectively applied to a hydrophilic region on a pattern composed of a hydrophilic region and a water-repellent region.

Step 6:
By drying the substrate after application and removing the solvent used in step 5, a member on which a pattern of the functional material is formed is obtained. Drying is preferably performed in the air or in a nitrogen stream. The drying is preferably performed at room temperature or under heating. When drying is performed under heating, it is preferable to appropriately change the temperature and time depending on the heat resistance of the base material.

Step 7:
In a member on which a pattern of a functional material is formed, a member from which a liquid-repellent film is further removed is useful as an electronic element. The reason why the liquid repellent film is removed is that the liquid repellent film may affect the operation of the element when the member is used as an electronic element.

  In order to remove the liquid repellent film, it is preferable to wash with an alkaline aqueous solution. Examples of the alkaline aqueous solution include an aqueous solution of an alkali metal hydroxide (sodium hydroxide, potassium hydroxide, etc.) or a methanol solution, an aqueous solution of tetramethylammonium hydroxide or a methanol solution, and among them, an aqueous solution of sodium hydroxide. Is preferred.

Examples that specifically illustrate the present invention are given below, but the present invention is not limited thereto. Here, the nuclear magnetic resonance method is referred to as NMR. ^{In the 1} H-NMR spectrum, tetramethylsilane was used as an internal standard, and in the ¹⁹ F-NMR spectrum, fluorotrichloromethane was used as an external standard.

  [Synthesis Example 1] Synthesis of Compound MA1

(Synthesis Example 1-1) Synthesis of Compound MA1-A Compound (MA1-A) was synthesized with reference to a method described in non-patent literature (J. Org. Chem. Vol. 55, 1990, page 6368). .
In a reactor equipped with a distiller, 136 g (1.00 mol) of pentaerythritol (manufactured by Wako Pure Chemical Industries, Ltd.), 100 mL of toluene, triethyl orthoformate (manufactured by Wako Pure Chemical Industries, Ltd.) 183 mL (1.00 mol) ), Taking 0.50 g of p-toluenesulfonic acid monohydrate, gradually raising the reactor temperature to 100 ° C. while removing the distilled ethanol, allowing the reaction to proceed for 12 hours, and further reacting at 125 ° C. for 1 hour. It was. After completion of the reaction, low-boiling components were distilled off under reduced pressure at 50 ° C., and the resulting product was dried to obtain a white solid.
To the reactor, 26.4 g (0.470 mol) of potassium hydroxide and 160 mL of dimethyl sulfoxide were added, and 16.0 g (0.100 mol) of the white solid was added while stirring at room temperature, and then 20.0 g of 1-bromohexane ( 0.121 mol) was added and allowed to react for 30 minutes. The reaction solution was added to 1.5 L of water, and this was extracted twice with 200 mL of ethyl acetate. The obtained organic layer was washed with water and dried, and then the low boiling point product was distilled off to obtain a white solid.
This white solid was dissolved in 70 mL of methanol, and then added with 250 mL of 0.01 mol / L hydrochloric acid, reacted at room temperature for 2 hours, and then added with 9.3 g of sodium bicarbonate and stirred at room temperature for 1 hour. After distilling off the solvent under reduced pressure from the obtained reaction liquid, 125 mL of methanol was added and stirred for 12 hours, then insoluble matters were filtered off, and the solvent was distilled off from the obtained filtrate to obtain colorless oily compound MA1. -A was obtained. Yield 18.5 g (83% yield).

(Synthesis example 1-2) Synthesis | combination of compound MA1-B Compound MA1-B was synthesize | combined with reference to the method as described in a patent document (Unexamined-Japanese-Patent No. 2009-149595).
In 40 mL of toluene, 17.6 g (0.080 mol) of the compound MA1-A, 13.4 g of 40 wt% potassium hydroxide aqueous solution, and 0.10 g of benzyltrimethylammonium chloride are taken and stirred at 15 to 20 ° C. while stirring in a water bath. Acrylonitrile (13.2 g, 0.249 mol) was added dropwise over 3 hours. 50 mL of toluene was added to the pale yellow reaction liquid and the phases were separated, and the resulting organic layer was washed with 5 wt% saline, dilute hydrochloric acid, and further 5 wt% saline. After drying over sodium sulfate, the solid was filtered and the solvent was distilled off under reduced pressure to obtain pale yellow oily compound MA1-B. Yield 28.5 g (94% yield).

(Synthesis Example 1-3) Synthesis of Compound MA1-C Compound MA1-C was synthesized with reference to a method described in non-patent literature (J. Fluorine Chem., 2004, No. 125, page 749).
25.0 g (0.066 mol) of the compound MA1-B was added to 125 mL of dehydrated methanol. While stirring at room temperature, hydrogen chloride gas was slowly poured to saturation, and the reaction was continued for 6 hours under heating and refluxing conditions while circulating chlorine gas. After circulating nitrogen gas, the solvent was distilled off, and the residue was dissolved in 200 mL of ethyl acetate and washed with saturated aqueous sodium hydrogen carbonate, water, and saturated brine. After drying over sodium sulfate, the solid was filtered and the solvent was distilled off under reduced pressure to obtain pale yellow oily compound MA1-C. Further purification by column chromatography (developing solvent: hexane / ethyl acetate = 5/1 to 1/1) gave colorless oily compound MA1-C. Yield 24.3 g (77% yield).

(Synthesis example 1-4) Synthesis | combination of compound MA1-D Cyclopentyl methyl ether 150mL, ethanol 20mL, MA1-C 20.0g (0.042mol) is taken, and sodium borohydride 5.7g is added to this in an ice water bath. While stirring, the solution of calcium chloride dihydrate 16.5g in 70 mL of ethanol was slowly added dropwise and allowed to stir for 1 hour. The mixture was heated to 50 ° C., then 17.7 mL of concentrated hydrochloric acid was added and stirred for 1 hour, and further neutralized with an aqueous sodium hydroxide solution, and the resulting solid was filtered off. After the solvent was distilled off from the obtained filtrate, 100 mL of methanol was added to the residue, and then the solvent was distilled off again to obtain colorless oily compound MA1-D. Yield 16.3 g (99% yield).

