JPWO2016063943A1 - Partition curable composition, partition, partition manufacturing method, partition repair method, repaired partition, and optical element - Google Patents

Abstract

A curable composition capable of forming or repairing a partition wall having a good ink repellency on the top surface and a good ink affinity on the side surface by applying a micro discharge method, and formed using such a composition. Provided is a partition wall that has been repaired or repaired, a method of manufacturing or repairing the partition wall using such a composition, and an optical element including such a partition wall. A curable composition for forming a partition wall having a top surface formed in a shape for partitioning a substrate surface into a plurality of dot forming sections and a side surface subsequent thereto, or for repairing defects generated in the partition wall, and having liquid repellency A curable composition for partition walls such as an organic EL device comprising a compound (A), a crosslinking agent (B), and a polymerization initiator (C), wherein the liquid repellent compound is lyophilic by light irradiation. And a partition wall formed or repaired using the composition, a method of manufacturing or repairing the partition wall using the composition, and an optical element such as an organic EL element having the partition wall.

Description

  The present invention relates to a partition wall curable composition, a partition wall, a partition wall manufacturing method, a partition wall repair method, a repaired partition wall, and an optical element.

  Recently, in the manufacture of optical elements such as organic EL (Electro-Luminescence) elements, quantum dot displays, TFT (Thin Film Transistor) arrays, thin film solar cells, etc., an ink jet (IJ) method using organic layers such as light emitting layers as dots. A pattern printing method has been used. The ink jet (IJ) method is a printing method that does not use a plate, and can reduce the cost for producing the plate, and also uses the necessary amount of material for the necessary part, so that the material cost can be reduced. Have

  By the way, in this method, it is necessary to provide a partition along the outline of the dot to be formed. A partition wall is provided, and ink containing an organic layer material is injected into a section surrounded by the partition wall (hereinafter, also referred to as “opening”), and a desired pattern is formed by drying and / or heating. Forming dots.

  Conventionally, a photolithography method is generally used for forming the partition wall. At this time, when pattern printing is performed by the inkjet (IJ) method, the upper surface of the partition wall needs to have ink repellency in order to prevent ink mixing between adjacent dots and to uniformly apply ink in dot formation. On the other hand, the dot forming opening surrounded by the partition including the partition side surface needs to have ink affinity. Therefore, in order to obtain a partition wall having ink repellency on the upper surface, the partition wall corresponding to the dot pattern is formed by photolithography using a photosensitive resin composition containing an ink repellent agent.

  However, the photolithography method requires a dedicated line equipped with an exposure machine, a developing machine, etc., and the process is complicated. There is also a problem that a development residue remains in the opening. If the inkjet (IJ) method can be applied to the formation of the partition walls, the manufacturing process can be simplified and the cost is advantageous.

  As this type of technology, for example, Patent Document 1 describes a photocurable inkjet ink in which a partition having a surface having ink repellency is formed by an inkjet (IJ) method. However, this photo-curable ink jet ink imparts ink repellency to the entire surface of the partition wall, and can impart ink repellency to the side surface of the partition wall while providing ink repellency to the side surface of the partition wall. Has not yet been found.

  By the way, it is very difficult to form such a partition wall on a substrate without defects such as poor formation in consideration of a narrow partition wall width. In particular, recently, barrier ribs have been increasingly miniaturized, and it has become difficult to form defect-free barrier ribs. Generation | occurrence | production of the defect of a partition reduces the yield of a product and leads to an increase in manufacturing cost by extension. For this reason, when a defect occurs in the partition wall, it is important to repair the defect, and a technique for that is required.

  As this type of technology, for example, Patent Document 2 describes a repair ink made of a resin binder and an ink repellent that corrects a pinhole defect generated in a partition wall. However, with this repair ink, ink repellency is imparted to the entire surface of the repaired portion, and the ink cannot be uniformly applied to the openings partitioned by the partition walls.

International Publication No. 2013/024764 International Publication No. 2010/13654

  The present invention has been made in response to the above-described problems of the prior art. By applying a micro discharge method (inkjet method or the like), the top surface has good ink repellency, while the side surface has good ink affinity. A curable composition capable of forming a partition wall having a barrier rib, and a defect such as a formation defect that has occurred in the partition wall during the manufacture of the partition wall, and the repaired portion of the partition wall has good ink repellency on the upper surface. In addition, an object of the present invention is to provide a curable composition that can be repaired so that the side wall becomes a partition having good ink affinity.

The present invention uses the above-described curable composition, the partition wall having good ink repellency on the upper surface and good ink-philicity on the side surface, a method for producing the same, and the curable composition described above. An object of the present invention is to provide a method for repairing a partition wall and a partition wall repaired using the curable composition.
Furthermore, an optical element having partition walls formed using the curable composition, or an optical element having partition walls repaired using the curable composition, specifically an organic EL element, a quantum dot display An object is to provide a TFT array, a thin film solar cell, and the like.

ただし、Ｃｆは、炭素数１〜２０のフルオロアルキル基、または炭素原子間にエーテル性酸素原子を有する炭素数２〜２０のフルオロアルキル基であり、
Ｒ^１およびＲ^２は、それぞれ独立に水素原子、炭素数１〜６のアルキル基、またはフェニル基であり、
Ｒ^３は、単結合、またはフッ素原子を有さない２価の有機基であり、
Ｒ^４〜Ｒ^８の少なくとも１つは下式（１）で表される基であり、その他はそれぞれ独立に水素原子、ハロゲン原子、それぞれ置換されていてもよい炭素数１〜１２のアルキル基、炭素数２〜１２のアルケノイル基、炭素数１〜１２のアルコキシ基、炭素数５〜８のシクロアルキル基、炭素数６〜２０のアリール基、炭素数７〜２０のベンゾイル基、炭素数２〜１２のアルカノイル基、炭素数２〜１２のアルコキシカルボニル基もしくは炭素数７〜２０のフェノキシカルボニル基、またはニトロ基である。

ただし、Ｘは、単結合、酸素原子、硫黄原子、窒素原子またはＮＨであり、
ｎは、０〜４の整数であり、
ｍは、Ｘが単結合、酸素原子、硫黄原子またはＮＨである場合には１であり、Ｘが窒素原子である場合には２であり、
Ｚは、架橋性官能基を有する基である。
［６］ 前記撥液性化合物（Ａ）が、波長３００ｎｍ以上の紫外線の照射によって親液化するものである［３］に記載の隔壁用硬化性組成物。
［７］ 前記撥液性化合物（Ａ）が、下式（ｍ２）で表される化合物に基づく単位（ｕ２−１）を有するものである［６］記載の隔壁用硬化性組成物。

ただし、Ｃｆは、炭素数１〜２０のフルオロアルキル基、または炭素原子間にエーテル性酸素原子を有する炭素数２〜２０のフルオロアルキル基であり、
Ｒ^１２は、水素原子、炭素数１〜１２のアルキル基、または炭素数６〜２０のアリール基であり、
Ｒ^３は、単結合、またはフッ素原子を有さない２価の有機基であり、
Ｒ^１３〜Ｒ^１７の少なくとも１つは末端に下式（１）で表される基を有する１価の有機基であり、その他はそれぞれ独立に水素原子、ハロゲン原子、それぞれ置換されていてもよい炭素数１〜１２のアルキル基、炭素数２〜１２のアルケノイル基、炭素数１〜１２のアルコキシ基、炭素数５〜８のシクロアルキル基、炭素数６〜２０のアリール基、炭素数７〜２０のベンゾイル基、炭素数２〜１２のアルカノイル基、炭素数２〜１２のアルコキシカルボニル基、炭素数が３〜２０のアルコキシカルボニルアルカノイル基、炭素数７〜２０のフェノキシカルボニル基、炭素数が８〜２０のフェノキシカルボニルアルカノイル基、炭素数が８〜２０のヘテロアリールオキシカルボニルアルカノイル基、−ＳＲ^１０１、−ＳＯＲ^１０１、−ＳＯ_２Ｒ^１０１、もしくは−ＮＲ^１０１Ｒ^１０２（ここで、Ｒ^１０１およびＲ^１０２はそれぞれ独立に水素原子、またはそれぞれ置換されていてもよい炭素数１〜１２のアルキル基、炭素数３〜１２のアルケニル基、炭素数２〜８のアルカノイル基、炭素数６〜２０のアリール基、もしくは炭素数が３〜１５のトリアルキルシリル基を表す。）、またはニトロ基であって、Ｒ^１３〜Ｒ^１７は、複数の置換基同士が結合してさらに置換基を有していてもよく、飽和もしくは不飽和芳香族環を形成していてもよく、
ｊは０または１である。

ただし、Ｘは、単結合、酸素原子、硫黄原子、窒素原子またはＮＨであり、
ｎは、０〜４の整数であり、
ｍは、Ｘが単結合、酸素原子、硫黄原子またはＮＨである場合には１であり、Ｘが窒素原子である場合には２であり、
Ｚは、架橋性官能基を有する基である。
［８］ 微量吐出法用組成物である［１］〜［７］のいずれかに記載の隔壁用硬化性組成物。
［９］ 前記隔壁の形成に用いる、前記微量吐出法が、インクジェット法、ノズルプリンティング法またはマイクロディスペンサ法である［８］に記載の隔壁用硬化性組成物。
［１０］ 前記隔壁の修復に用いる、粘度が１〜１０００００ｍＰａ・ｓである、［１］〜［８］のいずれかに記載の隔壁用硬化性組成物。
［１１］ 前記微量吐出法が、ディスペンサ法である［１０］に記載の隔壁用硬化性組成物。
［１２］ 基板表面をドット形成用の複数の区画に仕切る形に形成された上面とそれに続く側面を有する隔壁であって、［１］〜［９］のいずれかに記載の隔壁用硬化性組成物の硬化膜からなり、前記側面に親液性領域を有することを特徴とする隔壁。
［１３］ 前記基板表面の所定の位置に［１］〜［９］のいずれかに記載の隔壁用硬化性組成物を塗布し硬化させて、前記隔壁に対応する形状の、上面とそれに続く側面を有する硬化膜を形成する工程と、
前記基板の裏面から光を照射し、前記硬化膜の側面に親液性領域を形成する工程と
を有する［１２］に記載の隔壁の製造方法。
［１４］ 基板表面に複数のドットと隣接するドット間に位置する隔壁とを有する光学素子であって、前記隔壁が［１２］に記載の隔壁で形成されていることを特徴とする光学素子。
［１５］ 基板表面をドット形成用の複数の区画に仕切る形に形成された隔壁に発生した欠陥を修復する方法であって、
前記欠陥に［１］〜［８］、［１０］、［１１］のいずれかに記載の隔壁用硬化性組成物を塗布し硬化させて、前記隔壁に対応する形状の、上面とそれに続く側面を有する硬化膜を形成する工程と、
前記硬化膜の側面に光を照射して、前記側面に親液性領域を形成する工程と
を有することを特徴とする隔壁の修復方法。
［１６］ 基板表面をドット形成用の複数の区画に仕切る形に形成された隔壁であって、
［１］〜［８］、［１０］、［１１］のいずれかに記載の隔壁用硬化性組成物により形成された、上面とそれに続く側面を有する硬化膜からなる隔壁修復部を有し、前記硬化膜の側面に親液性領域を有することを特徴とする隔壁。
［１７］ 基板表面に複数のドットと隣接するドット間に位置する隔壁とを有する光学素子であって、
前記隔壁が［１６］に記載の隔壁で形成されていることを特徴とする光学素子。The present invention provides a curable composition for a partition, a partition, a repair method for the partition, a repaired partition, an optical element, and a method for producing the same, having the following configurations [1] to [17].
[1] A curable composition for forming a partition wall having an upper surface and a side surface following the upper surface formed to partition the substrate surface into a plurality of sections for forming dots, or for repairing defects generated in the partition wall. ,
A liquid repellent compound (A), a crosslinking agent (B), and a polymerization initiator (C) are contained, and the liquid repellent compound (A) is lyophilic by light irradiation. A curable composition for partition walls.
[2] The curable composition for a partition according to [1], wherein the liquid repellent compound (A) has a structure in which a liquid repellent site is decomposed by light irradiation.
[3] The curable composition for a partition according to [2], wherein the liquid repellent compound (A) has a crosslinkable functional group.
[4] The partition wall according to [3], wherein the liquid repellent compound (A) is lyophilic by irradiation with ultraviolet rays having a wavelength of less than 300 nm, and contains a photopolymerization initiator as a polymerization initiator (C). Curable composition.
[5] The curable composition for a partition wall according to [4], wherein the liquid repellent compound (A) has a unit (u1-1) based on a compound represented by the following formula (m1).

However, Cf is a C1-C20 fluoroalkyl group or a C2-C20 fluoroalkyl group having an etheric oxygen atom between carbon atoms,
R ¹ and R ² are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group,
R ³ is a single bond or a divalent organic group having no fluorine atom,
At least one of R ^{4 to} R ⁸ is a group represented by the following formula (1), and the others are each independently a hydrogen atom, a halogen atom, and an optionally substituted alkyl group having 1 to 12 carbon atoms, C2-C12 alkenoyl group, C1-C12 alkoxy group, C5-C8 cycloalkyl group, C6-C20 aryl group, C7-C20 benzoyl group, C2-C2 A alkanoyl group having 12 carbon atoms, an alkoxycarbonyl group having 2 to 12 carbon atoms, a phenoxycarbonyl group having 7 to 20 carbon atoms, or a nitro group.

However, X is a single bond, an oxygen atom, a sulfur atom, a nitrogen atom or NH,
n is an integer of 0 to 4,
m is 1 when X is a single bond, an oxygen atom, a sulfur atom or NH, and is 2 when X is a nitrogen atom,
Z is a group having a crosslinkable functional group.
[6] The curable composition for a partition wall according to [3], wherein the liquid repellent compound (A) is lyophilic by irradiation with ultraviolet rays having a wavelength of 300 nm or more.
[7] The curable composition for a partition according to [6], wherein the liquid repellent compound (A) has a unit (u2-1) based on a compound represented by the following formula (m2).

However, Cf is a C1-C20 fluoroalkyl group or a C2-C20 fluoroalkyl group having an etheric oxygen atom between carbon atoms,
R ¹² is a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or an aryl group having 6 to 20 carbon atoms,
R ³ is a single bond or a divalent organic group having no fluorine atom,
At least one of R ^{13 to} R ¹⁷ is a monovalent organic group having a group represented by the following formula (1) at the terminal, and the others are each independently substituted with a hydrogen atom or a halogen atom. C1-C12 alkyl group, C2-C12 alkenoyl group, C1-C12 alkoxy group, C5-C8 cycloalkyl group, C6-C20 aryl group, C7-C7 20 benzoyl groups, C2-C12 alkanoyl groups, C2-C12 alkoxycarbonyl groups, C3-C20 alkoxycarbonylalkanoyl groups, C7-C20 phenoxycarbonyl groups, C8 20 of phenoxycarbonyl alkanoyl group, heteroaryloxycarbonyl alkanoyl group having 8 to 20 carbon ^atoms, -SR ^{101, -SOR} 101, -SO ₂ R ¹⁰¹ , or —NR ¹⁰¹ R ¹⁰² (where R ¹⁰¹ and R ¹⁰² are each independently a hydrogen atom, or an optionally substituted alkyl group having 1 to 12 carbon atoms or an alkenyl having 3 to 12 carbon atoms) A nitro group, a alkanoyl group having 2 to 8 carbon atoms, an aryl group having 6 to 20 carbon atoms, or a trialkylsilyl group having 3 to 15 carbon atoms), wherein R ^{13 to} R ¹⁷ are A plurality of substituents may be bonded to each other to further have a substituent, may form a saturated or unsaturated aromatic ring,
j is 0 or 1.

However, X is a single bond, an oxygen atom, a sulfur atom, a nitrogen atom or NH,
n is an integer of 0 to 4,
m is 1 when X is a single bond, an oxygen atom, a sulfur atom or NH, and is 2 when X is a nitrogen atom,
Z is a group having a crosslinkable functional group.
[8] The curable composition for a partition wall according to any one of [1] to [7], which is a composition for a micro discharge method.
[9] The curable composition for a partition according to [8], wherein the micro discharge method used for forming the partition is an inkjet method, a nozzle printing method, or a microdispenser method.
[10] The curable composition for a partition according to any one of [1] to [8], which has a viscosity of 1 to 100,000 mPa · s and is used for repairing the partition.
[11] The partition wall curable composition according to [10], wherein the micro-discharge method is a dispenser method.
[12] A partition wall curable composition according to any one of [1] to [9], wherein the partition surface has a top surface formed in a shape that partitions the substrate surface into a plurality of dot forming sections and a side surface following the top surface. A partition wall comprising a cured film of an object and having a lyophilic region on the side surface.
[13] An upper surface and a side surface following the upper surface of the shape corresponding to the partition walls, by applying and curing the curable composition for partition walls according to any one of [1] to [9] at a predetermined position on the substrate surface Forming a cured film having:
And irradiating light from the back surface of the substrate to form a lyophilic region on the side surface of the cured film.
[14] An optical element having a plurality of dots and a partition located between adjacent dots on the substrate surface, wherein the partition is formed by the partition described in [12].
[15] A method for repairing a defect generated in a partition wall formed in a shape for partitioning a substrate surface into a plurality of sections for dot formation,
The partition wall curable composition according to any one of [1] to [8], [10], and [11] is applied to the defect and cured to form an upper surface and a side surface subsequent to the shape corresponding to the partition wall. Forming a cured film having:
Irradiating light on the side surface of the cured film to form a lyophilic region on the side surface.
[16] A partition formed in a shape that partitions the substrate surface into a plurality of sections for dot formation,
[1] to [8], [10], having a partition wall repairing portion formed of a cured film having a top surface and a side surface formed thereafter, formed by the partition wall curable composition according to any one of [11], A partition wall having a lyophilic region on a side surface of the cured film.
[17] An optical element having a plurality of dots and a partition located between adjacent dots on the substrate surface,
An optical element, wherein the partition wall is formed by the partition wall described in [16].

  According to the present invention, a curable composition that can form a partition wall having a good ink repellency on the top surface and a good ink-philic property on the side surface by applying a micro discharge method (inkjet method or the like), In the production of the partition walls, defects such as formation defects that occurred in the partition walls are easily repaired, and the partition walls in the repaired part have good ink repellency on the top surface and good ink affinity on the side surface. Thus, a curable composition that can be repaired can be provided.

According to the present invention, the partition wall formed by using the curable composition and having a good ink repellency on the upper surface and a good ink affinity on the side surface, a method for producing the partition, and the curable composition It is possible to provide a method of repairing a partition wall using the method, and a partition wall repaired using the curable composition.
Furthermore, an optical element having partition walls formed using the curable composition, or an optical element having partition walls repaired using the curable composition, specifically an organic EL element, a quantum dot display , TFT arrays, thin film solar cells and the like can be provided.

It is sectional drawing which shows typically an example of the partition of this invention. It is a top view which shows an example of the partition which has the defect which the curable composition for partition of this invention makes the object of restoration. It is a schematic sectional drawing which shows the repair process of the partition by embodiment of this invention. It is a schematic sectional drawing which shows the repair process after the process shown to FIG. 3A. It is a schematic sectional drawing which shows the repair process after the process shown to FIG. 3B. It is a figure which shows typically an example of the manufacturing method of the optical element of this invention. It is a figure which shows typically an example of the manufacturing method of the optical element of this invention.