(Synthesis Example 1-5) Synthesis of Compound MA1-E 16.3 g (0.041 mol) of MA1-D and 14.8 mL of pyridine were added to 200 mL of ethyl acetate, and H (CF ₂ ) ₆ COCl 66 was stirred at room temperature. 0.7 g (0.137 mol, manufactured by Daikin Industries, Ltd.) was added and stirred for 4 hours. Hexane 100mL was added to this, and it wash | cleaned by dilute hydrochloric acid, salt solution, sodium hydrogen carbonate solution, and also salt solution. After drying over sodium sulfate, the solid was filtered and the solvent was removed in vacuo to give colorless oily compound MA1-E. Yield 51.3 g (90% yield).

(Synthesis example 1-6) The synthesis | combination of compound MA1-F The process of compound MA1-F-compound MA1 was synthesize | combined with reference to the method as described in a patent document (Unexamined-Japanese-Patent No. 2010-53084).
In a 500 mL fluororesin container equipped with a raw material supply port, a fluorine supply port, a helium gas supply port and an exhaust port connected to a fluorine trap via a reflux device cooled with dry ice, 300 mL of FC-72 solvent (Sumitomo 30.6) and 70.6 g of sodium fluoride were taken, and helium gas was blown at an internal temperature of 10 ° C. at a flow rate of 100 mL / min for 30 minutes. Next, 20% F ₂ /80% N ₂ mixed gas (fluorine gas) was blown in at a flow rate of 100 mL / min for 30 minutes, and then the fluorine gas flow rate was increased to 250 mL / min and the compound MA1-E 27.6 g ( 0.020 mol) and 4.0 g (0.021 mol) of hexafluorobenzene were added at an internal temperature of 10 to 15 ° C. over 8.5 hours. The fluorine gas flow rate was lowered to 100 mL / min, a solution of 2.0 g of hexafluorobenzene in 25 mL of FC-7 was added over 1 hour, and fluorine gas was further circulated at 100 mL / min for 15 minutes. After replacing the inside of the reaction vessel with helium gas, the solid was filtered off. The obtained filtrate was added to a methanol 100 mL dispersion of 20 g of sodium fluoride and stirred at room temperature for 1 hour, and then the solvent was distilled off under reduced pressure. To the residue, 100 mL of HFE-7100 (manufactured by Sumitomo 3M Limited) was added and dissolved, and washed with aqueous sodium bicarbonate. After drying over magnesium sulfate, the solid was filtered off and the solvent was distilled off. The obtained residue was distilled under reduced pressure to obtain colorless oily compound MA1-F. Yield 13.9 g (65% yield).

(Synthesis Example 1-7) Synthesis of Compound MA1-G In an ice-water bath, 2.7 g (0.071 mol) of sodium borohydride was added to 120 mL of anhydrous THF and stirred in a nitrogen atmosphere. While adjusting at an internal temperature of 10 to 20 ° C., a solution of 20.4 g (0.019 mol) of compound MA1-F in 30 mL of anhydrous THF was added dropwise and stirred as it was for 1 hour, and further stirred at room temperature for 3 hours. 25 mL of 3 mol / L hydrochloric acid was added to bring the pH to 1, followed by stirring for 1 hour. Next, 60 mL of saturated brine and 60 mL of ethyl acetate were added, and the separated organic layer was washed with aqueous sodium bicarbonate and brine, dried over magnesium sulfate, the solid was filtered off, and the solvent was distilled off to remove colorless oil. Compound MA1-G was obtained. Yield 18.0 g (96% yield).

(Synthesis Example 1-8) Synthesis of Compound MA1 To 500 mL of acetonitrile, 88.9 g (0.090 mol) of Compound MA1-G and 186.3 g of potassium carbonate were taken, and 60.8 g (0 .672 mol) was added dropwise and then allowed to stir at room temperature for 5 hours. 120 mL of ethyl acetate and 120 mL of hexane were added to the reaction solution, and 135 mL of 64 wt% sulfuric acid was added dropwise at an internal temperature of 10 ° C. or lower, and the precipitated solid was separated by filtration. The obtained filtrate was washed with brine, aqueous sodium bicarbonate, and saturated brine, and then the solvent was distilled off to obtain a crude product. This was purified by column chromatography (developing solvent: hexane / ethyl acetate = 6/1 to 3/1) to obtain colorless oily compound MA1. Yield 56.9 g (55% yield).

  [Synthesis Example 2] Synthesis of Compound MA3

(Synthesis Example 2-1) Synthesis of Compound MA3-A Compound (MA3-A) was synthesized with reference to a method described in non-patent literature (J. Org. Chem. Vol. 55, 1990, page 6368). .
In a reactor equipped with a distiller, 136 g (1.00 mol) of pentaerythritol (manufactured by Wako Pure Chemical Industries, Ltd.), 100 mL of toluene, triethyl orthoformate (manufactured by Wako Pure Chemical Industries, Ltd.) 183 mL (1.00 mol) ), Taking 0.50 g of p-toluenesulfonic acid monohydrate, gradually raising the reactor temperature to 100 ° C. while removing the distilled ethanol, allowing the reaction to proceed for 12 hours, and further reacting at 125 ° C. for 1 hour. It was. After completion of the reaction, low-boiling components were distilled off under reduced pressure at 50 ° C., and the resulting product was dried to obtain a white solid.
To the reactor, 26.4 g (0.470 mol) of potassium hydroxide and 160 mL of dimethyl sulfoxide were added, and 16.0 g (0.100 mol) of the white solid was added while stirring in an ice-water bath, and then trifluoromethanesulfonic acid-1 84.0 g (0.130 mol, x =) of-(1H, 1H-perfluoro-3,6,9,12-tetraoxatridecyl) was added and allowed to react for 30 minutes. The reaction solution was added to 1.5 L of water, and this was extracted twice with 200 mL of ethyl acetate. The obtained organic layer was washed with water and dried, and then the low boiling point was distilled off to obtain a slightly yellow oil. .
This oily substance was dispersed in 100 mL of methanol, 250 mL of 0.01 mol / L hydrochloric acid was added and reacted at room temperature for 2 hours, and then 9.3 g of sodium bicarbonate was added and stirred at room temperature for 1 hour. After the solvent was distilled off from the obtained reaction solution under reduced pressure, 125 mL of methanol was added and the mixture was stirred for 12 hours, then insoluble matter was filtered off, and the solvent was distilled off from the obtained filtrate to give a slightly yellow oil. Obtained. This was further purified by column chromatography to obtain colorless oily compound MA3-A. Yield 36.0 g (54% yield).

(Synthesis example 2-2) The synthesis | combination of compound MA3 The process of synthesize | combining compound MA3-B-compound MA3 was performed like the synthesis example 1, and compound MA3 was obtained.

  [Synthesis Example 3] Synthesis of Compound MA15

(Synthesis example 3-1) Synthesis | combination of compound MA15-C Compound MA15-C was synthesize | combined with the said synthetic pathway combining the well-known method. Compound MA15-C was purified by column chromatography and used in the next step.

(Synthesis Example 3-2) Synthesis of Compound MA15 The step of synthesizing Compound MA15 was performed in the same manner as in Synthesis Example 1 to obtain Compound MA15.

  [Synthesis Example 4] Synthesis of Compound MA17

(Synthesis Example 4-1) Synthesis of Compound MA17-A 254 g (1.00 mol) of dipentaerythritol (manufactured by Wako Pure Chemical Industries, Ltd.), 200 mL of toluene, and 252 g of acetophenone were attached to a reactor equipped with a Dean-Stark distiller. (2.10 mol), taking 1.0 g of p-toluenesulfonic acid monohydrate, gradually raising the reactor temperature to reflux conditions until a defined amount of water is obtained in the Dean-Stark still The reaction was performed for 12 hours. After completion of the reaction, the low-boiling components were distilled off under reduced pressure, and the resulting product was dried to obtain a white solid.
To the reactor, 26.4 g (0.470 mol) of potassium hydroxide and 160 mL of dimethyl sulfoxide were added, and 45.9 g (0.100 mol) of the white solid was added while stirring in an ice-water bath, and then converted into methanesulfonic acid ester. 90.3 g (0.210 mol) of polyethylene glycol monomethyl ether (manufactured by Wako Pure Chemical Industries, Ltd., average molecular weight 350, x = 7.6) was added and allowed to react for 60 minutes. The reaction solution was added to 1.5 L of water, and this was extracted twice with 150 mL of ethyl acetate. The obtained organic layer was washed with water and dried, and then the low boiling point product was distilled off to obtain a slightly yellow oil. .
This oily substance was dispersed in 100 mL of methanol, 250 mL of 0.01 mol / L hydrochloric acid was added and reacted at room temperature for 2 hours, and then 9.3 g of sodium bicarbonate was added and stirred at room temperature for 1 hour. After the solvent was distilled off from the obtained reaction solution under reduced pressure, 125 mL of methanol was added and allowed to stir for 12 hours. Then, insoluble matters were filtered off, and the solvent was distilled off from the obtained filtrate to give a slightly yellow oily substance. Compound MA17-A was obtained. Yield 66.8 g (70% yield).

(Synthesis example 4-2) The synthesis | combination of compound MA17-C The process of synthesize | combining compound MA17-B and compound MA17-C was performed like the synthesis example 1, and compound MA17-C was obtained.

(Synthesis example 4-3) The synthesis | combination of compound MA17-D The process of compound MA17-D was synthesize | combined with reference to the method as described in a patent document (Unexamined-Japanese-Patent No. 2010-53084).
In a 300 mL fluororesin container equipped with a raw material supply port, a fluorine supply port, a helium gas supply port and an exhaust port connected to a fluorine trap via a reflux device cooled to 20 ° C., 200 mL of halocarbon 1.8 oil (Halocarbon Products Corporation) was taken, and helium gas was blown at an internal temperature of 30 ° C. at a flow rate of 100 mL / min for 30 minutes. Next, 20% F ₂ /80% N ₂ mixed gas (fluorine gas) was blown in at a flow rate of 100 mL / min for 30 minutes, and then the flow rate of the fluorine gas was increased to 250 mL / min while flowing 16.0 g of compound MA17-C ( 0.0124 mol), 0.80 g (0.043 mol) of hexafluorobenzene, and 30 mL of halocarbon 1.8 oil were added at an internal temperature of 30 to 40 ° C. over 20 hours. The fluorine gas flow rate was lowered to 100 mL / min, a 1.0 mL halocarbon 1.8 oil 5 mL solution of hexafluorobenzene was added over 1 hour, and fluorine gas was further circulated at 100 mL / min for 15 minutes. After replacing the inside of the reaction vessel with helium gas, the reaction solution was added to a methanol 100 mL dispersion of 20 g of sodium fluoride and stirred at room temperature for 1 hour, and then the solvent was distilled off under reduced pressure. To the residue, 100 mL of HFE-7100 (manufactured by Sumitomo 3M Co., Ltd.) was added and dissolved, washed with aqueous sodium bicarbonate, dried over magnesium sulfate, and then the solvent was distilled off. The obtained residue was distilled under reduced pressure to obtain colorless oily compound MA17-D. Yield 13.9 g (65% yield).