In the present specification, the following terms are respectively used with the following meanings.
A compound represented by the formula (m1) is referred to as a compound (m1). The same applies to compounds represented by other formulas. Moreover, group represented by Formula (1) is described as group (1). Groups represented by other formulas are also described in the same manner.
“Liquid repellency” is a general term for water repellency and oil repellency. In the present specification, “liquid repellency” is sometimes referred to as “ink repellency”. That is, in the present specification, “liquid repellency” and “ink repellency” are substantially synonymous.
“Lipophilicity” is a generic term for hydrophilicity and lipophilicity. In the present specification, “lyophilic” may be referred to as “ink-philic”. That is, in the present specification, “lyophilic” and “ink-philic” are substantially synonymous.
“Liquidification” means that the liquid repellency is changed to relatively lyophilic, specifically, the contact angle with water or an organic solvent is reduced.

The “methacryloyl (oxy) group” is a general term for a methacryloyl group and a methacryloyloxy group. The same applies to the “acryloyl (oxy) group”.
The “(meth) acryloyl group” is a general term for an acryloyl group and a methacryloyl group. The “(meth) acryloyloxy group”, (meth) acrylic acid, (meth) acrylate, (meth) acrylamide, and (meth) acrylic resin also conform to this.
A “unit” is a unit derived from a monomer formed by polymerization of the monomer. The unit may be a unit directly formed by polymerization, or may be a unit in which a part of the unit is converted into another structure by treating the polymer.
A “monomer” is a compound having a functional group that can be polymerized by a radical.

The “crosslinkable functional group” is a functional group that can be polymerized by a radical.
Examples of the crosslinkable functional group include a carbon-carbon unsaturated double bond that can be polymerized by a radical, a carbon-carbon unsaturated triple bond that can be polymerized by a radical, a ring that is opened by a radical, and a group containing these. The unsaturated double bond and unsaturated triple bond may be those present inside the molecular chain (hereinafter also referred to as internal olefin type), or those existing at the end of the molecule (hereinafter referred to as terminal olefin type). The terminal olefin type is preferable from the viewpoint of high reactivity. Internal olefin types also include the presence of unsaturated double bonds in some of the aliphatic rings, such as cycloolefins. The terminal olefin type crosslinkable functional group is preferably an alkenyl group having 4 or less carbon atoms or an alkynyl group having 4 or less carbon atoms.

Specific examples of the crosslinkable functional group include vinyl (oxy) group, allyl (oxy) group, isopropenyl group, 3-butenyl group, (meth) acryloyl (oxy) group, trifluorovinyl (oxy) group, Examples include ethynyl group, 1-oxocyclopenta-2,5-dien-3-yl group, cyano group, diallylhydroxymethyl group, hydroxyfluorenyl group, cyclobutalene ring, and oxirane ring.
The crosslinkable functional group comprises a vinyl group, an allyl group, an ethynyl group, a vinyloxy group, an allyloxy group, and a (meth) acryloyl (oxy) group from the viewpoint that a cured film having high reactivity and high crosslink density can be easily obtained. One or more crosslinkable functional groups selected from the group are preferred.

“Ink” is a generic term for liquids that have optical and / or electrical functions after drying, curing, and the like.
In an organic EL element, a quantum dot display, a TFT array, a thin film solar cell, and the like, dots as various components may be pattern-printed by an ink jet (IJ) method using the ink for forming the dots. “Ink” includes ink used in such applications.

  The “dot” indicates a minimum area where light modulation is possible in the optical element. In an organic EL element, a quantum dot display, a TFT array, and a thin film solar cell, 1 dot = 1 pixel in the case of black and white display, for example, 3 dots (R (red), G (green), B in the case of color display. (Blue) etc. = 1 pixel.

  The number average molecular weight (Mn) is a polystyrene equivalent molecular weight obtained by measuring with gel permeation chromatography using a calibration curve prepared using a standard polystyrene sample with a known molecular weight.

The viscosity is measured at 25 ° C. using a TVE25L viscometer (manufactured by Toki Sangyo Co., Ltd.) calibrated with viscometer calibration standard solution JS2.5 (trade name, manufactured by Nippon Grease Co., Ltd.). Value.
Embodiments of the present invention will be described below.

[Curable composition for partition walls]
The partition wall curable composition of the present invention (hereinafter, also simply referred to as “the curable composition of the present invention” or “the composition of the present invention”) is a composition that is cured by heat or light, and is a liquid repellent compound. It is a composition containing (A), a crosslinking agent (B), and a polymerization initiator (C). The composition of the present invention further contains an ultraviolet absorber (D), a binder resin (E), an acid generator (F), a thiol compound (G), a solvent (H), and other optional components as necessary. You may contain.
Hereinafter, each component will be described.

(Liquid repellent compound (A))
The liquid repellent compound (A) in the present invention has liquid repellency, and the liquid repellency is changed to lyophilic when irradiated with light, that is, has the property of becoming lyophilic. . The liquid repellent compound (A) preferably has a structure in which the liquid repellent site is decomposed by light irradiation.

  The liquid repellent compound (A) preferably has either a fluorine atom or a silicon atom at the liquid repellent site. Examples of the silicon atom-containing compound include dimethylpolysiloxane and compounds in which part or all of the methyl group of dimethylpolysiloxane is substituted with a phenyl group or a fluorine atom. The liquid repellent compound (A) preferably has a fluorine atom at the liquid repellent site, and particularly preferably has a fluorine atom and no silicon atom. The liquid repellent compound (A) preferably further has a crosslinkable functional group at a portion other than the liquid repellent portion.

  The light used for lyophilicity of the liquid repellent compound (A) is preferably ultraviolet rays. Specifically, as the liquid repellent compound (A), the following two types of liquid repellent compounds, that is, a liquid repellent compound (A1) which is a compound that becomes lyophilic with ultraviolet light of less than 300 nm, and The liquid repellent compound (A2) which is a compound that becomes lyophilic with light of 300 nm or more is preferred.

<Liquid repellent compound (A1)>
The liquid repellent compound (A1) is a compound that absorbs light of less than 300 nm. Specifically, a polymer having a unit based on the compound (m1) (hereinafter also referred to as “unit (u1-1)”) can be given.

In the formula, Cf is a C 1-20 fluoroalkyl group or a C 2-20 fluoroalkyl group having an etheric oxygen atom between carbon atoms.
The number of carbon atoms in the Cf group is preferably 2 to 20, more preferably 2 to 15 and particularly preferably 4 to 8 from the viewpoint of excellent liquid repellency and good compatibility with other monomers. Further, the number of carbon atoms in the Cf group is preferably 6 or less, more preferably 2 to 6 and particularly preferably 4 to 6 from the viewpoint of low environmental load.

The number of fluorine atoms in the Cf group is preferably 80% or more with respect to the total number of fluorine atoms and hydrogen atoms, from the viewpoint that the liquid repellency of the surface of the cured film becomes better. That is, a perfluoroalkyl group having 1 to 20 carbon atoms or a perfluoroalkyl group having 2 to 20 carbon atoms having an etheric oxygen atom between carbon atoms is more preferable, and a carbon number of 2 having an etheric oxygen atom between carbon atoms. Particularly preferred are ˜20 perfluoroalkyl groups. When the Cf group is a C 2-20 perfluoroalkyl group having an etheric oxygen atom between carbon atoms, the initial contact angle and the contact angle difference before and after exposure are good.
The Cf group may be linear or branched.

As the Cf group, specifically, —CF ₃ , —CF ₂ CF ₃ , —CF (CF ₃ ) ₂ , —CH (CF ₃ ) ₂ , —CF ₂ CHF ₂ , — (CF ₂ ) ₂ CF ₃ ,-(CF ₂ ) ₃ CF ₃ ,-(CF ₂ ) ₄ CF ₃ ,-(CF ₂ ) ₅ CF ₃ ,-(CF ₂ ) ₆ CF ₃ ,-(CF ₂ ) ₇ CF ₃ ,-(CF ₂ ) ₈ CF ₃ , — (CF ₂ ) ₉ CF ₃ , — (CF ₂ ) ₁₁ CF ₃ , — (CF ₂ ) ₁₅ CF ₃ , —CF (CF ₃ ) O (CF ₂ ) ₅ CF ₃ , —CF ₂ OCF ₂ CF ₂ OCF ₂ CF ₃ , —CF ₂ O (CF ₂ CF ₂ O) _p CF ₃ (p is an integer of 1 to 8), —CF (CF ₃ ) O (CF ₂ CF ( CF ₃ ) O) _q C ₆ F ₁₃ (where q is an integer of 1 to 4), —CF ( CF ₃ ) O (CF ₂ CF (CF ₃ ) O) _r C ₃ F ₇ (where r is an integer of 0 to 5), — (CF ₂ O) _s (CF ₂ CF ₂ O) _t C ₃ F ₇ (where s is an integer of 1 to 8, and an integer of t 1 to 8 is). —CF ₂ CF ₂ O (CF ₂ CF ₂ CF ₂ O) _u C ₃ F ₇ (where u is 1) Is an integer of ~ 8).

R ¹ and R ² are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group, and R ^1, from the point that a decomposition residue containing a Cf group is easily detached by irradiation with light of less than 300 nm. And at least one of R ² is preferably other than a hydrogen atom, more preferably both R ¹ and R ² are other than a hydrogen atom, and particularly preferably both R ¹ and R ² are methyl groups. .

R ³ is a divalent organic group having no single bond or fluorine atom. Note that the boundary between R ³ and Cf in the formula (m1) is determined so that the carbon number of Cf is the smallest. In other words, when R ³ is not a single bond, R ³ is a divalent organic group and is an organic group determined to have the maximum carbon number under the condition that it does not have a fluorine atom.

Examples of the divalent organic group for R ³ include — (CH ₂ ) _{w 0} — (where w 0 is an integer of 1 to 6), —C ₆ H ₄ —, —C ₆ H ₄ O (CH ₂ ). _w1 − (where w1 is an integer of 0 to 10), —C ₆ H ₄ COO (CH ₂ ) _w2 — (where w2 is an integer of 0 to 10), — (CH ₂ ) _w3 COO _{(CH 2) w4} - _(where w3 is an integer of from 1 to 10, w4 is an integer of _{0~10.), - CH 2 O} (CH 2) w5 - ( however, w5 0 of an _{integer), -. CH (CH 3} ) O (CH 2) w6 -. ( However, w6 is an integer of 0) can be mentioned.

Further, from the viewpoint of easily removing the decomposition residues containing Cf group, a single _{bond, - (CH 2) w0 -} , - (CH 2) w3 COO (CH 2) w4 -, - CH 2 O (CH 2) _{w5 -, - CH (CH 3} ) O (CH 2) w6 - it is preferred. In addition, w0 is preferably an integer of 1 to 3, w1 is preferably an integer of 0 to 4, and an integer of 0 to 2 is more preferable from the viewpoint of easy production. w2 is preferably an integer of 0 to 4, and more preferably an integer of 0 to 2 from the viewpoint of easy production. w3 is preferably an integer of 1 to 6, and more preferably an integer of 1 to 3 from the viewpoint of easy production. w4 is preferably an integer of 0 to 4, and more preferably an integer of 0 to 2 from the viewpoint of easy production. w5 is preferably an integer of 0 to 4, and more preferably an integer of 0 to 2 from the viewpoint of easy production. w6 is preferably an integer of 0 to 4, and more preferably an integer of 0 to 2 from the viewpoint of easy production.

At least one of R ^{4 to} R ⁸ is a group represented by the formula (1).
The number of groups represented by formula (1) can be up to 5 in terms of structure, but 1 to 3 is preferable from the viewpoint of availability of raw materials and compound stability. More preferably, it is 1-2, and most preferably.

  Others are each independently a hydrogen atom, a halogen atom, an optionally substituted alkyl group having 1 to 12 carbon atoms, an alkenoyl group having 2 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, and 5 to 8 carbon atoms. Cycloalkyl group, aryl group having 6 to 20 carbon atoms, benzoyl group having 7 to 20 carbon atoms, alkanoyl group having 2 to 12 carbon atoms, alkoxycarbonyl group having 2 to 12 carbon atoms or phenoxycarbonyl having 7 to 20 carbon atoms Group or nitro group. Further, from the viewpoint of compatibility with other components and availability of raw materials, the other group is preferably a hydrogen atom, a methyl group, or a methoxy group.

  In the formula, X is a single bond, an oxygen atom, a sulfur atom, a nitrogen atom or NH, and oxygen is easy to produce the liquid repellent compound (A1) (the liquid repellent compound (A1) is difficult to gel). An atom, a sulfur atom, and NH are preferable, and an oxygen atom is preferable from the viewpoint of easy availability of raw materials.

  m is 1 when X is an oxygen atom, sulfur atom or NH, and is 2 when X is a nitrogen atom, which makes it easy to produce the liquid repellent compound (A1) (liquid repellent compound). 1 is preferable from the viewpoint that (A1) is difficult to gel.

  n is an integer of 0 to 4, and an integer of 0 to 2 is preferable and an integer of 0 to 1 is more preferable from the viewpoint of availability of raw materials and ease of synthesis.

Z is not particularly limited as long as it is a group having a crosslinkable functional group. Specific examples include the crosslinkable functional groups described above. Preferably, Z is R ¹⁰ R ¹¹ C═CR ⁹ —CO— (wherein R ⁹ , R ¹⁰ and R ¹¹ are each independently a hydrogen atom or a methyl group). From the viewpoint of high reactivity, it is preferable that R ⁹ is a hydrogen atom or a methyl group, and R ¹⁰ and R ¹¹ are hydrogen atoms. That is, Z is preferably a (meth) acryloyl group.

(Method for producing compound (m1))
As a manufacturing method of a compound (m1), the method of performing reaction represented by the following Formula (Rf-1) is mentioned. Formula (Rf-1) is obtained by substituting —OH of the group (a1-1) of the starting compound (a1) with the compound (b1) to obtain the compound (c1), A method for obtaining a compound (m1) by esterifying —OH of c1) with a compound (d1) is shown.

In the following formula (Rf-1), R ¹ , R ² , R ³ , X, Z, Cf, n, and m are the same as defined in formula (m1). In the formula (a1), at least one of R ^{41 to} R ⁸¹ is a group represented by the following formula (a1-1), and the others may be independently substituted with a hydrogen atom or a halogen atom, respectively. Good C1-C12 alkyl group, C2-C12 alkenoyl group, C1-C12 alkoxy group, C5-C8 cycloalkyl group, C6-C20 aryl group, C7 A benzoyl group having 20 carbon atoms, an alkanoyl group having 2 to 12 carbon atoms, an alkoxycarbonyl group having 2 to 12 carbon atoms, a phenoxycarbonyl group having 7 to 20 carbon atoms, or a nitro group.

Furthermore, in formula (c1), at least one of R ^{42 to} R ⁸² is a group represented by the following formula (c1-1). The following formula (c1-1) represents a group similar to the formula (1). In the compound (a1), R ^{41 to} R ⁸¹ that were the group (a1-1) react with the compound (b1) to form the group (c1-1). In the compound (a1), R ^{41 to} R ^{81 which} are groups other than the group (a1-1) become groups other than the group (c1-1) in the compound (c1) without reacting. That is, groups other than the group (c1-1) among R ^{42 to} R ⁸² are each independently a hydrogen atom, a halogen atom, an optionally substituted alkyl group having 1 to 12 carbon atoms, or a group having 2 to 12 carbon atoms. Alkenoyl group, C1-C12 alkoxy group, C5-C8 cycloalkyl group, C6-C20 aryl group, C7-C20 benzoyl group, C2-C12 alkanoyl group, carbon It is an alkoxycarbonyl group having 2 to 12 carbon atoms, a phenoxycarbonyl group having 7 to 20 carbon atoms, or a nitro group.

In the compound (a1), for example, R ¹ and R ² are methyl groups, R ⁴¹ , R ⁵¹ , R ⁷¹ , R ⁸¹ are hydrogen atoms, R ⁶¹ is a structure represented by the formula (a1-1), and X is an oxygen atom In the case where n is 1 and m is 1, the compound is produced by the method for producing “4- (2-hydroxyethoxy) phenyl 2-hydroxy-2-propyl ketone” described in JP-A No. 62-81345. it can. Examples of commercially available products include IRGACURE 2959 (trade name, manufactured by Ciba Specialty Chemicals).

The liquid repellent compound (A1) is a unit having a crosslinkable functional group and having no Cf group (hereinafter referred to as “unit (u1-2)”) from the viewpoints of hardness and solvent resistance of the cured film. It is preferable to further include
The liquid repellent compound (A1) may have another unit (u1-3) other than the unit (u1-1) and the unit (u1-2).
The units (u1-1), units (u1-2), and other units (u1-3) in the liquid repellent compound (A1) may be bonded in a random manner or in a block shape.

  The fluorine content of the liquid repellent compound (A1) is preferably 5 to 70% by mass, more preferably 5 to 60% by mass, and particularly preferably 8 to 60% by mass. When the fluorine content is not less than the lower limit of the above range, the liquid repellency on the surface of the cured film becomes better. Adhesiveness of a cured film and the layer adjacent to this becomes favorable as it is below the upper limit of the said range.

  The number average molecular weight (Mn) of the liquid repellent compound (A1) is preferably from 1,000 to 50,000, particularly preferably from 3,000 to 20,000. When the number average molecular weight (Mn) is not less than the lower limit of the above range, the liquid repellent compound (A1) is sufficiently transferred to the surface of the cured film, so that better liquid repellency can be expressed. When the amount is not more than the upper limit of the above range, the compatibility with the crosslinking agent (B) in the curable composition becomes good, and a cured film having no defects can be formed.

(Unit (u1-1))
The unit (u1-1) is a unit derived from the compound (m1) formed by polymerizing the compound (m1) with a Z group.

  The proportion of the unit (u1-1) in the liquid repellent compound (A1) is preferably 10 to 90% by mass, more preferably 15 to 90% by mass, further preferably 20 to 90% by mass, and 30 to 90% by mass. Particularly preferred. When the proportion of the unit (u1-1) is not less than the lower limit of the above range, the liquid repellency on the surface of the cured film becomes better. It is easy to melt | dissolve in the solvent (H) mentioned later as it is below the upper limit of the said range.

(Unit (u1-2))
The unit (u1-2) is a unit having a crosslinkable functional group and not having a Cf group.
The crosslinkable functional group of the unit (u1-2) reacts with the crosslinkable functional group of the crosslinker (B) to form a cured film having high hardness and excellent solvent resistance together with these.

The number of crosslinkable functional groups in the unit (u1-2) is preferably 1 from the viewpoint of availability of raw materials and ease of synthesis.
The crosslinkable functional group in the unit (u1-2) is preferably a (meth) acryloyl (oxy) group from the viewpoint of high reactivity with the crosslinkable functional group of the crosslinker (B).
The crosslinkable functional group of the crosslinker (B) and the crosslinkable functional group of the liquid repellent compound (A1), which coexist in the curable composition, may be the same or different.

  Since the polymerizable functional group (a group of the same type as the crosslinkable functional group) possessed by the monomer is lost by polymerization, the crosslinkable functional group of the unit (u1-2) is the polymerizable functional group possessed by the monomer. Not a group. Therefore, the crosslinkable functional group of the unit (u1-2) is usually a crosslinkable functional group introduced into the copolymer by modification or the like after the monomer is polymerized to obtain a copolymer.

  The crosslinkable functional group of the unit (u1-2) is preferably introduced by various modification methods in which a copolymer having a reactive functional group is reacted with a compound having a crosslinkable functional group. As the modification method, a known method can be appropriately used. Specifically, a copolymer having a unit (u1-4) having a reactive functional group by copolymerizing a compound (m1-4) having a polymerizable functional group and a reactive functional group with the compound (m1). After obtaining the compound, the functional group that reacts with the reactive functional group of the unit (u1-4) and the compound (a3) having a crosslinkable functional group are reacted to form a liquid repellent compound having the unit (u1-2) This is a method for obtaining (A1). The unit (u1-2) is a unit generated by the bond between the unit (u1-4) formed by polymerization of the compound (m1-4) and the compound (a3).