(Synthesis Example 4-4) Synthesis of Compound MA17 The step of synthesizing Compound MA17-E to Compound MA17 was performed in the same manner as in Synthesis Example 1 to obtain Compound MA17.

  [Synthesis Example 5] Synthesis of Compound MA31

(Synthesis example 5-1) The synthesis | combination of compound MA31-E The process of synthesize | combining compound MA31-A-compound MA31-E was performed like the synthesis example 1, and compound MA31-E was obtained.

(Synthesis Example 5-2) Synthesis of Compound MA31 580 mL of THF was placed in a reactor, 20.7 g (0.548 mol) of sodium borohydride was added in an ice-water bath under a nitrogen atmosphere, and 140 mL of water was further added and stirred. It was. While adjusting the internal temperature at 10 to 20 ° C., a solution of compound MA31-E 100 g (0.110 mol) in 25 mL of THF was dropped, and the mixture was stirred as it was for 30 minutes and then at 20 ° C. for 3 hours. After setting the internal temperature to 10 ° C., 120 mL of 6 mol / L hydrochloric acid was added to adjust the pH to 1, and then 250 mL of brine was added and stirred for 1 hour. Next, 280 mL of ethyl acetate was added, and the separated organic layer was washed 4 times with brine. This solution was directly used in the next step.
The organic layer, 500 mL of n-hexane, 50 g of pyridine, 170 mL of water, and 133 g of sodium bicarbonate were taken in the reactor and stirred in an ice-water bath. To this was added dropwise 160 g (1.26 mol) of 3-chloropropionic acid chloride over 1.5 hours, and the mixture was stirred as it was for 3.5 hours. After the internal temperature was raised to 25 ° C., 600 mL of 10% aqueous potassium carbonate solution was added. And stirred for 1 hour. The organic layer was separated from this, washed with 10% aqueous potassium carbonate solution, 2 mol / L hydrochloric acid, and further with brine, and dried over magnesium sulfate. This solution was directly used in the next step.
The organic layer, 0.05 g of 4-methoxyphenol, and 81.8 g (0.808 mol) of triethylamine were taken in a reactor and stirred at 50 ° C. for 4 hours. The mixture was allowed to cool to room temperature, washed with 400 mL of 2 mol / L hydrochloric acid, aqueous sodium hydrogen carbonate, and brine, dried over magnesium sulfate, added with 40 g of activated alumina, stirred for 30 minutes, and then the solid was filtered off. After adding 0.05 g of 4-methoxyphenol to the obtained filtrate, the solvent was distilled off to obtain compound MA31 as a slightly yellow oil. Yield 92.5 g (83% yield).

  [Synthesis Example 6] Synthesis of Compound ME1

(Synthesis Example 6-1) Synthesis of Compound ME1-G The steps of synthesizing Compound ME1-A to Compound ME1-G were performed in the same manner as in Synthesis Example 1.

(Synthesis Example 6-2) Synthesis of Compound ME1 In a reactor, 2.00 g (0.05 mol) of sodium hydroxide and 4.63 g (0.05 mol) of epichlorohydrin were taken and stirred at 50 ° C. in a nitrogen atmosphere. Then, 9.88 g (0.01 mol) of ME1-G was slowly added and allowed to stir for 3 hours. After allowing to cool to room temperature, the precipitated solid was filtered off, and low-boiling substances were distilled off under reduced pressure. Then, 200 mL of ethyl acetate and 100 mL of water were added for liquid separation, and the resulting organic layer was dried over sodium sulfate. And the solvent was distilled off to obtain the crude product. This was purified by column chromatography to obtain a colorless oily compound ME1. Yield 4.05 g (41% yield).
Compound ME1:
¹ H-NMR (300 MHz, CDCl ₃ ) δ ppm 3.99 (m, 3H), 3.48 (dd, J = 12.6 Hz, 1H), 3.2 (m, 1H), 2.77 (dd, J = 5, 4 Hz, 1H), 2.58 (dd, J = 5, 3 Hz, 1H).
¹⁹ F-NMR (282.4 MHz, CDCl ₃ ) δ ppm −66.1 (s, 6F), −82.4 (t, J = 9 Hz, 3F), −83.3 (m, 2F), −85. 8 (s, 8F), -123.4 (m, 10F), -126.8 (m, 2F), -127.2 (m, 2F).

  [Synthesis Example 7] Synthesis of Compound ME6

  (Synthesis Example 7-1) Synthesis of Compound ME6-A

Compound (ME6-A) was synthesized in the same manner as in Synthesis Example 2-1, with reference to the method described in non-patent literature (J. Org. Chem. Vol. 55, 1990, page 6368).
This oily substance was dispersed in 100 mL of methanol, 250 mL of 0.01 mol / L hydrochloric acid was added and reacted at room temperature for 2 hours, and then 9.3 g of sodium bicarbonate was added and stirred at room temperature for 1 hour. After the solvent was distilled off from the obtained reaction solution under reduced pressure, 125 mL of methanol was added and the mixture was stirred for 12 hours, then insoluble matter was filtered off, and the solvent was distilled off from the obtained filtrate to give a slightly yellow oil. Obtained. Further, this was purified by column chromatography to obtain a colorless oily compound ME6-A. Yield 36.0 g (54% yield).

(Synthesis Example 7-2) Synthesis of Compound ME6-G The steps of synthesizing Compound ME6-B to Compound ME6-G were performed in the same manner as Synthesis Example 1.

(Synthesis Example 7-3) Synthesis of Compound ME6 The step of synthesizing Compound ME6 was performed in the same manner as in Synthesis Example 6-2.
Compound ME6:
¹ H-NMR (300 MHz, CDCl ₃ ) δ ppm 3.99 (m, 3H), 3.48 (dd, J = 12.6 Hz, 1H), 3.22 (m, 1H), 2.77 (dd, J = 5, 4 Hz, 1H), 2.58 (dd, J = 5, 3 Hz, 1H).
¹⁹ F-NMR (282.4 MHz, CDCl ₃ ) δ ppm -66.0 (s, 6F), -79.1 (m, 4F), -80.6 (m, 6F), -82.1 (s, 3F), -86.1 (m, 10F), -123.2 (m, 6F), -130.3 (s, 2F), -145.8 (m, 2F).

  [Synthesis Example 8] Synthesis of Compound ME29

(Synthesis Example 8-1) Synthesis of Compound ME29-F The steps of synthesizing Compound ME29-A to Compound ME29-F were performed in the same manner as in Synthesis Example 4.

(Synthesis Example 8-2) Synthesis of Compound ME29 The step of synthesizing Compound ME29 was performed in the same manner as in Synthesis Example 6-2.
Compound ME29:
¹ H-NMR (300 MHz, CDCl ₃ ) δ ppm 3.98 (m, 3H), 3.49 (dd, J = 12.6 Hz, 1H), 3.24 (m, 1H), 2.78 (dd, J = 5, 4 Hz, 1H), 2.59 (dd, J = 5, 3 Hz, 1H).
¹⁹ F-NMR (282.4 MHz, CDCl ₃ ) δ ppm −65.9 (s, 1F), −85.8 (s, 1F), −123.0 (t, J = 13 Hz, 1F).

  [Synthesis Example 9] Synthesis of Compound N1

  Compound N1 was synthesized according to the method described in Example 1 of WO08 / 018599.

[Example 1] Preparation of liquid repellent treatment agent (Examples 1-1 to 1-13)
In the sample bottle, the fluorine-containing compound represented by the general formula (1) of the types and addition amounts described in Table 1 below, and the general formula (12) or (13) of the types and addition amounts described in Table 1 below. 0.05 g of the fluorine-containing compound and the photopolymerization initiator, and if necessary, add the non-fluorine compound represented by the general formula (16), add 10.0 g of 2-butanone to this, and A homogeneous solution was obtained by stirring. Table 1 shows a list of the prepared liquid repellent treatment agents.
Photopolymerization initiator A: IRGACURE184, manufactured by BASF Japan Ltd.
Photopolymerization initiator B: WPAG-336, manufactured by Wako Pure Chemical Industries, Ltd.
DPHA: dipentaerythritol hexaacrylate, manufactured by Daicel-Cytec Corporation.
PETG: Pentaerythritol tetraglycidyl ether, manufactured by Nagase ChemteX Corporation.
AA-2: Acrylic acid-2- (perfluorohexyl) ethyl, manufactured by Daikin Industries, Ltd.
AA-12: CF ₃ O (CF ₂ CF ₂ CF ₂ O) ₃ CF ₂ CF ₂ CH ₂ OH is converted into an acrylate according to a known method as a compound in which Z in the structural formula AA-12 is 3 What was done was used.
AA-13: As a compound in which Z in the structural formula AA-13 is 3, CF ₃ CF ₂ CF ₂ O [CF (CF ₃ ) CF ₂ O] ₃ CF (CF ₃ ) CH ₂ OH (Sinquest Laboratories) Incorporated) was made into an acrylate according to a known method.
AA-15: Fluorolink D10-H (average molecular weight 700, fluorine atom content 61%, manufactured by Solvay Solexis) and acrylated according to a known method was used.
AE-2: 2- (perfluorohexyl) ethanol (manufactured by Daikin Industries, Ltd.) obtained by glycidyl etherification according to a known method was used.
AE-13: As a compound in which Z in the above structural formula AE-13 is 3, CF ₃ CF ₂ CF ₂ O [CF (CF ₃ ) CF ₂ O] ₃ CF (CF ₃ ) CH ₂ OH (Sinquest Laboratories) Incorporated) was used after glycidyl etherification according to a known method.
AE-15: Fluorolink D10-H (average molecular weight 700, fluorine atom content 61%, manufactured by Solvay Solexis) and glycidyl etherified according to a known method was used.

[Comparative Example 1] Preparation of treating agent (Comparative Examples 1-1 to 1-4)
In a sample bottle, the fluorine-containing compound represented by the general formula (1) or the fluorine-containing compound represented by the general formula (12) or (13), a photopolymerization initiator 0.05 g, and 2-butanone 10.0 g Was stirred sufficiently to obtain a uniform solution. Table 1 shows a list of prepared treatment agents.

[Comparative Example 2] Preparation of treating agent using Compound N1 (Comparative Examples 2-1 and 2-2)
A solution was prepared in the same manner as in Example 1 and Comparative Example 1 except that the compound N1 synthesized in Synthesis Example 9 was used instead of the fluorine-containing compound represented by the general formula (1). Table 1 shows a list of prepared treatment agents.

[Example 2] Preparation and evaluation of treated substrate and member (Examples 2-1 to 2-9)
After immersing a 5 cm square glass substrate in an aqueous potassium hydroxide solution for 1 hour, the glass substrate was thoroughly washed with pure water and then dried by heating in a 90 ° C. oven.
The liquid repellent treatment agent prepared in Example 1-1 to Example 1-9 was spin-coated on the glass substrate (3000 rpm, 20 seconds), then air-dried at room temperature, and further in an oven at 90 ° C. Heat-dried to form a coating film.
A high pressure mercury lamp i-line (365 nm) is applied at 300 mJ / cm ² on the photomask that forms a pattern with a line width of 100 μm and a spacing of 100 μm in a nitrogen atmosphere adjusted to an oxygen concentration of 200 ppm or less on the surface of the coating film prepared as described above. (Illuminance 20 mW / cm ² ) Exposure was performed.
The glass substrate after the light irradiation was washed with 2-butanone and then blown and dried to obtain a treated substrate.