  Examples of the reactive functional group include a hydroxyl group, an epoxy group, and a carboxy group. When the reactive functional group is a hydroxyl group, examples of the functional group that reacts with the reactive functional group include a carboxy group, an isocyanate group, and an acyl chloride group. When the reactive functional group is an epoxy group, examples of the functional group that reacts with the reactive functional group include a carboxy group. When the reactive functional group is a carboxy group, examples of the functional group that reacts with the reactive functional group include a hydroxyl group and an epoxy group.

Specific examples of the modification method include the following methods (i) to (vi).
(I) A method of reacting a copolymer obtained by copolymerizing a monomer having a hydroxyl group with an acid anhydride having a crosslinkable functional group.
(Ii) A method of reacting a copolymer obtained by copolymerizing a monomer having a hydroxyl group with a compound having an isocyanate group and a crosslinkable functional group.
(Iii) A method of reacting a copolymer obtained by copolymerizing a monomer having a hydroxyl group with a compound having an acyl chloride group and a crosslinkable functional group.
(Iv) A method of reacting a copolymer having a hydroxyl group and a crosslinkable functional group with a copolymer obtained by copolymerizing an acid anhydride having a polymerizable functional group.
(V) A method of reacting a copolymer obtained by copolymerizing a monomer having a carboxy group with a compound having an epoxy group and a crosslinkable functional group.
(Vi) A method of reacting a compound obtained by copolymerizing a monomer having an epoxy group with a compound having a carboxy group and a crosslinkable functional group.

  When the compound (a3) is reacted with the copolymer having the unit (u1-4), it may be reacted with all of the reactive functional groups of the copolymer, and may be part of the reactive functional groups of the copolymer. You may make it react. In the latter case, the obtained liquid repellent compound (A1) has units (u1-4) derived from the compound (m1-4).

  The liquid repellent compound (A1) used for the curable composition may have a unit (u1-4). In addition, when the reactive functional group of the unit (u1-4) may adversely affect the curable composition, the reactive functional group of the unit (u1-4) reacts with the reactive functional group. The reactive functional group can also be converted into an inactive group by reacting the compound (b3) having a functional group that does not have a crosslinkable functional group.

Examples of the compound (b3) include those described in, for example, paragraph [0049] of International Publication No. 2013/0889204, and ethyl isocyanate, propyl isocyanate, acetyl chloride and propionyl chloride are preferable.
A unit obtained by converting a reactive functional group into an inactive group is referred to as a unit (u1-5).

  Examples of the compound (m1-4) include 2-hydroxyethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate and the like in the methods (i), (ii), and (iii). In the method (iv), maleic anhydride, itaconic anhydride, citraconic anhydride, phthalic anhydride and the like can be mentioned. In the method (v), (meth) acrylic acid and the like can be mentioned. In the method (vi), glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl acrylate and the like can be mentioned.

  Examples of the compound (a3) include maleic anhydride, itaconic anhydride, citraconic anhydride, phthalic anhydride and the like in the method (i). In the method (ii), 2- (meth) acryloyloxyethyl isocyanate, 1,1-bis (acryloyloxymethyl) ethyl isocyanate and the like can be mentioned. In the method (iii), (meth) acryloyl chloride, 3-butenoyl chloride and the like can be mentioned. In the method (iv), 2-hydroxyethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate and the like can be mentioned. In the method (v), glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl acrylate and the like can be mentioned. In the method (vi), (meth) acrylic acid and the like can be mentioned.

  The unit (u1-2) is a unit obtained by reacting a compound having an isocyanate group and a crosslinkable functional group with a unit derived from a monomer having a hydroxyl group, or a unit derived from a monomer having a hydroxyl group. A unit obtained by reacting a compound having an acyl group and a crosslinkable functional group is preferred. In units derived from one or more monomers selected from the group consisting of 2-hydroxyethyl (meth) acrylate and 4-hydroxybutyl (meth) acrylate, (meth) acryloyl chloride, and 2- (meth) acryloyl Units formed by reacting one or more compounds selected from the group consisting of oxyethyl isocyanate are particularly preferred. The reactivity with the crosslinking agent (B) is improved.

(Unit (u1-3))
In the liquid repellent compound (A1), other units (u1-3) other than the unit (u1-1) and the unit (u1-2) may be added as necessary as long as the effect of improving the liquid repellency is not impaired. You may have. When the liquid repellent compound (A1) has units (u1-4) or units (u1-5), these units are regarded as units (u1-3).

  The unit (u1-3) is preferably introduced into the liquid repellent compound (A1) by polymerizing the compound (m1-3) having a polymerizable functional group.

  As the compound (m1-3) giving the unit (u1-3), in addition to the compound (m1-4), hydrocarbon-based olefins, vinyl ethers, isopropenyl ethers, allyl ethers, vinyl esters, allyl esters And (meth) acrylic acid esters, (meth) acrylamides, aromatic vinyl compounds, chloroolefins, conjugated dienes, and fluorine-containing monomers other than the compound (m1). The compound (m1-3) may have a reactive functional group. Examples of the reactive functional group include a hydroxyl group, a carbonyl group, and an alkoxy group. As the compound (m1-3), one type may be used alone, or two or more types may be used in combination.

  A copolymer having a unit (u1-1), preferably further having a unit (u1-2) and having a reactive functional group (m1-3) or a unit derived from the compound (m1-4) And a compound (a4) having a functional group that reacts with the reactive functional group of the copolymer may be reacted to form a liquid repellent compound (A1) having a unit (u1-3). As the compound (a4), the same compound as the above-mentioned compound (b3) can be used.

  Specific examples of the compound (m1-3) include those described in, for example, paragraph [0056] of International Publication No. 2013/0889204. From the point of availability, acrylic acid, methacrylic acid, methyl (meth) acrylate, n-butyl (meth) acrylate, n-hexyl (meth) acrylate, n-octyl (meth) acrylate, cyclohexyl (meth) acrylate, Isobornyl (meth) acrylate, n-decyl (meth) acrylate, and 2- (2′-hydroxy-5′-methacryloxyethylphenyl) -2H-benzotriazole are preferred.

  The proportion of the unit (u1-2) in the liquid repellent compound (A1) is preferably 5 to 90% by mass, more preferably 5 to 85% by mass, further preferably 5 to 80% by mass, and 5 to 60% by mass. Particularly preferred is 5 to 50% by mass. When the proportion of the unit (u1-2) is not less than the lower limit of the above range, the reaction with the crosslinking agent (B) becomes good. When the amount is not more than the upper limit of the above range, the liquid repellency on the surface of the cured film becomes better.

  The proportion of the unit (u1-3) in the liquid repellent compound (A1) is preferably 70% by mass or less, more preferably 60% by mass or less, and particularly preferably 50% by mass or less. As a lower limit, 0 mass% is preferable. When the proportion of the unit (u1-3) is not more than the upper limit of the above range, a sufficient proportion of the unit (u1-1) and the unit (u1-2) can be secured, and the liquid repellency and curing on the surface of the cured film can be ensured. The curability of the adhesive composition is not impaired.

When the liquid repellent compound (A1) is composed of units (u1-1) and units (u1-2), the content of the unit (u1-1) is the fluorine content in the liquid repellent compound (A1). Is an amount within the above preferred range, and the balance is preferably unit (u1-2).
When the liquid repellent compound (A1) is composed of the unit (u1-1), the unit (u1-2), and the unit (u1-3), the content of the unit (u1-1) is determined according to the content of the liquid repellent compound (A1). ) Is the amount within the above preferred range, the unit (u1-2) is preferably in the above-mentioned preferred range, and the remainder is preferably the unit (u1-3).

(Method for producing liquid repellent compound (A1))
The liquid repellent compound (A1) can be produced by polymerizing monomers to obtain a copolymer, and performing the above-described modification as necessary.
The polymerization of the monomer is preferably performed in a solvent. In the polymerization of monomers, a polymerization initiator is preferably used, and a chain transfer agent is preferably used as necessary. When storing the monomer, a polymerization inhibitor is preferably used as necessary.

  Examples of the solvent include those described in, for example, paragraph [0061] of International Publication No. 2013/089204. A solvent may be used individually by 1 type and may use 2 or more types together.

  Examples of the polymerization initiator include known organic peroxides, inorganic peroxides, azo compounds and the like. Organic peroxides and inorganic peroxides can also be used as redox catalysts in combination with a reducing agent. A polymerization initiator may be used individually by 1 type, and may use 2 or more types together.

  Examples of the organic peroxide include benzoyl peroxide, lauroyl peroxide, isobutyryl peroxide, tert-butyl hydroperoxide, tert-butyl-α-cumyl peroxide and the like.

Examples of inorganic peroxides include ammonium persulfate, sodium persulfate, potassium persulfate, hydrogen peroxide, percarbonate and the like.
As the azo compound, 2,2′-azobisisobutyronitrile, 1,1-azobis (cyclohexane-1-carbonitrile), 2,2′-azobis (2,4-dimethylvaleronitrile), 2,2 Examples include '-azobis (4-methoxy-2,4-dimethylvaleronitrile), dimethyl 2,2'-azobisisobutyrate, 2,2'-azobis (2-amidinopropane) dihydrochloride, and the like.

Examples of the chain transfer agent include known mercaptans and alkyl halides. A chain transfer agent may be used individually by 1 type, and may use 2 or more types together.
Examples of mercaptans include n-butyl mercaptan, n-dodecyl mercaptan, tert-butyl mercaptan, ethyl thioglycolate, 2-ethylhexyl thioglycolate, 2-mercaptoethanol and the like.
Examples of the halogenated alkyls include chloroform, carbon tetrachloride, carbon tetrabromide and the like.

Examples of the polymerization inhibitor include known polymerization inhibitors.
Specific examples of the polymerization inhibitor include 2,6-di-tert-butyl-p-cresol.

  When modifying the copolymer, the same solvent as described above can be used. However, it is preferable not to use a solvent that may react with the compound (a3). The polymerization of the monomer is carried out in a solvent, and subsequently the compound (a3) is added and reacted to obtain the liquid repellent compound (A1).

  The modification of the copolymer may be performed in the presence of a catalyst or a neutralizing agent. For example, when a compound having an isocyanate group and a crosslinkable functional group is reacted with a copolymer having a hydroxyl group, a tin compound or the like can be used as a catalyst.

  Examples of the tin compound include dibutyltin dilaurate, dibutyltin di (maleic acid monoester), dioctyltin dilaurate, dioctyltin di (maleic acid monoester), and dibutyltin diacetate. A tin compound may be used individually by 1 type, and may use 2 or more types together.

When the copolymer having a hydroxyl group is reacted with a compound having an acyl chloride group and a crosslinkable functional group, a basic catalyst can be used.
Examples of the basic catalyst include triethylamine, pyridine, dimethylaniline, tetramethylurea and the like. A basic catalyst may be used individually by 1 type, and may use 2 or more types together.

  The liquid repellent compound (A1) of the present invention contains a unit (u1-1) based on the compound (m1). Since the compound (m1) has a Cf group, the liquid repellent compound (A1) has good liquid repellency. Therefore, the surface of the cured film obtained by curing the curable composition containing the liquid repellent compound (A1) repels water and oil, and even if water, oil, etc. once adhere, Can be easily removed from. The deposit is not limited to a liquid, but may be a solid having an adhesive surface.

Further, since the compound (m1) is a compound in which R ³ in the “copolymerizable photoinitiator” described in JP-A No. 62-81345 is replaced with a Cf group, the “copolymerization” Similarly to the “photoinitiator”, even in the absence of a photocatalyst or the like, decomposition occurs in the molecule by irradiation with light having a wavelength of less than 300 nm, and a decomposition residue containing a Cf group can be eliminated. That is, in the liquid repellent compound (A1), the Cf group present in the side chain is easily detached by irradiation with ultraviolet rays containing light having a wavelength of less than 300 nm. Therefore, by partially irradiating the surface of the cured film obtained by curing the curable composition containing the liquid repellent compound (A1) with ultraviolet rays, the liquid repellency of the portion irradiated with the ultraviolet rays on the surface of the cured film is obtained. And can be made lyophilic relative to the portion not irradiated with ultraviolet rays.

  As described later, by irradiating the surface of the cured film obtained by curing the curable composition containing the liquid repellent compound (A1) with ultraviolet light containing light having a wavelength of less than 300 nm, the portion irradiated with ultraviolet light is treated as a parent. It can be set as the surface which has liquefied and the liquid-repellent area | region and lyophilic area | region which were not irradiated with the ultraviolet-ray.

<Liquid repellent compound (A2)>
The liquid repellent compound (A2) is a compound that can absorb light of 300 nm or more. The liquid repellent compound (A2) may or may not have an ability to absorb light of less than 300 nm.

Specific examples of the liquid repellent compound (A2) include a polymer having a unit based on the compound (m2) (hereinafter also referred to as “unit (u2-1)”). Note that the boundary between R ³ and Cf in the formula (m2) is determined so that the carbon number of Cf is the smallest, as in the case of the formula (m1).

  Compound (m2) has a cis-trans isomer due to an oxime double bond. The compound (m2) is not limited to those shown in the above formula, and may be only a cis isomer, only a trans isomer, or a mixture of both.

In formula (m2), R ³ and Cf are the same as defined in formula (m1).
As it is the terms that easily absorbs more UV wavelength 300 nm ^{R 3} in the compound _{(m2), -C 6 H 4} -, - C 6 H 4 O (CH 2) w1 -, - C 6 H 4 COO (CH ₂ ) _w2 — (wherein w1 and w2 are as described above) is preferable.

R ¹² is a hydrogen atom, an alkyl group having 1 to 12 carbon atoms or a phenyl group, and an alkyl group having 1 to 12 carbon atoms is preferable from the viewpoint of good solubility of the compound (m2).

At least one of R ^{13 to} R ¹⁷ is a monovalent organic group having a group represented by the above formula (1) at the terminal.
Although the number of monovalent organic groups having a group represented by the formula (1) can be up to 5 at the end of the structure, it is preferably 1 to 3 from the viewpoint of availability of raw materials and compound stability. More preferably, it is 1-2, and most preferably.

R ^{13 to} R ¹⁷ are specifically a group in which the terminal group (1) and the linking group (—L—) are bonded, that is, a group represented by the —L— group (1). The linking _{group, -L1- (C 6 H 4 O} ) k - (CH 2 CH 2 O) l - (L1 is .k showing sulfur atom, an oxygen atom, a CH ₂ or NH is an integer of 0 to 5 , L represents an integer of 0 to 5).

Others are each independently a hydrogen atom, a halogen atom, an optionally substituted alkyl group having 1 to 12 carbon atoms, an alkenoyl group having 2 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, and 5 to 8 carbon atoms. Cycloalkyl group, aryl group having 6 to 20 carbon atoms, benzoyl group having 7 to 20 carbon atoms, alkanoyl group having 2 to 12 carbon atoms, alkoxycarbonyl group having 2 to 12 carbon atoms, alkoxy having 3 to 20 carbon atoms carbonyl alkanoyl group, phenoxycarbonyl group having 7 to 20 carbon atoms, phenoxycarbonyl alkanoylamino group having a carbon number of 8-20, heteroaryloxycarbonyl alkanoyl group having 8 to 20 carbon ^atoms, -SR ^{101, -SOR} 101, -SO ₂ R ^101, or ^-NR 101 ^{R 102 (wherein, R 101} and ^{R 102} each A hydrogen atom, or an optionally substituted alkyl group having 1 to 12 carbon atoms, an alkenyl group having 3 to 12 carbon atoms, an alkanoyl group having 2 to 8 carbon atoms, and 6 to 20 carbon atoms An aryl group, or a trialkylsilyl group having 3 to 15 carbon atoms), or a nitro group.

In addition, R < ¹³ > -R < ¹⁷ > may combine several substituents and may have a substituent further and may form the saturated or unsaturated aromatic ring.
j is 0 or 1.

  From the point of shifting the ultraviolet absorption wavelength to the longer wavelength side, other groups include a phenyl group and a nitro group, or a plurality of substituents are bonded to each other and further have a substituent. Or a saturated or unsaturated aromatic ring is preferably formed. Moreover, a hydrogen atom, a methyl group, and a methoxy group are preferable from the viewpoint of compatibility with other components and availability of raw materials.

(Method for producing compound (m2))
As a manufacturing method of a compound (m2), the method of performing reaction represented by the following Formula (Rf-2) is mentioned. In formula (Rf-2), compound (c2) is obtained by subjecting —OH of group (a2-1) of compound (a2) which is a starting material to substitution reaction using compound (b2). Next, compound (c2) is oximed using nitrite (d2) to obtain compound (e2). Subsequently, -OH of compound (e2) is esterified using compound (f2) in the presence of carbodiimide to obtain a compound (m2).

In the following formula (Rf-2), R ³ , R ¹² , X, Z, Cf, n, and m are the same as defined in formula (m2). The linking group (-L-) is the same as above. In formula (a2), at least one of R ^{131 to} R ¹⁷¹ is a group represented by the following formula (a2-1), and the others may be independently substituted with a hydrogen atom or a halogen atom, respectively. Good C1-C12 alkyl group, C2-C12 alkenoyl group, C1-C12 alkoxy group, C5-C8 cycloalkyl group, C6-C20 aryl group, C7 -20 benzoyl group, C2-C12 alkanoyl group, C2-C12 alkoxycarbonyl group, C3-C20 alkoxycarbonylalkanoyl group, C7-C20 phenoxycarbonyl group, carbon number 8-20 phenoxycarbonyl alkanoyl group, heteroaryloxycarbonyl alkanoyl group having 8 to 20 carbon ^atoms, -SR 101, ^{-SOR 101,} - SO ₂ R ¹⁰¹ , or —NR ¹⁰¹ R ¹⁰² (wherein R ¹⁰¹ and R ¹⁰² are each independently a hydrogen atom or an optionally substituted alkyl group having 1 to 12 carbon atoms, or 3 to 12 carbon atoms) An alkenyl group, an alkanoyl group having 2 to 8 carbon atoms, an aryl group having 6 to 20 carbon atoms, or a trialkylsilyl group having 3 to 15 carbon atoms), or a nitro group.

Further, in the formulas (c2) and (e2), at least one of R ^{132 to} R ¹⁷² is a group represented by the following formula (c2-1). The following formula (c2-1) is a monovalent organic group in which the linking group (-L-) is bonded to the group (1). In the compound (a2), R ^{131 to} R ¹⁷¹ that were the group (a2-1) react with the compound (b2) to form the group (c2-1). In the compound (a2), R ^{131 to} R ^{171 which} are groups other than the group (a2-1) do not react with each other as they are in the compound (c2) and the group other than the group (c2-1) in the compound (e2). Become.

That is, groups other than the group (c2-1) among R ^{132 to} R ¹⁷² are each independently a hydrogen atom, a halogen atom, an optionally substituted alkyl group having 1 to 12 carbon atoms, or 2 to 12 carbon atoms. Alkenoyl group, an alkoxy group having 1 to 12 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, an aryl group having 6 to 20 carbon atoms, a benzoyl group having 7 to 20 carbon atoms, an alkanoyl group having 2 to 12 carbon atoms, C2-C12 alkoxycarbonyl group, C3-C20 alkoxycarbonylalkanoyl group, C7-C20 phenoxycarbonyl group, C8-C20 phenoxycarbonylalkanoyl group, C8-C20 A heteroaryloxycarbonylalkanoyl group, -SR ¹⁰¹ , -SOR ¹⁰¹ , -SO ₂ R ¹⁰¹ , or -NR ¹⁰¹ R ¹⁰² (wherein R ¹⁰¹ and R ¹⁰² are each independently a hydrogen atom, or an optionally substituted alkyl group having 1 to 12 carbon atoms, an alkenyl group having 3 to 12 carbon atoms, or 2 to 8 carbon atoms) An alkanoyl group, an aryl group having 6 to 20 carbon atoms, or a trialkylsilyl group having 3 to 15 carbon atoms), or a nitro group.