[Static contact angle measurement]
Using a contact angle meter [“CA-X” type contact angle meter, manufactured by Kyowa Interface Science Co., Ltd.] and using pure water as the liquid in a dry state (20 ° C./65% RH), a liquid volume of 1.0 μL Was made on the needle tip, and this was brought into contact with the surface of the water-repellent region of the treated substrate to form a droplet on the film. The angle formed by the film surface and the tangent to the liquid surface at the point where the film and the liquid contact each other, and the angle on the side containing the liquid was defined as the contact angle. The contact angle was also measured using methylene iodide instead of water.

[Abrasion resistance evaluation]
Using a rubbing tester, the rubbing resistance was evaluated by performing a rubbing test under the following conditions.
Evaluation environmental conditions: 25 ° C., 60% RH
Rubbing material: Steel wool (manufactured by Nippon Steel Wool Co., Ltd., Grade No. 0000)
Wrap around the tip (1cm x 1cm) of the scraper of the tester that comes into contact with the sample, and fix the band.
Travel distance (one way): 3cm
Rubbing speed: 3cm / second,
Load: 200 g / cm ² ,
Tip contact area: 1 cm × 1 cm,
Number of rubs: 10 round trips.
An oil-based black ink was applied to the back side of the antireflection film sample that had been rubbed, and visually observed with reflected light, and scratches on the rubbed portion were evaluated according to the following criteria.
A: Even if you look carefully, no scratches are visible.
B: Slight scratches can be seen when looking carefully.
C: A weak wound is visible.
D: There is a scratch that can be seen at first glance.

  Table 2 shows a list of the prepared treatment base materials, static contact angle measurement results in a water-repellent region where no pattern is formed, and friction resistance evaluation.

  After spray-coating an alkaline ink aqueous solution (pH 10.8) in which the pigment was dispersed on the treated substrate, the substrate was blown and dried at room temperature, and further heated and cured in a 90 ° C. oven to prepare a member. Also, as a comparative member, after spray-coating a neutral ink aqueous solution (pH 8.0) in which carbon black is dispersed on the treated substrate, it is blown and dried at room temperature, and further heated and cured in a 90 ° C. oven. A member was produced.

[Boundary contrast evaluation]
The boundary between the area where the ink adhered and the area where the ink did not adhere was visually observed with an optical microscope, and the boundary contrast was evaluated as follows. The results are shown in Table 2.
A: The boundary linearity was at the same level as that of the comparative control member, and ink adhesion to the water repellent area was not observed.
B: Although the boundary linearity was the same level as that of the comparative control member, ink adhesion to the water-repellent area was slightly observed.
C: The boundary linearity was clearly disturbed with respect to the comparative member, and ink adhesion to the water-repellent region was observed.

[Comparative Example 3] Preparation and evaluation of treated substrate and member (Comparative Examples 3-1 to 3-4)
Except having used the processing agent prepared by Comparative Examples 1-1 to 1-2 and Comparative Examples 2-1 to 2-2, the processing base material and member were produced and evaluated similarly to Example 2. The results are shown in Table 2.

[Example 3] Preparation and evaluation of treated substrate and member (Examples 3-1 to 3-4)
After immersing a 5 cm square glass substrate in an aqueous potassium hydroxide solution for 1 hour, the glass substrate was thoroughly washed with pure water and then dried by heating in a 90 ° C. oven.
The liquid repellent treatment agent prepared in Examples 1-10 to 1-13 was spin-coated on the glass substrate (3000 rpm, 20 seconds), then air-dried at room temperature, and further in an 80 ° C. oven for 3 minutes. A coating film was prepared by heating and drying.
The coating film is exposed to 300 mJ / cm ² (illuminance 30 mW / cm ² ) with a high-pressure mercury lamp i-line (365 nm) from a photomask that forms a pattern with a line width of 100 μm and a spacing of 100 μm in an air atmosphere, and then 80 ° C. Heat-treated in an oven for 3 minutes. This glass substrate was washed with 2-butanone and ethanol and then blown and dried to obtain a treated substrate.
About the produced process base material, the static contact angle in a water-repellent area | region and friction resistance were evaluated similarly to Example 2. FIG.
Table 3 shows a list of the prepared processing base materials, a static contact angle measurement result in a water-repellent region where no pattern is formed, and an evaluation result of friction resistance.

  After spray-coating a colored ink for liquid crystal display and color filter containing an organic solvent on the treatment substrate shown in Table 3, it is blown and dried at room temperature and further heated and dried in an oven at 120 ° C. to produce a member. did.

[Boundary contrast evaluation]
The boundary between the area where the colored ink agent adhered and the area where the colored ink agent did not adhere on the surface of the member was visually observed with an optical microscope, and the contrast was evaluated as follows. The results are shown in Table 3.
A: The location where the colored ink agent cured material adhered to the water-repellent region was not observed.
B: Many locations where the colored ink agent cured product adhered to the water-repellent region were observed.

[Comparative Example 4] Preparation and evaluation of treated substrate and member (Comparative Examples 4-1 and 4-2)
Except having used the processing agent prepared by Comparative Examples 1-3 to 1-4, the process base material and the member were produced similarly to Example 3, and were evaluated. The results are shown in Table 3.

[Example 4] Preparation of liquid repellent treatment agent (Examples 4-1 to 4-3)
In a sample bottle, a fluorine-containing compound represented by the general formula (1), a fluorine-containing compound represented by the general formula (12) or (13), a non-fluorine compound represented by the general formula (16), photocationic polymerization A 10% 2-butanone solution 0.24 g of an initiator (WPAG-336, manufactured by Wako Pure Chemical Industries, Ltd.) was taken and sufficiently stirred to obtain a uniform solution.

[Comparative Example 5] Preparation of treatment agent Except that the fluorine-containing compound represented by the general formula (12) or (13) and the non-fluorine compound represented by the general formula (16) were not used, Example 4 and Similarly, a treatment solution was prepared.

[Comparative Example 6] Preparation of Comparative Treatment Agent In a sample bottle, 10.0 g of polydimethylsiloxane having an epoxy group at both ends (X-22-163c, manufactured by Shin-Etsu Chemical Co., Ltd., molecular weight 5,400), light Take 0.60 g of cationic polymerization initiator (IRGACURE250, manufactured by BASF Japan Ltd.) and 0.30 g of photosensitizer (DETX-S, manufactured by Nippon Kayaku Co., Ltd.) and stir well to obtain a uniform solution. It was.

[Example 5] Preparation and evaluation of treated substrate and member (Examples 5-1 to 5-3)
The liquid repellent treatment agent prepared in Example 4 was applied to a bar coater No. 5 on a 5 cm square glass substrate. 5 (11.45 μm), and then dried by heating in an 80 ° C. oven for 3 minutes to form a coating film.
A high pressure mercury lamp i-line (on a photomask in which a pore pattern having a line width of 100 μm, a line length of 200 μm, and an interval of 50 μm is formed in a square of 1.5 cm in length and 1.5 cm in width on the surface of the coating film in an air atmosphere ( (365 nm) was exposed to 800 mJ / cm ² (illuminance 50 mW / cm ² ), and further heat-treated in an 80 ° C. oven for 3 minutes. This glass substrate was washed with 2-butanone and ethanol and then blown and dried to obtain a treated substrate. Hereinafter, the pores having no water-repellent region created here are referred to as pixels. The volume of the pixel formed here is 0.229 μL in calculation.
0.20 μL of a color ink for liquid crystal display and color filter (green and red, 70% by weight of evaporation residue) containing an organic solvent is added to the pixel of the treated substrate prepared above by an inkjet method. Red pixels were provided so as to be alternately formed. The member was produced by air drying at room temperature and then heat drying in a 120 ° C. oven. The surface of the member was visually observed with an optical microscope, and the phenomenon in which the ink agent was mixed between adjacent pixels and the pixel color changed (hereinafter referred to as color mixing) was evaluated as follows. The results are shown in Table 4.
A: The ratio of mixed pixels is less than 5%.
B: The ratio of mixed pixels is 5% or more.

[Comparative Example 7] Preparation of treated substrate (Comparative Examples 7-1 and 7-2)
Except having used the processing agent prepared by the comparative example 5 and the comparative example 6, the process base material and the member were produced similarly to Example 5, and were evaluated. The results are shown in Table 4.

DESCRIPTION OF SYMBOLS 1 Substrate 2 Hydrophilic surface 3 Coating film containing liquid repellent treatment agent of the present invention 4 Liquid repellent film 5 Photomask 6 Light 7 Hydrophilic region 8 Water repellent region 9 Treated substrate 10 Inkjet device 11 Functionality Liquid containing material 12 Functional material 13 Member in which pattern of functional material is formed

Claims (13)

A liquid repellent treatment agent comprising a fluorine-containing compound represented by the following general formula (1) and a fluorine-containing compound represented by the following general formula (12) or (13).

In general formula (1), a represents an integer of 3 to 8, b represents an integer of 0 to 3, c represents an integer of 0 to 10, d and e each independently represents 0 or 1, r represents 0 or 1, Y represents a group represented by the following general formula (2), (3), (4) or (5), an allyl group, or a vinyl group, and L ₁ represents the following general formula ( 6) or a group represented by (7), L ₂ and L ₃ each independently represent a group represented by the following general formula (8), (9), (10) or (11) , Rf ₁ represents a (a + b) -valent, may contain an etheric oxygen atom, a linear, branched or cyclic saturated perfluoroalkyl group having 3 to 20 carbon atoms, Rf ₂ is etheric oxygen atoms may contain, represents a monovalent perfluoroalkyl group or a fluorine atom, linear or branched C1-5, Rf ₃ is It may contain ether oxygen atoms, a straight, branched or cyclic, monovalent perfluoroalkyl group of 3 to 100 carbon atoms.

In general formula (2), X represents a hydrogen atom, a fluorine atom, a chlorine atom, a methyl group, a trifluoromethyl group, or a hydroxyl group.
In general formulas (3), (4) and (5), R ₁ , R ₂ , R ₃ , R ₄ , R ₅ and R ₆ may each independently have a hydrogen atom or a substituent. It represents a good linear or branched monovalent alkyl group having 1 to 5 carbon atoms.
In general formula (5), k represents 1 or 2.
In general formulas (6) and (7), m represents an integer of 0 to 10.
In general formula (8), (9), (10), (11), n represents the integer of 0-10.
In the general formula (7), Y represents a group represented by the general formula (2), (3), (4) or (5), an allyl group, or a vinyl group.

In general formula (12), f represents an integer of 1 to 5, g represents 0 or 1, and Y represents a group represented by the general formula (2), (3), (4) or (5). , An allyl group, or a vinyl group, L ₄ represents a group represented by the general formula (6) or (7), or the following general formula (14) or (15), and Rf ₄ represents an etheric oxygen A linear, branched or cyclic monovalent perfluoroalkyl group having 1 to 100 carbon atoms which may contain an atom is represented.
In general formula (13), h and i each independently represent an integer of 1 to 5, Y is a group represented by general formula (2), (3), (4) or (5), or an allyl group. Or L ₄ represents a group represented by the general formula (6) or (7) or the following general formula (14) or (15), and Rf ₅ represents an etheric oxygen. A linear, branched or cyclic divalent perfluoroalkyl group having 1 to 100 carbon atoms which may contain an atom is represented.