Compound (a2) can be produced by a known production method. For example, R ¹³¹ , R ¹⁴¹ , R ¹⁶¹ , R ¹⁷¹ are hydrogen atoms, R ¹⁵¹ is a structure represented by the formula (a2-1), L is —S—C ₆ H ₄ O—, X is a single bond, When n is 0 and m is 1, it can be produced by reacting HO—C ₆ H ₄ —SH with Br—C ₆ H ₄ —CO—CH ₂ —R ¹² .

  The liquid repellent compound (A2) is a polymer produced by using the compound (m2) instead of the compound (m1) in the liquid repellent compound (A1), and can be produced by a common method. The preferred molecular weight, fluorine content range, etc. are the same as in (A1).

In addition, the compound (m2) was prepared by replacing R ¹ of the formula (I) in the “novel O-oxime photoinitiator” described in JP-A-2000-080068 with an R ³ -Cf group and replacing R ⁵ with a group (c2 -1) [Z— (OCH ₂ CH ₂ ) _n ] _m XL-group is a compound, so that the photocatalyst and the like are similar to the “new O-oxime photoinitiator” described in the publication. Even if it does not exist, light with a wavelength of less than 300 nm is possible, but it can be decomposed with ultraviolet light including light with a wavelength of 300 nm or more. In particular, decomposition occurs in the molecule by irradiation with ultraviolet rays having a wavelength of 350 to 370 nm, and a decomposition residue containing a Cf group can be eliminated.

  That is, in the liquid repellent compound (A2), the Cf group present in the side chain is easily detached by irradiation with ultraviolet rays containing light having a wavelength of 300 nm or more. Therefore, by partially irradiating the surface of the cured film obtained by curing the curable composition containing the liquid repellent compound (A2) with ultraviolet rays, the liquid repellency of the portion irradiated with ultraviolet rays on the surface of the cured film is obtained. And can be made lyophilic relative to the portion not irradiated with ultraviolet rays. As will be described later, the surface of the cured film obtained by curing the curable composition containing the liquid repellent compound (A2) is irradiated with ultraviolet rays containing light having a wavelength of 300 nm or more through a photomask having a pattern. Thus, a portion irradiated with ultraviolet rays can be made lyophilic, and a surface having a pattern of lyophobic regions and lyophilic regions not irradiated with ultraviolet rays can be obtained.

  The liquid repellent compound (A) may consist of one or more of the liquid repellent compounds (A1), may consist of one or more of the liquid repellent compounds (A2), and It may consist of a combination of the liquid repellent compound (A1) and the liquid repellent compound (A2).

  The content of the liquid repellent compound (A) in the composition of the present invention is preferably 0.01 to 20% by mass, more preferably 0.05 to 10% by mass, and even more preferably 0.1 to 5% by mass. preferable. When the content is not less than the lower limit of the above range, the surface of the cured film is excellent in liquid repellency. The film physical property of a cured film becomes it favorable that it is below the upper limit of the said range. In addition, content in the composition of this liquid repellent compound (A) is with respect to the total weight except the solvent (H) which is an arbitrary component, and composition of each component other than the solvent (H) demonstrated below. Unless otherwise specified, the content in the product is based on the total weight excluding the solvent (H).

(Crosslinking agent (B))
The crosslinking agent (B) in the present invention is a compound having a crosslinkable functional group (however, excluding the component (A)). By including the crosslinking agent (B) in the curable composition, the hardness is high. A cured film can be formed.

  The number average molecular weight (Mn) of the crosslinking agent (B) is preferably 50 to 5,000, more preferably 200 to 3,000, and particularly preferably 250 to 2,500. When the number average molecular weight (Mn) is not less than the lower limit of the above range, the crosslinking agent (B) is not easily volatilized by heating. When the amount is not more than the upper limit of the above range, the viscosity of the crosslinking agent (B) is kept low, and a uniform curable composition is easily obtained when mixed with other components.

The number of crosslinkable functional groups of the crosslinking agent (B) is preferably 1 or more, more preferably 1 to 20, and particularly preferably 1 to 8 from the viewpoint that the molecules can be crosslinked.
As for the crosslinkable functional group of the crosslinker (B), at least the crosslinkable functional groups react to cause crosslinking or chain extension. Moreover, it reacts with the crosslinkable functional group of the liquid repellent compound (A) and forms a cured film together with these.

The crosslinkable functional group of the crosslinking agent (B) is not particularly limited. Specifically, the aforementioned crosslinkable functional group can be used. A (meth) acryloyl (oxy) group is preferable from the viewpoint of high reactivity and availability, and an acryloyl (oxy) group is more preferable from the viewpoint of higher reactivity. The crosslinkable functional group may have two or more kinds in one molecule.
In addition, the crosslinkable functional group in a crosslinking agent (B) and a liquid repellent compound (A) may be the same, and may differ.

  As a specific example of the crosslinking agent (B), as a radical polymerizable monomer in which the number of crosslinkable functional groups in one molecule, that is, the number of radical polymerizable double bonds is 1, JP-A-2008-106165 Those described in paragraph [0114] and the like can be mentioned.

  Moreover, as a radically polymerizable monomer having two or more crosslinkable functional groups in one molecule, that is, the number of radically polymerizable double bonds, for example, paragraphs [0102] to [0102] of [International Publication No. 2013/089204]. [0104] and the like.

  The crosslinking agent (B) used in the present invention includes ethoxylated isocyanuric acid triacrylate, 1,6-hexanediol diacrylate, 1,10-decanediol diacrylate, 1 from the viewpoint of availability and reactivity. , 9-nonanediol diacrylate, 1,9-nonanediol dimethacrylate, trimethylolpropane triacrylate, dipentaerythritol hexaacrylate, pentaerythritol tetraacrylate, ditrimethylolpropane tetraacrylate, tricyclodecane dimethanol diacrylate, ε- Caprolactone-modified tris- (2-acryloxyethyl) isocyanurate and fluorene type epoxy acrylate / acid anhydride polymerization adduct are preferred.

  Moreover, the prepolymer containing a fluorine atom etc. can also be used as a crosslinking agent (B). Specifically, a prepolymer described in WO2013 / 115195 can be used.

  When the crosslinking agent (B) is contained in the curable composition of the present invention, the content thereof is preferably 10 to 99 mass%, more preferably 15 to 99 mass%, and more preferably 20 to 99 mass% with respect to the entire composition. % Is particularly preferred. When the content is at least the lower limit of the above range, curing at a low temperature is facilitated, so that the solvent resistance of the cured film is sufficiently improved. It can be applied to a low temperature process using a substrate having low heat resistance. The storage stability of a composition improves that it is below the upper limit of the said range.

(Polymerization initiator (C))
The composition of the present invention may be thermosetting, photocurable, thermosetting and photocurable. In the case of thermosetting, the thermal polymerization initiator (C1) is used, and in the case of photocurable, the photopolymerization initiator (C2) is used.
The thermal polymerization initiator (C1) in the present invention is not particularly limited as long as it is a compound that generates radicals by heat. From the viewpoint of handling, a compound having a 10-hour half-life temperature of 20 to 100 ° C. is preferable, and a compound having a 40 to 80 ° C. is more preferable.

  The photopolymerization initiator (C2) in the present invention is not particularly limited as long as it is a compound having a function as a photopolymerization initiator. A compound that generates a radical by light is preferable. The photopolymerization initiator (C2) is more preferably a compound that generates radicals with ultraviolet rays of 200 to 500 nm, and more preferably a compound that generates radicals with ultraviolet rays of 300 to 400 nm.

  As the thermal polymerization initiator (C1), known organic peroxides, inorganic peroxides, azo compounds and the like can be used. Organic peroxides and inorganic peroxides can also be used as redox catalysts in combination with a reducing agent.

  Specifically, for example, 2,2′-azobisisobutyronitrile, 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile), benzoyl peroxide, tert-butyl hydroperoxide, cumene hydro Peroxide, di-tert-butyl peroxide, dicumyl peroxide and the like can be mentioned. From the viewpoint of decomposition temperature, 2,2'-azobisisobutyronitrile and benzoyl peroxide are preferable. As the thermal polymerization initiator (C1), one type may be used alone, or two or more types may be used in combination.

  When using a thermal-polymerization initiator (C1), 0.1-20 mass% is preferable, and, as for the content, 0.5-15 mass% is more preferable. When the content is at least the lower limit of the above range, curing at a low temperature is facilitated, so that the solvent resistance of the cured film is sufficiently improved. The storage stability of a curable composition becomes it favorable that it is below the upper limit of the said range.

  Examples of the photopolymerization initiator (C2) include those described in paragraph [0054] of Patent Document 2, specifically acetophenones, acylphosphine oxides, oxime esters, triethanolamine, methyl, and the like. Examples include aliphatic amines such as diethanolamine, triisopropanolamine, n-butylamine, N-methyldiethanolamine, and diethylaminoethyl methacrylate. When oxime esters are used, the curability with ultraviolet rays of 300 nm or more becomes good, which is more preferable.

  When using a photoinitiator (C2), 0.1-20 mass% is preferable, and, as for the content, 0.5-15 mass% is more preferable. When the content is at least the lower limit of the above range, curing at a low temperature is facilitated, so that the solvent resistance of the cured film is sufficiently improved. The storage stability of a curable composition becomes it favorable that it is below the upper limit of the said range.

(Photoinitiator or sensitizer)
The composition of the present invention may further contain a photoinitiator assistant or a sensitizer together with the photopolymerization initiator (C2). Examples of the photoinitiation assistant or sensitizer include benzoin compounds, acetophenone compounds, anthraquinone compounds, thioxanthone compounds, ketal compounds, benzophenone compounds, tertiary amine compounds, and xanthone compounds. These compounds may be used as a photopolymerization initiator (C2), but are preferably used in combination with a photopolymerization initiator (C2). One photoinitiator or sensitizer may be used alone, or two or more may be used in combination.

Examples of the benzoin compound include benzoin, benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl ether.
Examples of the acetophenone compound include acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, and the like.

Examples of the anthraquinone compound include 2-methylanthraquinone, 2-ethylanthraquinone, 2-t-butylanthraquinone, 1-chloroanthraquinone and the like.
Examples of the thioxanthone compound include 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-diisopropylthioxanthone, and the like.

Examples of the ketal compound include acetophenone dimethyl ketal and benzyl dimethyl ketal.
Examples of the benzophenone compound include benzophenone, 4-benzoyl diphenyl sulfide, 4-benzoyl-4′-methyl diphenyl sulfide, 4-benzoyl-4′-ethyl diphenyl sulfide, 4-benzoyl-4′-propyl diphenyl sulfide, and the like. .

  As the tertiary amine compound, for example, an ethanolamine compound, a compound having a dialkylaminobenzene structure, for example, a dialkylaminobenzophenone such as 4,4′-dimethylaminobenzophenone and 4,4′-diethylaminobenzophenone, 7- (diethylamino) -4 Dialkylamino group-containing coumarin compounds such as -methyl-2H-1-benzopyran-2-one (7- (diethylamino) -4-methylcoumarin), ethyl 4-dimethylaminobenzoate, ethyl 2-dimethylaminobenzoate, 4 Examples include -dimethylaminobenzoic acid (n-butoxy) ethyl, p-dimethylaminobenzoic acid isoamyl ethyl ester, 4-dimethylaminobenzoic acid 2-ethylhexyl, and the like.

  When using a photoinitiator auxiliary or a sensitizer, the content is preferably 0.5 to 10% by mass, and more preferably 1 to 7% by mass. When the content is not less than the lower limit of the above range, the curability is sufficiently improved. Curability becomes favorable as it is below the upper limit of the said range.

(Ultraviolet absorber (D))
The curable composition of this invention can contain a ultraviolet absorber (D) as needed. The ultraviolet absorber is not particularly limited as long as it is a compound that absorbs ultraviolet rays of 200 to 500 nm. For example, UV absorbers such as benzophenone skeleton, benzotriazole skeleton, cyanoacrylate skeleton or triazine skeleton, chromatic pigments such as red pigment, blue pigment, green pigment, yellow pigment, carbon black, aniline black, anthraquinone black pigment, perylene Black pigments such as black pigments and azomethine pigments.

  From the viewpoint of improving the contrast of the organic EL display, a black pigment is preferable, and from the viewpoint of electrical characteristics, an organic pigment is more preferable. Specific examples of preferred organic pigments include 2- (2′-hydroxy-5 ′-(meth) acryloyloxyethylphenyl) -2H-benzotriazole, 2-hydroxy-4-n-octoxybenzophenone, methyl-2- Cyanoacrylate, 2,4-bis [2-hydroxy-4-butoxyphenyl] -6- (2,4-dibutoxyphenyl) -1,3,5-triazine, C.I. I. Pigment black 1, 6, 7, 12, 20, 31, C.I. I. Pigment Blue 15: 6, Pigment Red 254, Pigment Green 36, Pigment Yellow 150, and the like.

  When using an ultraviolet absorber (D), the content is preferably 5 to 70% by mass, and more preferably 10 to 60% by mass. When the content is not less than the lower limit of the above range, the concealing property is sufficiently improved. If it is not more than the upper limit of the above range, the developability will be good.

(Binder resin (E))
The curable composition of the present invention can contain a binder resin (E) as necessary. The binder resin (E) is a compound having no crosslinkable functional group. By containing the binder resin (E), the rigidity of the cured film is improved, and the outgas can be suppressed and the solvent resistance can be improved.

  As the binder resin, a resin having a phenolic hydroxyl group or a carboxy group, an amino resin, an oxazoline compound, an epoxy resin, an oxetane compound, a fluororesin, or the like can be used. These may be used alone or in combination of two or more.

When a resin having a phenolic hydroxyl group or a carboxy group is used in combination with an amino resin, an oxazoline compound, an epoxy resin, or an oxetane compound, the curability of the film may be improved and the solvent resistance of the film may be excellent. A combination of a resin having a carboxy group and an amino resin or an epoxy resin is particularly preferable.
Moreover, by using a fluororesin, chemical resistance and light resistance can be improved in some cases.

  As the amino resin, a compound obtained by hydroxymethylating a part or all of amino groups such as a melamine compound, a guanamine compound, a urea compound, or the like, a part or all of the hydroxyl groups of the hydroxymethylated compound are converted to methanol, ethanol, n- Examples include melamine compounds etherified with butyl alcohol, 2-methyl-1-propanol, guanamine compounds, urea compounds, or resins thereof.

  As the oxazoline compound, 2-vinyl-2-oxazoline, 2-vinyl-4-methyl-2-oxazoline, 2-vinyl-5-methyl-2-oxazoline, 2-isopropenyl-2-oxazoline, 2-isopropenyl And a copolymer of polymerizable monomers such as -4-methyl-2-oxazoline.

  Epoxy resins include bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, dicyclopentadiene type epoxy resin, naphthalene type epoxy resin, trisphenolmethane type epoxy resin, brominated Glycidyl ethers such as epoxy resins, alicyclic epoxy resins such as 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, bis (2,3-epoxycyclopentyl) ether, diglycidyl hexahydrophthalate, di Glycidyl esters such as glycidyltetrahydrophthalate and diglycidylphthalate, glycidyl such as tetraglycidyldiaminodiphenylmethane and triglycidylparaaminophenol Amines, heterocyclic epoxy resins such as triglycidyl isocyanurate.

  As the oxetane compound, any compound having an oxetane ring can be arbitrarily used. Specifically, for example, oxetane compounds as described in JP-A Nos. 2001-220526 and 2001-310937 can be used. As the oxetane compound, those having no polymerizable functional group are preferable, and specific examples thereof include OXT221, OXT121, RSOX, HQOX, and BPOX (trade names) manufactured by Toagosei Co., Ltd.

  Examples of the fluororesin include a copolymer of a fluorine-containing monomer and other monomers. Examples of the fluorine-containing monomer include chlorotrifluoroethylene (CTFE), tetrafluoroethylene (TFE), hexafluoropropylene (HFP), vinylidene fluoride (VdF), vinyl fluoride (VF), and perfluoroalkyl vinyl ether. And fluorine-containing unsaturated compounds such as (PAVE). Examples of other monomers include unsaturated compounds having a hydroxyl group, carboxyl group, amino group, epoxy group, silyl group, carbonyl group, or isocyanate group.

(Acid generator (F))
The curable composition of the present invention may further contain an acid generator (F) as necessary. The acid generator (F) is not particularly limited as long as it is a compound that decomposes to generate an acid upon irradiation with an actinic ray. Specific examples include onium salt acid generators and nonionic acid generators.

  Examples of the nonionic acid generator include a naphthalimide skeleton, a nitrobenzene skeleton, a diazomethane skeleton, a phenylacetophenone skeleton, a thiochitosan skeleton, a triazine skeleton, and a structure in which a chlorine atom, an alkanesulfonic acid, an arylsulfonic acid, or the like is bonded. And the like.

  Specifically, N-trifluoromethanesulfonic acid-1,8-naphthalimide, 2-phenyl-2- (p-toluenesulfonyloxy) acetophenone, 2- (4-methoxyphenyl) ethenyl-4,6-bis (Trichloromethyl) -1,3,5-triazine, 2- [2- (n-propylsulfonyloxyimino) thiophene-3 (2H) -ylidene] -2- (2-methylphenyl) acetonitrile and the like are preferable.

  When using an acid generator (F), the content is preferably 0.05 to 10% by mass, and more preferably 0.1 to 5% by mass. When the content is not less than the lower limit of the above range, the curability is sufficiently improved. Curability becomes favorable as it is below the upper limit of the said range.

(Thiol compound (G))
The curable composition of the present invention can further contain a thiol compound (G) as necessary. The thiol compound (G) that can be optionally contained in the curable composition is a compound having two or more mercapto groups in one molecule. If the composition of this invention contains a thiol compound (G), the radical of a thiol compound (G) will produce | generate by the radical produced | generated from the polymerization initiator (C) at the time of hardening, and the ethylenic double of a crosslinking agent (B) A so-called ene-thiol reaction occurs that affects the binding. This ene-thiol reaction is different from normal radical polymerization of ethylenic double bonds, and is not subject to reaction inhibition by oxygen. Therefore, it has high chain mobility and also undergoes crosslinking simultaneously with polymerization. The shrinkage rate is low, and there is an advantage that a uniform network can be easily obtained.

  When the curable composition of the present invention contains the thiol compound (G), it can be sufficiently cured even at a low exposure amount as described above, and particularly in the upper layer portion including the upper surface of the partition wall that is susceptible to reaction inhibition by oxygen. In addition, since photocuring is sufficiently performed, it is possible to impart good ink repellency to the upper surface of the partition wall.

  It is preferable that 2-10 mercapto groups in a thiol compound (G) are contained in 1 molecule, 3-8 are more preferable, and 3-5 are especially preferable.

  The molecular weight of the thiol compound (G) is not particularly limited. The mercapto group equivalent (hereinafter also referred to as “SH equivalent”) represented by [molecular weight / number of mercapto groups] in the thiol compound (G) is preferably 40 to 1,000 from the viewpoint of curability at low exposure. 40-500 are more preferable, and 40-250 are particularly preferable.

Specific examples of the thiol compound (G) include tris (2-mercaptopropanoyloxyethyl) isocyanurate, pentaerythritol tetrakis (3-mercaptobutyrate), pentaerythritol tetrakis (3-mercaptobutyrate), and dipenta. Erythritol hexa (3-mercaptobutyrate), 1,3,5-tris (3-mercaptobutyryloxyethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, Examples include 1,4-bis (3-mercaptobutyryloxy) butane.
A thiol compound (G) may be used individually by 1 type, or may use 2 or more types together.

  When the curable composition of the present invention contains a thiol compound (G), the content thereof is 0.0001 mercapto group per 1 mol of ethylenic double bonds of the total solid content in the curable composition. The amount of ˜1 mol is preferable, the amount of 0.0005 to 0.5 mol is more preferable, and the amount of 0.001 to 0.5 mol is particularly preferable. When the content is in the above range, the photocurability and developability of the curable composition are good even at a low exposure amount.

(Solvent (H))
The composition of the present invention can contain a solvent (H) in order to improve the dischargeability of the composition. However, the solvent (H) is a compound that does not contain a crosslinkable functional group. In addition, a solvent (H) is removed in the process of forming a partition using the composition of this invention. Usually, the solvent (H) is removed by evaporating the solvent (H).
The solvent (H) is preferably a solvent having a boiling point of 100 ° C. or more from the viewpoint of inkjet ejection stability.

  As the solvent (H), known solvents such as ketones, esters, ethers, amides, and aromatics can be used. Specific examples thereof include those described in paragraph [0112] of JP-A-2008-106165. Among these solvents, N-methyl-2-pyrrolidone, dimethylimidazolidinone, γ-butyrolactone, ethylene glycol monobutyl ether, diethylene glycol monoethyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, propylene glycol monomethyl ether acetate ( PGMEA), diethylene glycol methyl ethyl ether, diethylene glycol ethyl methyl ether, methyl 3-methoxypropionate and the like are preferable.

A solvent (H) may be used individually by 1 type, or may mix and use 2 or more types.
0-99.995 mass% is preferable, as for content of the solvent (H) in the composition of this invention, 0-70 mass% is more preferable, and 0-60 mass% is still more preferable.

(Other additives)
The composition of the present invention may further include, if necessary, adhesion improvers (such as silane coupling agents), stabilizers (such as UV absorbers, antioxidants, thermal polymerization inhibitors), surfactants. Various additives well known in the coating field such as plasticizers (leveling agents, antifoaming agents, precipitation inhibitors, dispersants, dispersion aids, etc.), plasticizers, thickeners, antistatic agents, aminosilicon compounds, phosphate compounds, etc. An additive selected from the above can be blended within a range not impairing the effects of the present invention.
The compounding quantity of another additive is 0.0001-30 mass% normally, Preferably it is 0.0001-20 mass%.

-Surfactant For example, a surfactant can be added for the purpose of improving coatability. Specific examples thereof include silicon such as Byk-300, Byk-306, Byk-335, Byk-310, Byk-341, Byk-344, Byk-370 (above, trade name, manufactured by BYK Chemie). Acrylic surfactants such as Byk-354, ByK-354, ByK-358, Byk-361 (above, trade name, manufactured by Big Chemie Co., Ltd.), DFX-18, Aftergent 250, Aftergent 251 ( As mentioned above, fluorine-type surfactants, such as a product made from Neos Co., Ltd., etc. are mentioned. Only one surfactant may be used, or two or more surfactants may be mixed and used. The surfactant is preferably used by adding 0.0001 to 1% by mass in the composition.

-Coupling agent Moreover, a silane coupling agent can be added in order to improve adhesiveness. Examples of the silane coupling agent include trialkoxysilane compounds and dialkoxysilane compounds. Specific examples thereof include those described in paragraph [0126] of JP-A-2008-106165. Among these, γ-vinylpropyltrimethoxysilane, γ-acryloylpropyltrimethoxysilane, γ-methacryloylpropyltrimethoxysilane, and γ-isocyanatopropyltriethoxysilane are more preferable.

(Preferable combination of curable compositions)
Examples of preferable combinations of the components in the composition of the present invention include the following combinations 1 and 2.

Combination 1:
Liquid repellent compound (A1): The content of the liquid repellent compound (A1) in the composition is 0.1 to 5% by mass.
Crosslinking agent (B): The content of the crosslinking agent (B) in the composition is 20 to 99% by mass.
Photopolymerization initiator (C2): The content of the photopolymerization initiator (C2) in the composition is 0.5 to 15% by mass.

Combination 2:
Liquid repellent compound (A2): The content of the liquid repellent compound (A2) in the composition is 0.1 to 5% by mass.
Crosslinking agent (B): The content of the crosslinking agent (B) in the composition is 20 to 99 parts by mass.
Thermal polymerization initiator (C1): The content of the thermal polymerization initiator (C1) in the composition is 0.5 to 15 parts by mass.

  The composition of the present invention can be obtained by mixing a predetermined amount of each of the above components by a known method. The composition of the present invention is used for forming partition walls of optical elements such as organic EL elements, quantum dot displays, TFT arrays, and thin film solar cells. If the composition of the present invention is used, a simple and economical method such as a micro-ejection method such as an ink jet method is used, and the ink-repellent property has a good ink repellency on the top surface and a good side surface. Therefore, the partition wall which can apply | coat an ink uniformly can be manufactured.

[Partition wall]
The partition wall of the present invention is a partition wall that is used in an optical element, for example, an organic EL element, a quantum dot display, a TFT array, a thin film solar cell, etc., and is formed in a shape that partitions the substrate surface into a plurality of sections for dot formation. .
The partition of the first aspect of the present invention is a partition obtained by forming the entire partition using the curable composition of the present invention.
The partition wall according to the second aspect of the present invention is a partition wall repair portion in which defects generated in the partition wall formed to partition the substrate surface into a plurality of dot forming sections are repaired using the curable composition of the present invention. It is a partition which has. In the partition wall according to the second aspect, the partition wall other than the partition repair portion may be the partition wall according to the first aspect, or may be another partition wall.
Hereinafter, the partition wall of the present invention refers to both the partition wall of the first aspect and the partition wall of the second aspect of the present invention.

  Hereafter, an example of the manufacturing method of the partition of the 1st aspect of this invention is demonstrated. This method includes the following steps (1) to (3).

Process (1)
First, a coating film is formed on one main surface of the substrate by applying the composition of the present invention in a predetermined pattern by a micro discharge method, that is, in the form of partitioning the surface of the substrate 1 into a plurality of sections for forming dots. To do. The micro discharge method is not particularly limited, and a known method such as an ink jet method, a nozzle printing method, or a dispenser method can be used.
The ink jet method is a method in which a material is ejected from an ink jet nozzle and applied to a predetermined pattern, and there are a method in which mechanical energy is applied to the material and a method in which thermal energy is applied to the material and a method in which the material is discharged. Any method may be used.

The nozzle printing method is a method in which a head provided with several tens of fine nozzles is multiplexed and a small amount of material is ejected with a single stroke. The dispenser method is a method that uses a liquid dispensing device, and the material dispensing system includes a flow rate control system, a pressure ON / OFF type, a flow rate ON / OFF type, a volumetric metering system, a measuring chamber fixed type, and a measuring chamber. There are variations.
In addition, the preferable viscosity range of the composition of this invention at the time of using each of these methods is as follows.

Inkjet method: 0.5 to 50 mPa · S, more preferably 1 to 20 mPa · S.
Nozzle printing method: 1 to 100,000 mPa · S, more preferably 3 to 10,000 mPa · S.
Dispenser method: 1 to 100,000 mPa · S, more preferably 3 to 10,000 mPa · S.

Process (2)
Next, the coating film is cured to form a cured film.
<When curing is performed by light irradiation (photocuring)>
In the case where the composition contains a solvent (H) or the like, the coating film may be dried as necessary to form a dry film. Examples of the drying method include heat drying, reduced pressure drying, and reduced pressure heat drying. This heating step for the purpose of mainly drying the solvent is hereinafter referred to as pre-baking.

Next, light is irradiated.
The light to be irradiated is not particularly limited as long as the photopolymerization initiator (C2) contained in the composition of the present invention has a wavelength with sensitivity. Usually, the light used for curing is ultraviolet light (wavelength 200 to 400 nm, preferably 300 to 400 nm), but is not limited thereto. In addition, it is preferable not to use light having a wavelength that causes decomposition in the side chain of the unit (u1-1) in the liquid repellent compound (A1) or the unit (u2-1) in the liquid repellent compound (A2).

In the photocurable preferably be cured by irradiation of 1~10000mJ / cm ^2, for convenience of processing time, it is more preferably cured at 1~1000mJ / cm ^2. When the sensitivity is less than the above exposure amount, a problem occurs in the stability of the composition.
Immediately after exposure, if necessary, it may be heated (hereinafter referred to as PEB process). By the PEB step, for example, when the acid generator (F) or the like is contained in the composition, the acid generated by light irradiation can be diffused to promote crosslinking.
Next, a cured film is obtained by performing a heating process (hereinafter referred to as a curing process) as necessary.

<When curing is performed by heating (thermal curing)>
First, pre-baking is performed as necessary.
Next, a curing process is performed to obtain a cured film.

The prebaking heating temperature is preferably 40 to 200 ° C, more preferably 60 to 200 ° C. The heating time is preferably 1 to 10 minutes, and more preferably 1 to 5 minutes.
40-200 degreeC is preferable and the heating temperature of a PEB process has more preferable 60-200 degreeC. The heating time is preferably 1 to 20 minutes, more preferably 1 to 10 minutes.
100-200 degreeC is preferable and the heating temperature of a curing process has more preferable 120-200 degreeC. Further, the heating time is preferably 1 to 60 minutes, and more preferably 1 to 30 minutes.

Step (3)
Next, the side surface of the cured film obtained in the step (2) is selectively irradiated with light for making the liquid repellent compound (A) lyophilic, particularly ultraviolet rays, so that the side surface of the cured film becomes the lyophilic side surface. And By this step (3), a diaphragm having an upper surface having liquid repellency and a side surface having lyophilicity is formed. As a method of selectively irradiating the side surface of the cured film with ultraviolet rays, a method of selectively irradiating the side surface of the cured film with ultraviolet rays using a laser or an LED light source, a method of selectively irradiating ultraviolet rays through a mask, The method etc. which irradiate an ultraviolet-ray from the main surface side on the opposite side to the main surface in which the cured film of the board | substrate was formed are mentioned.

  The exposure machine is not particularly limited as long as it is equipped with a low-pressure mercury lamp lamp, a high-pressure mercury lamp lamp, an ultra-high pressure mercury lamp lamp, a metal halide lamp, a halogen lamp, etc., and irradiates ultraviolet rays or visible rays in the range of 250 to 500 nm. .

  The liquid repellent compound (A1) is preferably subjected to a lyophilic process using an apparatus such as a low-pressure mercury lamp that includes a wavelength of less than 300 nm. As the liquid repellent compound (A2), it is preferable to use a light source capable of irradiating ultraviolet rays having a wavelength of 300 nm or more, such as an ultrahigh pressure mercury lamp (i-line 365 nm), a YAG laser (third harmonic wave 355 nm). In addition, since the surface of the cured film of the liquid repellent compound (A2) can be lyophilic even by ultraviolet light having a wavelength of less than 300 nm, a light source that can irradiate ultraviolet light having a wavelength of less than 300 nm may be used.

In light lyophilic preferably be lyophilic by irradiation of 10~100000mJ / cm ^2, for convenience of processing time, it is more preferable to lyophilic by 10 to 10000 mJ / cm ^2. When the sensitivity is less than the exposure amount, a problem occurs in the stability of the liquid repellent portion.

  After the step (3), the decomposition residue including the liquid repellent portion of the liquid repellent compound (A) may be removed. For example, it can be removed under heating or vacuum conditions.

  The material of the base material for forming the partition wall of the first aspect is not particularly limited. For example, glass, metal oxide, polyester resin such as polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyethylene, polypropylene Polyolefin resin such as polyvinyl chloride, fluororesin, acrylic resin, polyamide, polycarbonate, polyimide, etc. plastic film, cellophane, acetate, metal foil, glassine paper, parchment paper, or polyethylene, clay binder with sealing effect, Examples thereof include paper treated with polyvinyl alcohol, starch, carboxymethylcellulose (CMC) and the like. In addition, in the range which does not have a bad influence on the effect of this invention in the substance which comprises these base materials, a pigment, dye, antioxidant, a deterioration inhibitor, a filler, a ultraviolet absorber, an antistatic agent, electromagnetic wave prevention Additives such as agents may be included.

The thickness of the substrate is appropriately adjusted depending on the application and is not particularly limited, but is usually about 10 μm to 2 mm, preferably 15 μm to 1.5 mm, and more preferably 20 μm to 1 mm.
As the material for the base material, materials capable of transmitting ultraviolet light from the back surface, such as alkali-free glass, transparent metal oxide, and transparent film are preferable.

  FIG. 1 is a cross-sectional view schematically showing an example of the partition wall according to the first aspect of the present invention obtained as described above. 1 is a substrate, 2 is a partition wall according to the first aspect, and 3 is a partition wall 2. An enclosed opening is shown. In the partition wall 2, the upper surface 2 a has good liquid repellency, and the side surface 2 b has good lyophilicity, so that uniform ink applicability in the opening 3 can be sufficiently ensured.

  In the composition of the preferred combination 1 described above, the composition is drawn on a substrate by a micro-discharge method, and if necessary, the solvent (H) is removed by pre-baking and cured by irradiation with light having a wavelength of 300 nm or more. A film is formed and, if necessary, the crosslinking density is increased by post-baking (curing process), and then light of less than 300 nm is irradiated. Thereby, the partition of the 1st aspect which made only the side wall part lyophilic can be obtained. From the viewpoints of storage stability and ink ejection stability, the composition preferably does not contain a thermal initiator.

  In the composition of the preferred combination 2 described above, the composition was drawn on a substrate by a micro discharge method, the solvent (H) was removed by pre-baking as necessary, and a cured film was obtained by post-baking (curing process). Later, light of less than 300 nm or 300 nm or more is irradiated. Thereby, the partition of the 1st aspect which made only the side wall part lyophilic can be obtained. From the viewpoint of versatility of the apparatus, the present composition that can use a process of irradiating light of 300 nm or more is more preferable.

  For example, the partition wall of the first aspect formed from the composition of the present invention preferably has a width of 100 μm or less, more preferably 50 μm or less, and particularly preferably 20 μm or less. The distance between adjacent partition walls (pattern width) is preferably 300 μm or less, more preferably 200 μm or less, and particularly preferably 100 μm or less. The height of the partition wall is preferably 0.05 to 50 μm, and more preferably 0.2 to 10 μm.

  The partition wall according to the first aspect of the present invention can be used as a partition wall having the opening as an ink injection region when pattern printing is performed by the IJ method. When pattern printing is performed by the IJ method, if the partition wall according to the first aspect of the present invention is formed so that the opening thereof coincides with a desired ink injection region, the top surface of the partition wall has good ink repellency. In addition, since the side wall of the partition wall has good ink affinity, it is possible to suppress undesired openings beyond the partition wall, that is, to prevent ink from being injected into the ink injection region and to be surrounded by the partition wall Since the ink spreads well, it is possible to print the ink uniformly without causing white spots or the like in a desired region.

  If the partition wall of the first aspect of the present invention is used, pattern printing by the IJ method can be performed precisely as described above. Therefore, the partition of the first aspect of the present invention is an optical element having a partition located between a plurality of dots and adjacent dots on the surface of the substrate on which dots are formed by the IJ method, such as an organic EL element and a quantum dot display. It is useful as a partition for TFT arrays, thin film solar cells and the like.

  The cured film constituting the partition wall of the first aspect of the present invention (cured film before being lyophilic by light irradiation) is contacted with PGMEA in order to improve the color separation of the pixels in the partition wall by the micro discharge method. The angle is preferably 20 degrees or more, and more preferably 30 degrees or more. Further, in order to uniformly spread and spread the ink in the region surrounded by the partition walls, the contact angle difference before and after the light irradiation of the cured film is preferably 5 degrees or more, and more preferably 10 degrees or more. Here, the contact angle of the PGMEA (propylene glycol monomethyl ether acetate) is measured by a droplet method under a condition of 25 ° C. using a contact angle meter CA-A (product name) manufactured by Kyowa Interface Science Co., Ltd. Value.

[Partition repair method]
The method for repairing partition walls of the present invention is a method for repairing defects generated in partition walls formed in a shape that partitions a substrate surface into a plurality of sections for forming dots using the curable composition of the present invention. The obtained partition repair portion has the characteristics that the partition top surface has good liquid repellency and the partition wall side surface has good lyophilicity, like the partition of the first aspect of the present invention.

  The partition repaired by the composition of the present invention is preferably formed so that the upper surface has liquid repellency and the side surface has lyophilicity, like the partition repair portion. The partition wall having a liquid repellency on the upper surface and a lyophilic surface on the side surface can be formed by, for example, a photolithography method using a photosensitive resin composition containing an ink repellent agent. Is not to be done. The partition to be repaired may be the partition according to the first aspect of the present invention. The partition to be repaired can have the same shape as exemplified in the partition of the first aspect of the present invention, specifically, the width, the width of the pattern, and the height. Further, the liquid repellency of the upper surface of the partition wall to be repaired and the lyophilicity of the side surface can be the same as those of the partition wall of the first aspect of the present invention.

The partition wall repair method of the present invention will be described below with reference to the drawings.
Examples of the defect include a partial defect of a partition wall as shown in FIG. In FIG. 2, 1 is a substrate, 2 'is a partition formed on the substrate, 3 is an opening for dot formation, and 4 is a defective portion where the partition 2' is missing. Hereinafter, the method for repairing the partition wall according to the present invention will be described with reference to FIGS. 3A to 3C, taking as an example the case of repairing the defect portion 4 of the partition wall as shown in FIG.

Here, as a board | substrate 1, the thing similar to the partition of the said 1st aspect is mentioned about a material and a form including a preferable aspect. Further, the partition wall 2 'is as described above as the partition wall repaired.
This method includes the following steps (1) to (3).

Process (1)
First, as shown in FIG. 3A, the composition of the present invention is applied to the defect portion 4 of the partition wall 2 ′ on the surface of the substrate 1 by a dispenser method, which is a kind of a micro-discharge method, to form a coating film. In addition, there are an ink jet method, a nozzle printing method, and the like as the micro discharge method, and any of them can be used, but the dispenser method is preferable from the viewpoint of pattern uniformity.

  The dispenser method is a method using a liquid dispensing apparatus (indicated by 5 in FIG. 3A), and the material dispensing system is a flow rate control system, a pressure ON / OFF type, a flow rate ON / OFF type. In addition, a volumetric measurement method, a measurement chamber fixed type, a measurement chamber change type, and the like are known. When the dispenser method is used, the composition of the present invention preferably has a viscosity of 1 to 100,000 mPa · s, more preferably 3 to 10,000 mPa · s.

The ink jet method is a method in which a material is ejected from an ink jet nozzle and applied, and there are a method in which mechanical energy is applied to the material for ejection, and a method in which thermal energy is applied to the material for ejection.
The nozzle printing method is a method in which a head provided with several tens of fine nozzles is multiplexed and a small amount of material is ejected with a single stroke.

Process (2)
Next, as shown in FIG. 3B, the coating film is cured to form a cured film 6A.
<When curing is performed by light irradiation (photocuring)>
In the case where the composition contains a solvent (H) or the like, the coating film may be dried as necessary to form a dry film. Examples of the drying method include heat drying, reduced pressure drying, and reduced pressure heat drying. This heating step for the purpose of mainly drying the solvent is hereinafter referred to as pre-baking.

Next, light is irradiated.
The light to be irradiated is not particularly limited as long as the photopolymerization initiator (C2) contained in the composition of the present invention has a wavelength with sensitivity. Usually, the light used for curing is ultraviolet light (wavelength 200 to 400 nm, preferably 300 to 400 nm), but is not limited thereto. In addition, it is preferable not to use light having a wavelength that causes decomposition in the side chain of the unit (u1-1) in the liquid repellent compound (A1) or the unit (u2-1) in the liquid repellent compound (A2).