In general formula (14), m represents an integer of 0 to 10.
In the general formula (15), Y represents a group represented by the general formula (2), (3), (4) or (5), an allyl group, or a vinyl group.   The content ratio of the fluorine-containing compound represented by the general formula (1) is 5% by mass or more and 90% by mass or less, and the content ratio of the fluorine-containing compound represented by the general formula (12) or (13) is The liquid repellent treatment agent according to claim 1, which is 10% by mass or more and 95% by mass.   The liquid repellent treatment agent according to claim 1 or 2, wherein a fluorine atom content of the fluorine-containing compound represented by the general formula (12) or (13) is 30% by mass or more and 75% by mass or less. Furthermore, the liquid-repellent processing agent of any one of Claims 1-3 containing the non-fluorine compound represented by following General formula (16).

In general formula (16), j represents an integer of 1 to 6, and Y represents a group represented by the following general formula (21), (3), (4) or (5), an allyl group, or a vinyl group. L ₅ represents a group represented by the following general formula (6), (7), (14) or (15), and R ₇ is a hydrogen atom or a carbon number which may have a substituent. 1-20 linear, branched or cyclic j-valent organic groups are represented.

In General Formula (21), X ¹ represents a hydrogen atom, a chlorine atom, a methyl group, or a hydroxyl group.
In general formulas (3), (4) and (5), R ₁ , R ₂ , R ₃ , R ₄ , R ₅ and R ₆ may each independently have a hydrogen atom or a substituent. It represents a good linear or branched monovalent alkyl group having 1 to 5 carbon atoms.
In general formula (5), k represents 1 or 2.
In general formulas (6), (7), and (14), m represents an integer of 0 to 10.
In the general formulas (7) and (15), Y represents a group represented by the general formula (21), (3), (4) or (5), an allyl group, or a vinyl group.   (A + b) in General formula (1) is an integer of 3-8, The liquid-repellent processing agent of any one of Claims 1-4.   D and e in General formula (1) are 1, The liquid-repellent processing agent of any one of Claims 1-5. The fluorine-containing compound represented by the general formula (1) is a fluorine-containing compound represented by the following general formula (17), and the fluorine-containing compound represented by the general formula (12) or (13) is The liquid repellent treatment agent according to any one of claims 1 to 6, which is a fluorine-containing compound represented by the general formula (18) or (19).

In general formula (17), a represents an integer of 3 to 8, b represents an integer of 0 to 3, c represents an integer of 0 to 10, Y represents the following formulas (2), (3), ( 4) or a group represented by (5), an allyl group, or a vinyl group, L ₁ represents a group represented by the following formula (6) or (7), and Rf ₁ is an (a + b) -valent group. may contain an etheric oxygen atom, a linear, branched or cyclic saturated perfluoroalkyl group having 3 to 20 carbon atoms, Rf ₂ may contain an etheric oxygen atom, 1 to carbon atoms 5 represents a linear or branched monovalent perfluoroalkyl group or a fluorine atom, and Rf ₆ may contain an etheric oxygen atom having at least one trifluoromethyl group, having 3 to 3 carbon atoms 100 linear, branched or cyclic monovalent perfluoroalkyl groups are represented.

In general formula (2), X represents a hydrogen atom, a fluorine atom, a chlorine atom, a methyl group, a trifluoromethyl group, or a hydroxyl group.
In general formulas (3), (4) and (5), R ₁ , R ₂ , R ₃ , R ₄ , R ₅ and R ₆ may each independently have a hydrogen atom or a substituent. It represents a good linear or branched monovalent alkyl group having 1 to 5 carbon atoms.
In general formula (5), k represents 1 or 2.
In general formulas (6) and (7), m represents an integer of 0 to 10.
In general formula (8), (9), (10), (11), n represents the integer of 0-10.
In the general formula (7), Y represents a group represented by the general formula (2), (3), (4) or (5), an allyl group, or a vinyl group.

In general formula (18), f represents an integer of 1 to 5, and Y represents a group represented by the general formula (2), (3), (4) or (5), an allyl group, or a vinyl group. Rf ₇ represents a linear, branched or cyclic monovalent perfluoroalkyl group having 1 to 100 carbon atoms, which may contain an etheric oxygen atom, and has at least one trifluoromethyl group. .
In general formula (19), h and i each independently represent an integer of 1 to 5, Y is a group represented by the general formula (2), (3), (4) or (5), or an allyl group Or Rf ₈ represents a linear or branched divalent perfluoroalkyl group having 1 to 100 carbon atoms, which may contain an etheric oxygen atom. The liquid repellent treatment agent according to any one of claims 1 to 7, wherein Rf1 in the general formula (1) is a group selected from the following f- ₁ to f-14.

Wherein * _{Y-L 1 -O-CH 2} - (CF 2) c - [CF (Rf 2)] r - (O) d -L 2 - or _{Rf 3 - (O) e -L} 3 - Represents the position to be combined.   A liquid repellent film obtained by curing the liquid repellent treatment agent according to claim 1.   A member having a water-repellent region and a hydrophilic region on the surface of a substrate, wherein the water-repellent region is a liquid-repellent material obtained by curing the liquid-repellent treatment agent according to any one of claims 1 to 8. A member made of a film.   The member according to claim 10, wherein the water-repellent region and the hydrophilic region form a pattern.   The process of forming the coating film containing the liquid-repellent processing agent of any one of Claims 1-8 on the surface of the base material which has a hydrophilic surface, Then, light is irradiated to a part of this coating film. The member according to claim 10 or 11, comprising a step of curing a coating film containing a liquid repellent treatment agent, and then a step of removing the uncured liquid repellent treatment agent on the substrate surface to expose a hydrophilic surface. Manufacturing method.   The step of applying a liquid containing a functional material to the hydrophilic region of the member according to claim 10 or 11, or the member manufactured by the manufacturing method according to claim 12, and then drying the member to which the liquid is applied The manufacturing method of the member in which the pattern of the functional material was formed including the process to make.

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