In the photocurable preferably be cured by irradiation of 1~10000mJ / cm ^2, for convenience of processing time, it is more preferably cured at 1~1000mJ / cm ^2. When the sensitivity is less than the above exposure amount, a problem occurs in the stability of the composition.
Immediately after exposure, if necessary, it may be heated (hereinafter referred to as PEB process). By the PEB step, for example, when the acid generator (F) or the like is contained in the composition, the acid generated by light irradiation can be diffused to promote crosslinking.
Next, a cured film is obtained by performing a heating process (hereinafter referred to as a curing process) as necessary.

<When curing is performed by heating (thermal curing)>
First, pre-baking is performed as necessary.
Next, a curing process is performed to obtain a cured film.

The prebaking heating temperature is preferably 40 to 200 ° C, more preferably 60 to 200 ° C. The heating time is preferably 1 to 10 minutes, and more preferably 1 to 5 minutes.
40-200 degreeC is preferable and the heating temperature of a PEB process has more preferable 60-200 degreeC. The heating time is preferably 1 to 20 minutes, more preferably 1 to 10 minutes.
100-200 degreeC is preferable and the heating temperature of a curing process has more preferable 120-200 degreeC. Further, the heating time is preferably 1 to 60 minutes, and more preferably 1 to 30 minutes.

Step (3)
Next, as shown in FIG. 3C, the side surface of the cured film 6A formed in the step (2) is selectively irradiated with light for making the liquid repellent compound (A) lyophilic, particularly ultraviolet rays, Make the side of the cured film lyophilic. In FIG. 3C, 6B shows the lyophilic side. By this step (3), the partition repair portion 6 having the upper surface having liquid repellency and the side surfaces having lyophilic properties is completed. As a method of selectively irradiating the side surface 6B of the cured film with ultraviolet rays, a method of selectively irradiating the side surfaces of the cured film with ultraviolet rays using a laser or an LED light source, or a method of selectively irradiating ultraviolet rays through a mask. And a method of irradiating ultraviolet rays from the main surface side opposite to the main surface on which the cured film 6A of the substrate 1 is formed.

  The exposure machine is not particularly limited as long as it is equipped with a low-pressure mercury lamp lamp, a high-pressure mercury lamp lamp, an ultra-high pressure mercury lamp lamp, a metal halide lamp, a halogen lamp, etc., and irradiates ultraviolet rays or visible rays in the range of 250 to 500 nm. .

  The liquid repellent compound (A1) is preferably subjected to a lyophilic process using an apparatus such as a low-pressure mercury lamp that includes a wavelength of less than 300 nm. As the liquid repellent compound (A2), it is preferable to use a light source capable of irradiating ultraviolet rays having a wavelength of 300 nm or more, such as an ultrahigh pressure mercury lamp (i-line 365 nm), a YAG laser (third harmonic wave 355 nm). In addition, since the surface of the cured film of the liquid repellent compound (A2) can be lyophilic even by ultraviolet light having a wavelength of less than 300 nm, a light source that can irradiate ultraviolet light having a wavelength of less than 300 nm may be used.

In light lyophilic preferably be lyophilic by irradiation of 10~100000mJ / cm ^2, for convenience of processing time, it is more preferable to lyophilic by 10 to 10000 mJ / cm ^2. When the sensitivity is less than the exposure amount, a problem occurs in the stability of the liquid repellent portion.

  After the step (3), the decomposition residue including the liquid repellent portion of the liquid repellent compound (A) may be removed. For example, it can be removed under heating or vacuum conditions.

  The partition repair portion formed in this manner has liquid repellency on the upper surface and lyophilicity on the side surface, so that no ink color mixing occurs at the partition repair site, and the ink is uniformly applied. Sex is not impaired. In addition, since the repair can be performed with a small number of steps using a micro-discharge method such as a dispenser method, it can be performed easily and economically with higher accuracy.

  In the composition of the preferred combination 1 described above, the composition is applied to the defect portion of the partition wall on the surface of the substrate by a micro discharge method, and the solvent (H) is removed by pre-baking as necessary, and light having a wavelength of 300 nm or more is obtained. A cured film is formed by irradiating with, and if necessary, the crosslinking density is increased by post-baking (curing step), and then light with a wavelength of less than 300 nm is irradiated. As a result, it is possible to obtain a partition repairing part in which only the side wall part is lyophilic. From the viewpoints of storage stability and ink ejection stability, the composition preferably does not contain a thermal initiator.

  In the composition of the preferred combination 2 described above, the composition is applied to the defect portion of the partition wall on the substrate surface by a micro discharge method, and the solvent (H) is removed by pre-baking as necessary, and post-baking (curing step). After obtaining a cured film by irradiating with light of less than 300 nm or 300 nm or more. As a result, it is possible to obtain a partition repairing part in which only the side wall part is lyophilic. From the viewpoint of versatility of the apparatus, the present composition that can use a process of irradiating light of 300 nm or more is more preferable.

  The partition wall according to the second aspect of the present invention has a partition repair portion in which the defect is repaired by the repair method of the present invention. The partition repair portion is formed so that the upper surface has liquid repellency and the side surface has lyophilicity, like the partition of the first aspect of the present invention. In addition, as described above, the partition wall that is normally repaired is formed so that the upper surface has liquid repellency and the side surface has lyophilicity, similar to the repaired portion.

  As described above, the partition wall repaired by the composition of the present invention, that is, the partition wall of the second embodiment of the present invention generally has liquid repellency on the upper surface and lyophilic side surfaces in the entire partition wall including the repair portion. Therefore, it is useful as an optical element having a partition wall between dots adjacent to a plurality of dots on a substrate surface on which dots are formed by the IJ method, particularly as an organic EL element or a quantum dot display partition wall.

[Optical element]
The optical element of the present invention, for example, an organic EL element, a quantum dot display, a TFT array, or a thin film solar cell is an optical element having a plurality of dots and a partition wall of the present invention located between adjacent dots on the substrate surface. . In the optical element of the present invention, for example, an organic EL element, a quantum dot display, a TFT array, or a thin film solar cell, the dots are preferably formed by the IJ method.

  The organic EL element has a structure in which a light emitting layer of an organic thin film is sandwiched between an anode and a cathode. The partition wall of the present invention is used for a partition wall separating an organic light emitting layer, a partition wall partition separating an organic TFT layer, and a coating type oxide semiconductor. It can be used for a partition wall.

With respect to the optical element of the present invention, for example, an organic EL element, an example in which dots are formed in the opening by the IJ method using the partition obtained above will be described below. In addition, the formation method of the dot in optical elements, such as the organic EL element of this invention, is not limited to the following.
4A and 4B schematically show a method of manufacturing an organic EL element using the partition wall 2 formed on the substrate 1 shown in FIG. Here, the partition 2 on the substrate 1 is formed so that the opening 3 matches the dot pattern of the organic EL element to be manufactured. The method for manufacturing the organic EL element using the partition walls repaired as shown in FIGS. 3A to 3C can be similarly performed.

  As shown in FIG. 4A, the ink 12 is dropped from the inkjet head 11 into the opening 3 surrounded by the partition wall 2, and a predetermined amount of ink 12 is injected into the opening 3. As the ink, known inks for organic EL elements are appropriately selected and used in accordance with the function of dots.

  Next, depending on the type of the ink 12 used, for example, a drying and / or heating process is performed to remove or cure the solvent, and as shown in FIG. The organic EL element 14 in which 13 is formed is obtained.

In addition, although an organic EL element can be manufactured as follows, for example, it is not limited to this.
A light-transmitting electrode such as tin-doped indium oxide (ITO) is formed on a light-transmitting substrate such as glass by a sputtering method or the like. The translucent electrode is patterned as necessary.

Next, partition walls are formed in a lattice shape in plan view along the outline of each dot using the composition of the present invention.
Next, the materials of the hole injection layer, the hole transport layer, the light emitting layer, the hole blocking layer, and the electron injection layer are applied and dried in the dots by the IJ method, and these layers are sequentially stacked. The kind and number of organic layers formed in the dots are appropriately designed.
Finally, a reflective electrode such as aluminum is formed by vapor deposition or the like.

Further, the quantum dot display can be manufactured, for example, as follows, but is not limited thereto.
The composition of the present invention is used for a translucent substrate such as glass, and partition walls are formed in a lattice pattern in plan view along the outline of each dot.
Next, a nanoparticle solution that converts blue light into green light by the IJ method, a nanoparticle solution that converts blue light into red light, and a blue color ink as necessary are coated in the dots and dried. Create A liquid crystal display having excellent color reproducibility can be obtained by using a light source that emits blue as a backlight and using the module as a color filter alternative.

The organic TFT array element is provided as a TFT array substrate in, for example, an organic EL element or a liquid crystal element.
The TFT array can be manufactured, for example, as follows, but is not limited thereto.
A gate electrode such as aluminum or an alloy thereof is formed on a light-transmitting substrate such as glass by a sputtering method or the like. This gate electrode is patterned as necessary.

  Next, a gate insulating film such as silicon nitride is formed by a plasma CVD method or the like. A source electrode and a drain electrode may be formed over the gate insulating film. The source electrode and the drain electrode can be formed by forming a metal thin film such as aluminum, gold, silver, copper, or an alloy thereof by, for example, vacuum deposition or sputtering. As a method of patterning the source electrode and the drain electrode, after forming a metal thin film, a resist is coated, exposed and developed to leave the resist in a portion where the electrode is to be formed, and then exposed with phosphoric acid or aqua regia. There is a method of removing the metal and finally removing the resist. In addition, when a metal thin film such as gold is formed, a resist is applied in advance, exposed and developed to leave the resist in a portion where it is not desired to form an electrode, and after forming the metal thin film, the photoresist is applied together with the metal thin film. There is also a technique to remove. Further, the source electrode and the drain electrode may be formed by a method such as ink jet using a metal nanocolloid such as silver or copper.

Next, partition walls are formed in a lattice shape in plan view along the outline of each dot using the composition of the present invention.
Next, a semiconductor solution is applied in the dots by the IJ method, and the solution is dried to form a semiconductor layer. As this semiconductor solution, an organic semiconductor solution or an inorganic coating type oxide semiconductor solution can also be used. The source electrode and the drain electrode may be formed by using a method such as inkjet after forming the semiconductor layer.
Finally, a transparent electrode such as ITO is formed by sputtering or the like, and a protective film such as silicon nitride is formed.

  The optical element of the embodiment of the present invention, for example, an organic EL element, a quantum dot display, a TFT array, or a thin film solar cell, can produce an optical element having dots formed with high accuracy by using the partition wall of the present invention.

  Hereinafter, the present invention will be described in more detail using examples, but the present invention is not limited to these examples. Examples 1 to 10 and 14 to 23 are examples, and examples 11 to 13 and 24 to 26 are comparative examples. In the following description, “part” and “%” mean “part by mass” and “% by mass”, respectively, unless otherwise specified.

Each measurement was performed by the following method.
(Number average molecular weight (Mn) and weight average molecular weight (Mw))
A gel permeation chromatography (GPC) of a plurality of types of monodisperse polystyrene polymers having different degrees of polymerization, which is commercially available as a standard sample for molecular weight measurement, is a commercially available GPC measurement device (manufactured by Tosoh Corporation, device name: HLC-8320GPC). It measured using. A calibration curve was prepared based on the relationship between the molecular weight of polystyrene and the retention time (retention time).
Each sample was diluted to 1.0 mass% with tetrahydrofuran, passed through a 0.5 μm filter, and then GPC was measured using the above apparatus. Using the calibration curve, the number average molecular weight (Mn) and the weight average molecular weight (Mw) of the sample were determined by computer analysis of the GPC spectrum.

(viscosity)
The measurement was performed at 25 ° C. using a TVE25L viscometer (manufactured by Toki Sangyo Co., Ltd.) calibrated with a standard solution JS2.5 for viscometer calibration (manufactured by Nippon Grease Co., Ltd., trade name).
(PGMEA contact angle)
The contact angle was measured by the droplet method under the condition of 25 ° C. using a product name: contact angle meter CA-A manufactured by Kyowa Interface Science Co., Ltd. About 1 μL of PGMEA (propylene glycol monomethyl ether acetate) was dropped onto the measurement surface, and the contact angle was measured.

The components other than the liquid repellent compound (A) and the liquid repellent polymer (2) used in each example are as follows. Liquid repellent polymers (1), (2), and (3) are liquid repellent agents used in comparative examples.
(Crosslinking agent (B))
B-1: Dipentaerythritol hexaacrylate B-2: Pentaerythritol tetraacrylate B-3: 1,6-hexanediol diacrylate B-4: ε-caprolactone-modified tris (acryloxyethyl) isocyanurate B-5: Fluorene Type epoxy acrylate / acid anhydride polymerization adduct (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., trade name V259-ME)

(Thermal polymerization initiator (C1)
C1-1: Benzoyl peroxide C1-2: 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile)
(Photopolymerization initiator (C2))
C2-1: 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one C2-2: 1,2-octanedione, 1- [4- (phenylthio)-, 2 -(O-benzoyloxime)
C2-3: 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide C2-4: Ethanone 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime)

(Liquid repellent)
Liquid repellent polymer (1): Rf (C4) α-Cl acrylate / GMA (glycidyl methacrylate) / 2-HEMA (2-hydroxyethyl methacrylate) / iBMA (isobornyl methacrylate) = 45/10/35/10 (mass) %) Copolymer and 50% solvent (diethylene glycol monobutyl ether acetate)
Rf (C4) α-Cl acrylate is a compound represented by the following formula.
_{C 4 F 9 CH 2 CH 2} -O (C = O) C (Cl) -CH 2
Liquid repellent polymer (3) (Ink repellent agent of International Publication No. 2013/161829 (C6)): CF ₃ (CF ₂ ) ₅ CH ₂ CH ₂ Si (OCH ₃ ) ₃ / SH (CH ₂ ) ₃ Si (OCH) _{3) 3 / Si (OC 2} H 5) 4 / CH 2 = CHCOO (CH 2) 3 Si (OCH 3) 3 / (CH 3) 3 SiOCH 3 = 14/9/33/22/22 ( molar ratio) 10% by weight propylene glycol monomethyl ether solution (photosensitizer) of partially hydrolyzed condensate (weight average molecular weight (Mw) 1520)
EAB: 4,4′-bis (diethylamino) benzophenone

(Ultraviolet absorber (D))
D-1: PGMEA dispersion of black organic pigment (azomethine black organic pigment 12%, polymer dispersant 7.2%, PGMEA (propylene glycol monomethyl ether acetate) 80.8%, solid content acid value: 7.2 mgKOH / G)
(Solvent (H))
EDM: Diethylene glycol ethyl methyl ether PGMEA: Propylene glycol monomethyl ether acetate NMP: N-methyl-2-pyrrolidone γ-BL: γ-butyrolactone

[Production of liquid repellent compound (A) and liquid repellent polymer (2)]
(Production Example 1: Production of liquid repellent compound (A1-1))
Compound (a11) (in the compound (a1), R ¹ and R ² are methyl groups, R ⁴¹ , R ⁵¹ , R ⁷¹ , R ⁸¹ are hydrogen atoms, R ⁶¹ is a structure represented by the formula (a1-1), and X Is an oxygen atom, a compound in which n is 1, and m is 1, 2.5 g of Ciba Specialty Chemicals, trade name: IRGACURE 2959) and 2.3 g of triethylamine are mixed and dissolved in 62 mL of dichloromethane. Got. While the solution was stirred at 0 ° C., a solution of 1.2 g of methacrylic acid chloride (compound (b11)) dissolved in 8 mL of dichloromethane was added dropwise to the solution. After completion of the dropwise addition, the mixture was stirred at 0 ° C. for 1 hour, and the compound (c11) (in the compound (c1), R ¹ and R ² were methyl groups, R ⁴² , R ⁵² , R ⁷² , and R ⁸² were hydrogen atoms, R ⁶² Is a structure represented by the formula (c1-1), wherein X is an oxygen atom, n is 1, m is 1, and Z is a methacryloyl group.

  While stirring the solution containing the compound (c11) at 0 ° C., 1.7 g of triethylamine was added. Subsequently, 4.6 g of 2,2-difluoro-2- (1,1,2,2-tetrafluoro-2- (perfluoroethoxy) ethoxy) acetyl fluoride (compound d11) was added dropwise. After completion of the dropwise addition, the mixture was stirred at room temperature for 1 hour to obtain a solution containing the compound of the following formula (m1-1).

A solution containing the compound (m1-1) was poured into ice water and extracted three times with ethyl acetate. Thereafter, the organic layer was dried using magnesium sulfate, the solvent was removed, and the residue was purified by a silica gel column chromatogram (ethyl acetate / hexane = 1/2 (volume ratio) was used as the distillate). By performing, 2.0 g of compound (m1-1) was obtained.
The compound (m1-1) was identified by ¹ H-NMR and ¹⁹ F-NMR.

NMR spectrum of compound (m1-1);
¹ H-NMR (300.4 MHz, solvent: CDCl ₃ , standard: TMS) δ (ppm): 1.85 (s, 6H), 1.95 (s, 3H), 4.27 (t, J = 4 .8, 2H), 4.52 (t, J = 4.8, 2H), 5.60 (s, 1H), 6.13 (s, 1H), 6.92 (d, J = 8.7) 2H), 7.92 (d, J = 8.7, 2H).
¹⁹ F-NMR (282.7 MHz, solvent: CDCl ₃ , reference: CFCl ₃ ) δ (ppm): −88.9 (m, 4F), −88.7 (m, 2F), −87.1 (m 3F), -78.5 (m, 2F).

  In 2.2 g of 2-butanone, 0.80 g of compound (m1-1), 0.03 g of 2-hydroxyethyl methacrylate, and 0.04 g of octyl acrylate, 0.031 g of n-dodecyl mercaptan and The reaction was carried out at 50 ° C. for 24 hours in the presence of 0.004 g of 2,2′-azobis (2,4-dimethylvaleronitrile). After cooling to room temperature (20-25 ° C.), add 0.09 g of 2-acryloyloxyethyl isocyanate, 0.0004 g of dibutyltin dilaurate and 0.0045 g of 2,6-di-tert-butyl-p-cresol And a liquid repellent compound (A1-1) having a unit (u1-1-1), a unit (u1-2-1) and a unit (u1-3-1) represented by the following formula: Of 2-butanone was obtained. The obtained 2-butanone solution of the liquid repellent compound (A1-1) is precipitated by adding it to hexane, and the obtained solid is vacuum-dried to obtain a powdery liquid repellent compound (A1-1). 0.72 g was obtained.

(Production Example 2: Production of liquid repellent compound (A1-2))
In 2.4 g of 2-butanone, 0.90 g of compound (m1-1), 0.03 g of 2-hydroxyethyl methacrylate, and 0.08 g of styrene were mixed with 0.035 g and 2 of n-dodecyl mercaptan. , 2′-azobis (2,4-dimethylvaleronitrile) was reacted at 50 ° C. for 24 hours in the presence of 0.005 g. After cooling to room temperature (20-25 ° C.), add 0.03 g of 2-acryloyloxyethyl isocyanate, 0.0001 g of dibutyltin dilaurate and 0.0017 g of 2,6-di-tert-butyl-p-cresol And a liquid repellent compound (A1-2) having a unit (u1-1-1), a unit (u1-2-1) and a unit (u1-3-2) represented by the following formula: 2-butanone solution was obtained. The obtained 2-butanone solution of the liquid repellent compound (A1-2) was precipitated by adding it to hexane, and the obtained solid was vacuum-dried to obtain a powdery liquid repellent compound (A1-2). 0.44 g was obtained.

(Production Example 3: Production of liquid repellent compound (A1-3))
In 2.8 g of 2-butanone, 1.00 g of compound (m1-1), 0.04 g of 2-hydroxyethyl methacrylate, and 0.14 g of hexyl methacrylate, 0.039 g of n-dodecyl mercaptan and The reaction was carried out at 50 ° C. for 24 hours in the presence of 0.005 g of 2,2′-azobis (2,4-dimethylvaleronitrile). After cooling to room temperature (20-25 ° C.), add 0.04 g of 2-acryloyloxyethyl isocyanate, 0.0002 g of dibutyltin dilaurate and 0.0019 g of 2,6-di-tert-butyl-p-cresol And a liquid repellent compound (A1-3) having a unit (u1-1-1), a unit (u1-2-1), and a unit (u1-3-3) represented by the following formula: 2-butanone solution was obtained. The obtained 2-butanone solution of the liquid repellent compound (A1-3) is precipitated by adding it to hexane, and the obtained solid is vacuum-dried to obtain a powdery liquid repellent compound (A1-3). 0.88 g was obtained.

(Production Example 4: Production of liquid repellent compound (A1-4))
In 2.5 g of 2-butanone, 0.80 g of compound (m1-1), 0.03 g of 2-hydroxyethyl methacrylate, and 2- (2′-hydroxy-5′-methacryloxyethylphenyl)- 0.21 g of 2H-benzotriazole was reacted at 50 ° C. for 24 hours in the presence of 0.031 g of n-dodecyl mercaptan and 0.004 g of 2,2′-azobis (2,4-dimethylvaleronitrile). It was. After cooling to room temperature (20-25 ° C.), add 0.03 g of 2-acryloyloxyethyl isocyanate, 0.0001 g of dibutyltin dilaurate and 0.0015 g of 2,6-di-tert-butyl-p-cresol And a liquid repellent compound (A1-4) having a unit (u1-1-1), a unit (u1-2-1), and a unit (u1-3-4) represented by the following formula: 2-butanone solution was obtained. The obtained 2-butanone solution of the liquid repellent compound (A1-4) is precipitated by adding it to hexane, and the obtained solid is vacuum-dried to obtain a powdery liquid repellent compound (A1-4). 0.66 g was obtained.

(Production Example 5: Production of liquid repellent compound (A2-1))
The reaction represented by the following formula was performed. 17.7 g of 4-hydroxybenzenethiol and 20.0 g of 4′-bromopropiophenone were dissolved in 151 g of DMAc (dimethylacetamide) to obtain a solution. While the solution was stirred at 80 ° C., 25.9 g of potassium carbonate was added to the solution. The mixture was stirred at 80 ° C. for 12 hours to obtain a solution of compound (a21). Next, the obtained solution of the compound (a21) was poured into water, and the precipitate was vacuum-dried to obtain 24.0 g of the compound (a21).

  20.0 g of compound (a21) and 19.0 g of triethylamine were dissolved in 100 g of tetrahydrofuran (hereinafter also referred to as “THF”) to obtain a solution. While the solution was stirred at 0 ° C., 9.3 g of the compound (b21) was added dropwise to the solution. The mixture was further stirred at 0 ° C. for 1 hour to obtain a solution of compound (c21). Subsequently, the obtained compound (c21) solution was poured into water and extracted three times with ethyl acetate. The organic phase was dried under vacuum to obtain 28.0 g of compound (c21).

  25.0 g of compound (c21), 15.0 g of isoamyl nitrite, and 12.5 g of 35% aqueous hydrochloric acid were dissolved in 125 g of THF to obtain a solution. The solution was stirred at room temperature for 3 days to obtain a solution of compound (e21). Subsequently, the obtained compound (e21) solution was poured into water and extracted three times with ethyl acetate. The organic phase was vacuum dried to obtain 25.0 g of compound (e21).

  7.5 g of phthalic anhydride, 20.0 g of 1H, 1H, 2H, 2H-perfluorooctanol, 8.9 g of 4-dimethylaminopyridine, and 7.5 g of triethylamine are dissolved in 200 g of dichloromethane to obtain a solution. It was. The solution was stirred at room temperature for 5 hours to obtain a solution of compound (f21). The resulting compound (f21) solution was then washed 3 times with 1N hydrochloric acid and once with water. The organic phase was vacuum dried to obtain 25.0 g of compound (f21).

7.5 g of the compound (e21) and 3.3 g of diisopropylcarbodiimide were dissolved in 50 g of THF to obtain a solution. While the solution was stirred at 0 ° C., a solution of 13.5 g of compound (f21) dissolved in 13 g of THF was added dropwise. Furthermore, after stirring at 0 degreeC for 1 hour, it stirred at room temperature for 5 hours, and obtained the solution of the compound (m2-1). The solvent was removed from the solution with an evaporator and then vacuum-dried to obtain 18 g of compound (m2-1).
The compound (m2-1) was identified by ¹ H-NMR and ¹⁹ F-NMR.

NMR spectrum of compound (m2-1);
¹ H-NMR (300.4 MHz, solvent: CDCl ₃ , reference: TMS) δ (ppm): 2.11 (s, 3H), 2.54 (m, 2H), 4.60 (t, J = 6 .3, 2H), 5.88 (m, 1H), 6.12 (m, 1H), 6.46 (m, 1H), 7.19 (m, 5H), 7.86 (m, 7H) .
¹⁹ F-NMR (282.7 MHz, solvent: CDCl ₃ , reference: CFCl ₃ ) δ (ppm): -126.6 (m, 2F), -124.0 (m, 4F), -123.3 (m 2F), -122.3 (m, 2F), -114.0 (m, 2F), -81.2 (m, 3F).

  In 20.0 g of 2-butanone, 9.8 g of compound (m2-1) and 1.5 g of 2-hydroxyethyl methacrylate, 0.34 g of n-dodecyl mercaptan and 2,2′-azobis (4 -Methoxy-2,4-dimethylvaleronitrile) was allowed to react at 50 ° C. for 24 hours. After cooling to room temperature (20-25 ° C.), add 1.7 g of 2-acryloyloxyethyl isocyanate, 0.007 g of dibutyltin dilaurate and 0.084 g of 2,6-di-tert-butyl-p-cresol The mixture was reacted at 40 ° C. for 24 hours to obtain a 2-butanone solution of a polymer (A2-1) having units (u2-1-1) and units (u2-2-1) of the following formula. The 2-butanone solution of the obtained polymer (A2-1) was put into hexane, and the precipitate was vacuum-dried to obtain 10.1 g of a powdery polymer (A2-1).

(Production Example 6: Production of liquid repellent compound (A2-2))
The reaction represented by the following formula was performed. 20.2 g of the compound (a21) obtained in Production Example 5 and 9.7 g of triethylamine were dissolved in 89 g of THF to obtain a solution. While the solution was stirred at 0 ° C., 9.0 g of the compound (b22) was added dropwise to the solution. The mixture was further stirred at 0 ° C. for 1 hour and then at room temperature for 3.5 hours to obtain a solution of compound (c22). Subsequently, the obtained compound (c22) solution was poured into water and extracted three times with ethyl acetate. The organic phase was dried under vacuum to obtain 26.6 g of compound (c22).

  20.0 g of compound (c22), 10.9 g of isoamyl nitrite and 5.0 g of 35% aqueous hydrochloric acid solution were dissolved in 107 g of THF to obtain a solution. The solution was stirred at room temperature for 1 day to obtain a solution of compound (e22). Next, the obtained solution of the compound (e22) was poured into water and extracted three times with ethyl acetate. The organic phase was dried under vacuum to obtain 14.2 g of compound (e22).

10.0 g of compound (e22) and 5.5 g of diisopropylcarbodiimide were dissolved in 70 g of THF to obtain a solution. While the solution was stirred at 0 ° C., a solution of 21.8 g of compound (f21) dissolved in 20 g of THF was added dropwise. The mixture was further stirred at 0 ° C. for 1 hour and then at room temperature for 20 hours to obtain a suspension of the compound (m2-2). The suspension was filtered, and the solvent was removed from the resulting solution with an evaporator. Then, the suspension was vacuum-dried to obtain 15.0 g of the compound (m2-2).
The compound (m2-2) was identified by ¹ H-NMR and ¹⁹ F-NMR.

NMR spectrum of compound (m2-2);
¹ H-NMR (300.4 MHz, solvent: CDCl ₃ , standard: TMS) δ (ppm): 2.11 (s, 3H), 2.28 (s, 3H), 2.54 (m, 2H), 4.60 (t, J = 6.3, 2H), 5.88 (s, 1H), 6.38 (s, 1H), 7.20 (m, 5H), 7.86 (m, 7H) .
¹⁹ F-NMR (282.7 MHz, solvent: CDCl ₃ , reference: CFCl ₃ ) δ (ppm): -126.6 (m, 2F), -124.0 (m, 4F), -123.3 (m 2F), -122.3 (m, 2F), -114.0 (m, 2F), -81.2 (m, 3F).

  In 2.7 g of 2-butanone, 1.0 g of compound (m2-2) and 0.15 g of 2-hydroxyethyl methacrylate, 0.33 g of n-octadecyl mercaptan and 2,2′-azobis (2 , 4-dimethylvaleronitrile) in the presence of 0.005 g at 50 ° C. for 24 hours. After cooling to room temperature (20-25 ° C.), add 0.17 g of 2-acryloyloxyethyl isocyanate, 0.0007 g of dibutyltin dilaurate and 0.008 g of 2,6-di-tert-butyl-p-cresol The mixture was reacted at 40 ° C. for 24 hours to obtain a 2-butanone solution of a polymer (A2-2) having units (u2-1-2) and units (u2-2-1) of the following formula. In the same manner as in Production Example 5, 1.18 g of a powdery polymer (A2-2) was obtained.

(Production Example 7: Production of liquid repellent compound (A2-3))
Dissolve 3.5 g of succinic anhydride, 13.7 g of 1H, 1H, 2H, 2H-perfluorooctanol, 1.1 g of 4-dimethylaminopyridine and 5.4 g of triethylamine in 106 g of dichloromethane to obtain a solution. It was. The solution was stirred at room temperature for 17 hours to obtain a solution of compound (f22). Subsequently, the solution of the obtained compound (f22) was washed 3 times with 1N hydrochloric acid and once with water. The organic phase was vacuum dried to obtain 15.7 g of compound (f22).

The reaction represented by the following formula was performed. 5.1 g of the compound (e22) obtained in Production Example 5 and 2.7 g of diisopropylcarbodiimide were dissolved in 30 g of THF to obtain a solution. While the solution was stirred at 0 ° C., a solution of 9.7 g of compound (f22) dissolved in 10 g of THF was added dropwise. Furthermore, after stirring at 0 degreeC for 1 hour, it stirred at room temperature for 19 hours, and obtained the solution of the compound (m2-3). The solvent was removed from the solution with an evaporator and then vacuum-dried to obtain 9.7 g of the compound (m2-3).
The compound (m2-3) was identified by ¹ H-NMR and ¹⁹ F-NMR.

NMR spectrum of compound (m2-3);
¹ H-NMR (300.4 MHz, solvent: CDCl ₃ , standard: TMS) δ (ppm): 2.11 (s, 3H), 2.28 (s, 3H), 2.54 (m, 2H), 2.80 (m, 4H), 4.60 (t, J = 6.3, 2H), 5.88 (s, 1H), 6.38 (s, 1H), 7.19 (m, 4H) 7.55 (m, 2H), 7.98 (m, 2H).
¹⁹ F-NMR (282.7 MHz, solvent: CDCl ₃ , reference: CFCl ₃ ) δ (ppm): -126.6 (m, 2F), -124.0 (m, 4F), -123.3 (m 2F), -122.3 (m, 2F), -114.0 (m, 2F), -81.2 (m, 3F).

  In 2.2 g of 2-butanone, 0.8 g of compound (m2-3) and 0.13 g of 2-hydroxyethyl methacrylate, 0.03 g of n-octadecyl mercaptan and 2,2′-azobis (2 , 4-dimethylvaleronitrile) in the presence of 0.004 g at 50 ° C. for 24 hours. After cooling to room temperature (20-25 ° C.), add 0.14 g of 2-acryloyloxyethyl isocyanate, 0.0006 g of dibutyltin dilaurate and 0.007 g of 2,6-di-tert-butyl-p-cresol The mixture was reacted at 40 ° C. for 24 hours to obtain a 2-butanone solution of a polymer (A2-3) having units (u2-1-3) and units (u2-2-1) of the following formula. In the same manner as in Production Example 5, 0.89 g of a powdery polymer (A2-3) was obtained.

(Production Example 8: Production of liquid repellent compound (A2-4))
In 2.2 g of 2-butanone, 0.8 g of compound (m2-3), 0.08 g of 2-hydroxyethyl methacrylate and 2- (1H-benzo [d] [1,2,3] triazole- 0.11 g of 1-carboxamido) ethyl methacrylate in the presence of 0.02 g of n-octadecyl mercaptan and 0.003 g of 2,2′-azobis (2,4-dimethylvaleronitrile) at 50 ° C. Reacted for hours. After cooling to room temperature (20-25 ° C.), add 0.08 g of 2-acryloyloxyethyl isocyanate, 0.0003 g of dibutyltin dilaurate and 0.004 g of 2,6-di-tert-butyl-p-cresol. Of the polymer (A2-4) having a unit (u2-1-3), a unit (u2-2-1) and a unit (u2-3-1) represented by the following formula by reacting at 40 ° C. for 24 hours: A butanone solution was obtained. In the same manner as in Production Example 5, 0.86 g of a powdery polymer (A2-4) was obtained.

(Production Example 9: Production of liquid repellent compound (A2-5))
5 g of succinic anhydride, 18.6 g of 2,2-difluoro-2 (1,1,2,2-tetrafluoro-2- (2-perfluoroethoxy) ethanol, 1.5 g of 4-dimethylaminopyridine, triethylamine Was dissolved in 113 g of dichloromethane to obtain a solution, which was stirred at room temperature for 17 hours to obtain a solution of compound (f23). This was washed 3 times with 1N hydrochloric acid and once with water, and the organic phase was dried under vacuum to obtain 21.4 g of compound (f23).

The reaction represented by the following formula was performed. 12 g of the compound (e22) obtained in Production Example 6 and 5.6 g of diisopropylcarbodiimide were dissolved in 81 g of THF to obtain a solution. While the solution was stirred at 0 ° C., a solution of 17.5 g of compound (f23) dissolved in 20 g of THF was added dropwise. Furthermore, after stirring at 0 degreeC for 1 hour, it stirred at room temperature for 19 hours, and obtained the solution of the compound (m2-4). The solvent was removed from the solution with an evaporator and then vacuum-dried to obtain 21 g of the compound (m2-4).
The compound (m2-4) was identified by ¹ H-NMR and ¹⁹ F-NMR.

NMR spectrum of compound (m2-4);
¹ H-NMR (300.4 MHz, solvent: CDCl ₃ , reference: TMS) δ (ppm): 2.27 (s, 3H), 2.88 (m, 7H), 4.76 (t, J = 9 .9, 2H), 5.88 (s, 1H), 6.34 (s, 1H), 7.30 (m, 4H), 7.65 (m, 2H), 8.03 (m, 2H) .
¹⁹ F-NMR (282.7 MHz, solvent: CDCl ₃ , reference: CFCl ₃ ) δ (ppm): −88.1 (m, 6F), −86.4 (m, 3F), −76.6 (m 2F).

  In 2.4 g of 2-butanone, 0.9 g of compound (m2-4) and 0.10 g of 2-hydroxyethyl methacrylate, 0.03 g of n-octadecyl mercaptan and 2,2′-azobis (2 , 4-dimethylvaleronitrile) in the presence of 0.004 g at 50 ° C. for 24 hours. After cooling to room temperature (20-25 ° C.), add 0.11 g of 2-acryloyloxyethyl isocyanate, 0.0004 g of dibutyltin dilaurate and 0.006 g of 2,6-di-tert-butyl-p-cresol The mixture was reacted at 40 ° C. for 24 hours to obtain a 2-butanone solution of a polymer (A2-5) having units (u2-1-4) and units (u2-2-1) described later. In the same manner as in Production Example 5, 0.82 g of a powdery polymer (A2-5) was obtained.

(Production Example 10: Production of liquid repellent compound (A2-6))
In 2.3 g of 2-butanone, 0.19 g of compound (m2-4), 0.03 g of 2-hydroxyethyl methacrylate and 2- (2′-hydroxy-5′-methacryloxyethylphenyl) -2H 0.06 g of benzotriazole was reacted at 50 ° C. for 24 hours in the presence of 0.03 g of n-octadecyl mercaptan and 0.004 g of 2,2′-azobis (2,4-dimethylvaleronitrile) . After cooling to room temperature (20-25 ° C.), add 0.03 g of 2-acryloyloxyethyl isocyanate, 0.0001 g of dibutyltin dilaurate and 0.001 g of 2,6-di-tert-butyl-p-cresol 2 of the polymer (A2-6) having a unit (u2-1-4), a unit (u2-2-1) and a unit (u2-3-3) described later by reacting at 40 ° C. for 24 hours. -A butanone solution was obtained. In the same manner as in Production Example 5, 0.89 g of a powdery polymer (A2-6) was obtained.

(Production Example 11: Production of liquid repellent polymer (2) as a liquid repellent)
In an autoclave with an internal volume of 1 L equipped with a stirrer, 556 g of acetone, 96 g of C6FMA (CH ₂ ═C (CH ₃ ) COOCH ₂ CH ₂ (CF ₂ ) ₆ F), 4.8 g of MAA (methacrylic acid), 96 g of 2-HEMA (2-hydroxyethyl methacrylate), 43.2 g of MMA (methyl methacrylate), 6.2 g of chain transfer agent 2-ME (2-mercaptoethanol) and polymerization initiator 2,2′-azobis ( 4.5 g of 4-methoxy-2,4-dimethylvaleronitrile was charged and polymerized at 40 ° C. for 18 hours with stirring in a nitrogen atmosphere to obtain an acetone solution of the polymer (1). Water was added to the acetone solution of the union (1) for reprecipitation purification, followed by reprecipitation purification with petroleum ether and vacuum drying to obtain 237 g of the polymer (1).

  Next, in a glass flask having an internal volume of 500 mL equipped with a thermometer, a stirrer, and a heating device, 100 g of the polymer (1), 47.7 g of MOI (2-methacryloyloxyethyl isocyanate), DBTDL (dibutyltin dilaurate) ), 0.19 g of BHT (2.4 g of 2,6-di-t-butyl-p-cresol) and 100 g of acetone were polymerized at 30 ° C. for 18 hours with stirring to obtain a polymer (2). An acetone solution of was obtained. Water was added to the acetone solution of the obtained polymer (2) for reprecipitation purification, followed by reprecipitation purification with petroleum ether and vacuum drying to obtain 135 g of a powdery liquid repellent polymer (2). The liquid repellent polymer (2) had a weight average molecular weight (Mw) of 8,800.

Table 1 shows the fluorine content and number average molecular weight (Mn) of the liquid repellent compounds (A1-1) to (A2-6).

[Example 1: Preparation of partition wall-forming resin composition and preparation of partition walls]
(Preparation of partition wall forming resin composition)
0.44 parts of the liquid repellent compound (A1-1) obtained in Production Example 1 above, 87.7 parts of B-1, 5.00 parts of C2-1, 6.84 parts of EAB, and solid content Was put in a stirring vessel and stirred for 5 hours to prepare a partition wall-forming resin composition.

(Formation of partition walls)
Using the inkjet printing apparatus LaboJet-500 (manufactured by Microjet), the partition wall-forming resin composition was formed on a non-alkali glass substrate having a thickness of 0.7 mm under the conditions of a head temperature of 25 ° C. and a piezoelectric voltage of 100 V. A pattern (opening 100 × 200 μm, pattern width 30 μm, pattern thickness 1.0 μm) was drawn. Next, this pattern was cured using an exposure apparatus MA-8 (manufactured by SUSS Micro Tec) under the conditions of an ultraviolet ray having a wavelength of 365 nm under an exposure time of 4.9 s and an exposure amount of 200 mJ / cm ² .
Thereafter, ultraviolet rays (including a wavelength of 254 nm) are exposed to an exposure time of 5.5 s using an exposure apparatus (SX-UI501HQ, manufactured by USHIO INC.) Through a mask on the patterned surface of the glass substrate. Irradiation was performed under the condition of an amount of 500 mJ / cm ² to form a partition wall exposed at both ends of 1 μm.

[Examples 2-3, 11-13]
A partition wall-forming resin composition and partition walls were formed in the same manner as in Example 1 except that the composition of the partition wall-forming resin composition was changed as shown in Table 2.

[Example 4]
The resin composition for partition wall formation was changed in the same manner as in Example 1 except that the composition of the resin composition for partition wall formation was changed as shown in Table 2 and the drawn pattern was cured at 150 ° C. for 30 minutes. And partition walls were formed.

[Example 5]
The composition of the partition wall forming resin composition was changed as shown in Table 2, and after the drawn pattern was cured under the condition of heating at 150 ° C. for 30 minutes, the surface of the glass substrate opposite to the surface on which the pattern was formed was changed. In addition to using an exposure apparatus (manufactured by SUS Micro Tec, model number MA-8) without using a mask, ultraviolet rays (wavelength 365 nm) were irradiated under conditions of an exposure time of 24.5 s and an exposure dose of 1 J / cm ^2. Were the same as in Example 1 to form a partition wall-forming resin composition and partition walls.

[Examples 6 to 10]
The partition wall forming resin composition was changed as shown in Table 2, and the ultraviolet irradiation method was the same as in Example 5 except that the patterned surface of the glass substrate was irradiated through a mask. A resin composition and partition walls were formed.

(Evaluation)
The following evaluation was implemented about the partition formed in Examples 1-13. The results are shown in the lower column of Table 2.

<Liquid repellency on top of partition wall>
The PGMEA contact angle on the upper surface of the partition wall obtained above was measured by the above method and evaluated according to the following criteria.
◎: Contact angle 30 degrees or more ○: Contact angle 20 degrees or more and less than 30 degrees ×: Contact angle 20 degrees or less

<Particle top and side repellency contrast (difference in contact angle before and after exposure)>
Apart from the partition walls, the partition wall forming resin composition is applied onto the entire surface of the substrate by spin coating and cured to form a cured film. After measuring the PGMEA contact angle for the cured film, the cured film is exposed to the parent film. It liquefied, the PGMEA contact angle of the surface was again measured, the difference was computed, and the following reference | standard evaluated. In addition, hardening and exposure were performed on the conditions similar to the case of formation of the said partition.
◎: Contact angle difference is 10 degrees or more ○: Contact angle difference is 5 degrees or more and less than 10 degrees ×: Contact angle difference is less than 5 degrees

<Wetting and spreading of ink>
6.25 g of liquid epoxy resin Pernox ME-562 (trade name, manufactured by Nippon Pernox Co., Ltd.), 6.25 g of curing agent Percure HV-562 (trade name, manufactured by Nippon Pernox Co., Ltd.), 3-butylene glycol di 33.75 g of acetate and 3.75 g of 4-butyrolactone were stirred and mixed using a stirrer for 1 hour, and water was added while stirring until the surface tension reached 35 mN / m to prepare an ink.

By applying about 20 pL or 40 pL of the ink prepared above to the opening surrounded by the partition wall of the glass substrate using an inkjet method, and observing with an ultra-deep shape measuring microscope VK-8500 (manufactured by Keyence Corporation) The wetting and spreading properties of the ink in the opening surrounded by the partition walls were evaluated according to the following criteria.
A: The entire surface of the opening is wet with ink at an ink amount of 20 pL. O: The entire surface of the opening is wet with ink at an ink amount of 40 pL. X: A part of the opening repels ink.

As is clear from Table 2, Examples 1 to 10 contain the liquid repellent compound (A), so that the side walls are made lyophilic by performing exposure after the partition walls are formed. While the wet spreading property is good, since Examples 11 to 13 do not contain the liquid repellent compound (A), the liquid repellency on the upper surface of the partition wall is good, but the liquid repellency is changed by light irradiation. Therefore, the contact angle difference before and after the exposure and the ink spreading property are insufficient.
Moreover, since Examples 1-4 and 9-10 use the perfluoroalkyl group which has an etheric oxygen atom between carbon atoms for Cf group of a liquid repellent compound, initial liquid repellency, the contact angle difference before and behind exposure, Ink wetting and spreading properties are better.

[Example 14: Preparation of curable composition for barrier rib repair and barrier rib repair]
(Preparation of curable composition for partition wall repair)
0.44 parts of the liquid repellent compound (A1-1) obtained in Production Example 1 above, 87.7 parts of B-1, 5.00 parts of C2-1, 6.84 parts of EAB, and solid An EDM amount of 70% was placed in a stirring vessel and stirred for 10 hours to prepare a curable composition for partition wall repair. The viscosity of the obtained curable composition for barrier rib repair was 25.3 mPa · s.

(Preparation of partition wall forming composition)
DPHA (dipentaerythritol hexaacrylate) 45.2 parts, ZCR1569H (manufactured by Nippon Kayaku Co., Ltd., trade name; solid content 70%) as a dispersion of alkali-soluble photosensitive resin 47.1 parts, photopolymerization started 2- (benzoyloxyimino) -1- [4- (phenylthio) phenyl] -1-octanone (manufactured by BASF) as an agent, 3-glycidoxypropyltrimethoxysilane as a silane coupling agent 5.8 parts and 570 parts of PGMEA as a solvent were mixed to obtain a diluted solution of the partition wall forming composition.

(Partition formation and defect detection)
After applying the diluted solution of the obtained partition wall forming composition on a non-alkali glass substrate using a slit coater, vacuum drying is performed at 130 Pa for 30 seconds, and further drying is performed on a hot plate at 100 ° C. for 2 minutes. Formed. Above this coating film, a mask (line = 20 μm, lattice space = 100 μm × 200 μm) on which a lattice pattern was formed was placed with a gap of 30 μm, and irradiated with 100 mJ / cm ² by an ultrahigh pressure mercury lamp. Next, the substrate was developed using a 0.1% by mass tetramethylammonium hydroxide aqueous solution containing a surfactant at 25 ° C. for 40 seconds, washed with water, and dried to form partition walls.

The substrate on which the partition wall is formed is irradiated with halogen lamp light using a device FAD320s (manufactured by Musashi Engineering Co., Ltd.) equipped with a micro-dispenser having a defect detection and coating needle, and the partition wall is imaged by a CCD camera. As a result of inspection by comparing with a reference pattern prepared in advance, a defect portion (defect portion) was detected in the partition wall. The apparatus is equipped with a defective partition wall observation unit for detecting a chip defect portion of the partition wall, a laser for removing the chip defect portion of the partition wall, and a micro dispenser for chip defect correction.
Thereafter, a pulse laser (wavelength of 532 nm) was irradiated with a laser output of 20% to the pinhole defect of the partition wall for which position data was acquired by an inspection apparatus, and the defect was easily corrected.

(Partition repair)
The partition wall repairing curable composition was applied to the defect portion of the partition wall formed on the glass substrate using the apparatus FAD320s. Next, the coating film was cured by using an exposure apparatus MA-8 (manufactured by SUSS Micro Tec) and irradiating with ultraviolet light having a wavelength of 365 nm under the conditions of an exposure time of 4.9 s and an exposure amount of 200 mJ / cm ^2. It was. This cured film is exposed to ultraviolet rays (including a wavelength of 254 nm) using an exposure apparatus SX-UI501HQ (manufactured by USHIO INC.) Through a mask, with an exposure time of 5.5 s and an exposure dose of 500 mJ / cm ² . Were exposed to 1 μm at both ends, and repair of the defect part of the partition wall and lyophilic treatment were performed.

[Examples 15-16, 24-26]
A partition wall repair curable composition was prepared and the partition wall was repaired in the same manner as in Example 14 except that the composition of the partition wall repair curable composition was changed as shown in Table 3.

[Example 17]
The composition of the curable composition for repairing barrier ribs was changed as shown in Table 3, and the method for curing a coating film made of the curable composition for repairing barrier ribs was changed to heating for 30 minutes at 150 ° C. In the same manner, a curable composition for partition wall repair was prepared and the partition wall was repaired.

[Examples 18 to 23]
While changing the composition of the curable composition for barrier rib repair as shown in Table 3, the curing method of the coating film made of the curable composition for barrier rib repair was changed to heating at 150 ° C. for 30 minutes, and exposure apparatus MA-8 (SSUS Micro Tec), the wavelength of ultraviolet rays irradiated to the cured film was 365 nm, and the exposure conditions were the same as in Example 14 except that the exposure time was 24.5 s and the exposure amount was 1 J / cm ^2. Thus, the partition wall repair curable composition was prepared and the partition wall was repaired.

(Evaluation)
The following evaluation was implemented about the partition repair part formed in Examples 14-26. The results are shown in the lower column of Table 3.
<Viscosity>
The viscosity of the composition obtained above was measured by the above method and evaluated according to the following criteria.
○: Viscosity 1 mPa · s or more and 100,000 mPa · s or less ×: Viscosity less than 1 mPa · s or 100,000 mPa · s or more

<Liquid repellency on the upper surface of the partition repair portion>
The PGMEA contact angle on the upper surface of the partition repair portion obtained above was measured by the above method.
◎: Contact angle 30 degrees or more ○: Contact angle 20 degrees or more and less than 30 degrees ×: Contact angle 20 degrees or less

<Particle top and side repellency contrast (difference in contact angle before and after exposure)>
Separately from the repair of the partition wall, the curable composition for partition wall repair is applied to the entire surface of the substrate by spin coating and cured to form a cured film. After measuring the PGMEA contact angle for the cured film, the cured film is exposed to light. Then, it was made lyophilic, the PGMEA contact angle on the surface was measured again, the difference was calculated, and evaluated according to the following criteria. In addition, hardening and exposure were performed on the conditions similar to the case of the said repair of the partition.
◎: Contact angle difference is 10 degrees or more ○: Contact angle difference is 5 degrees or more and less than 10 degrees ×: Contact angle difference is less than 5 degrees

<Wetting and spreading of ink>
6.25 g of liquid epoxy resin Pernox ME-562 (trade name, manufactured by Nippon Pernox Co., Ltd.), 6.25 g of curing agent Percure HV-562 (trade name, manufactured by Nippon Pernox Co., Ltd.), 3-butylene glycol di 33.75 g of acetate and 3.75 g of 4-butyrolactone were stirred and mixed using a stirrer for 1 hour, and water was added while stirring until the surface tension reached 35 mN / m to prepare an ink.

Using an ink jet method, about 20 pL or 40 pL of the ink prepared above is applied to an opening surrounded by a partition wall (including a repair portion) of a glass substrate, and an ultradeep shape measuring microscope VK-8500 (manufactured by Keyence Corporation) is used. By using and observing, the wetting and spreading property of the ink in the opening surrounded by the partition wall was evaluated according to the following criteria.
A: The partition repair portion is wet with ink at an ink amount of 20 pL. O: The partition repair portion is wet with ink at an ink amount of 40 pL. X: A part of the opening repels ink.

As is clear from Table 3, Examples 14 to 23 contain the liquid repellent compound (A), so that the side walls are made lyophilic by exposure after the partition walls are formed. Whereas wet spreadability is good, Examples 24 to 26 do not contain the liquid repellent compound (A), so the liquid repellency on the upper surface of the partition wall is good, but the liquid repellency is not changed by light irradiation. For this reason, the contact angle difference before and after exposure and the ink wetting and spreading property are insufficient.
In Examples 14-17 and 22-23, a perfluoroalkyl group having an etheric oxygen atom between carbon atoms is used as the Cf group of the liquid repellent compound, so that the liquid repellency on the upper surface of the partition wall and the contact angle before and after exposure are as follows. Difference and ink wettability are better.

The curable composition for barrier ribs of the present invention is a curing agent for forming barrier ribs or repairing barrier ribs when performing pattern printing by the IJ method in optical elements such as organic EL elements, quantum dot displays, TFT arrays, and thin film solar cells. It is suitable as an adhesive composition.
The barrier ribs formed or repaired according to the present invention are barrier ribs (banks) for pattern printing of organic layers such as light emitting layers by the IJ method in organic EL elements, or quantum dot layers and hole transport layers in quantum dot displays. Etc. can be used as partition walls (banks) for pattern printing by the IJ method.

  DESCRIPTION OF SYMBOLS 1 ... Board | substrate, 2 ... Partition, 2a ... Liquid-repellent upper surface, 2b ... Lipophilic side surface, 3 ... Opening part, 4 ... Defect part, 5 ... Liquid fixed quantity discharge apparatus, 6A ... Hardened film, 6B ... Side surface made lyophilic, 6 ... partition repairing part, 11 ... inkjet head, 12 ... ink, 13 ... dot, 14 ... organic EL element.

Claims (17)

A curable composition for forming a partition wall having an upper surface formed in a shape for partitioning the substrate surface into a plurality of sections for forming dots and a side surface subsequent thereto, or for repairing defects generated in the partition wall,
A liquid repellent compound (A), a crosslinking agent (B), and a polymerization initiator (C) are contained, and the liquid repellent compound (A) is lyophilic by light irradiation. A curable composition for partition walls.   The curable composition for a partition according to claim 1, wherein the liquid repellent compound (A) has a structure in which a liquid repellent site is decomposed by light irradiation.   The curable composition for a partition according to claim 2, wherein the liquid repellent compound (A) has a crosslinkable functional group.   The partition wall curable composition according to claim 3, wherein the liquid repellent compound (A) is lyophilic by irradiation with ultraviolet rays having a wavelength of less than 300 nm and contains a photopolymerization initiator as the polymerization initiator (C). Composition. The curable composition for a partition wall according to claim 4, wherein the liquid repellent compound (A) has a unit (u1-1) based on a compound represented by the following formula (m1).

However, Cf is a C1-C20 fluoroalkyl group or a C2-C20 fluoroalkyl group having an etheric oxygen atom between carbon atoms,
R ¹ and R ² are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group,
R ³ is a single bond or a divalent organic group having no fluorine atom,
At least one of R ^{4 to} R ⁸ is a group represented by the following formula (1), and the others are each independently a hydrogen atom, a halogen atom, and an optionally substituted alkyl group having 1 to 12 carbon atoms, C2-C12 alkenoyl group, C1-C12 alkoxy group, C5-C8 cycloalkyl group, C6-C20 aryl group, C7-C20 benzoyl group, C2-C2 A alkanoyl group having 12 carbon atoms, an alkoxycarbonyl group having 2 to 12 carbon atoms, a phenoxycarbonyl group having 7 to 20 carbon atoms, or a nitro group.

However, X is a single bond, an oxygen atom, a sulfur atom, a nitrogen atom or NH,
n is an integer of 0 to 4,
m is 1 when X is a single bond, an oxygen atom, a sulfur atom or NH, and is 2 when X is a nitrogen atom,
Z is a group having a crosslinkable functional group.   The curable composition for partition walls according to claim 3, wherein the liquid repellent compound (A) is lyophilic when irradiated with ultraviolet rays having a wavelength of 300 nm or more. The curable composition for a partition wall according to claim 6, wherein the liquid repellent compound (A) has a unit (u2-1) based on a compound represented by the following formula (m2).

However, Cf is a C1-C20 fluoroalkyl group or a C2-C20 fluoroalkyl group having an etheric oxygen atom between carbon atoms,
R ¹² is a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or an aryl group having 6 to 20 carbon atoms,
R ³ is a single bond or a divalent organic group having no fluorine atom,
At least one of R ^{13 to} R ¹⁷ is a monovalent organic group having a group represented by the following formula (1) at the terminal, and the others are each independently substituted with a hydrogen atom or a halogen atom. C1-C12 alkyl group, C2-C12 alkenoyl group, C1-C12 alkoxy group, C5-C8 cycloalkyl group, C6-C20 aryl group, C7-C7 20 benzoyl groups, C2-C12 alkanoyl groups, C2-C12 alkoxycarbonyl groups, C3-C20 alkoxycarbonylalkanoyl groups, C7-C20 phenoxycarbonyl groups, C8 20 of phenoxycarbonyl alkanoyl group, heteroaryloxycarbonyl alkanoyl group having 8 to 20 carbon ^atoms, -SR ^{101, -SOR} 101, -SO ₂ R ¹⁰¹ , or —NR ¹⁰¹ R ¹⁰² (where R ¹⁰¹ and R ¹⁰² are each independently a hydrogen atom, or an optionally substituted alkyl group having 1 to 12 carbon atoms or an alkenyl having 3 to 12 carbon atoms) A nitro group, a alkanoyl group having 2 to 8 carbon atoms, an aryl group having 6 to 20 carbon atoms, or a trialkylsilyl group having 3 to 15 carbon atoms), wherein R ^{13 to} R ¹⁷ are A plurality of substituents may be bonded to each other to further have a substituent, may form a saturated or unsaturated aromatic ring,
j is 0 or 1.

However, X is a single bond, an oxygen atom, a sulfur atom, a nitrogen atom or NH,
n is an integer of 0 to 4,
m is 1 when X is a single bond, an oxygen atom, a sulfur atom or NH, and is 2 when X is a nitrogen atom,
Z is a group having a crosslinkable functional group.   The curable composition for a partition according to any one of claims 1 to 7, which is a composition for a micro discharge method.   The curable composition for a partition wall according to claim 8, wherein the micro discharge method used for forming the partition wall is an inkjet method, a nozzle printing method, or a microdispenser method.   The curable composition for a partition according to any one of claims 1 to 8, having a viscosity of 1 to 100000 mPa · s, used for repairing the partition.   The curable composition for a partition according to claim 10, wherein the micro discharge method is a dispenser method.   It is a partition which has the upper surface formed in the shape which partitions off the board | substrate surface into the some division for dot formation, and the side surface following it, Comprising: The curable composition for partition of any one of Claims 1-9 is used. A partition wall having a lyophilic region on the side surface formed by the step. Curing having a top surface and a side surface subsequent to the shape corresponding to the partition wall, by applying and curing the curable composition for a partition wall according to any one of claims 1 to 9 at a predetermined position on the substrate surface. Forming a film;
The method for manufacturing a partition wall according to claim 12, comprising: irradiating light from the back surface of the substrate to form a lyophilic region on a side surface of the cured film.   An optical element having a plurality of dots and a partition located between adjacent dots on the surface of the substrate, wherein the partition is formed by the partition according to claim 12. A method of repairing a defect generated in a partition wall formed in a shape of partitioning a substrate surface into a plurality of sections for dot formation,
A cured film having an upper surface and a side surface following the upper surface, in a shape corresponding to the partition wall, by applying and curing the partition wall curable composition according to any one of claims 1 to 8, 10, and 11 to the defect. Forming a step;
Irradiating light on the side surface of the cured film to form a lyophilic region on the side surface. A partition formed in the form of partitioning the substrate surface into a plurality of sections for dot formation,
A partition repair portion comprising a cured film having an upper surface and a side surface subsequent thereto, which is formed from the curable composition for a partition according to any one of claims 1 to 8, 10, and 11, A partition wall having a lyophilic region on a side surface. An optical element having a plurality of dots and a partition wall located between adjacent dots on the substrate surface,
The said partition is formed with the partition of Claim 16, The optical element characterized by the above-mentioned.

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