CN109661855B

CN109661855B - Photosensitive resin composition for forming organic electroluminescent element spacer, organic electroluminescent element, image display device, and lighting

Info

Publication number: CN109661855B
Application number: CN201780054034.0A
Authority: CN
Inventors: 木村明日香; 中谷和裕; 土谷达格
Original assignee: Mitsubishi Chemical Corp
Current assignee: Mitsubishi Chemical Corp
Priority date: 2016-09-05
Filing date: 2017-09-04
Publication date: 2022-07-08
Anticipated expiration: 2037-09-04
Also published as: TW202141185A; TWI826804B; JP7099319B2; KR20220139427A; CN109661855A; JPWO2018043746A1; WO2018043746A1; CN115185156A; TWI819333B; TW202140680A; TWI806838B; KR102451212B1; KR20190046834A; TW201826025A

Abstract

The invention provides a photosensitive resin composition for forming partition walls of an organic electroluminescent element, which has a small amount of outgas generation during operation of the light-emitting element, high reliability and a large taper angle. The photosensitive resin composition for forming an organic electroluminescent element partition wall of the present invention comprises (A) an ethylenically unsaturated compound, (B) a photopolymerization initiator, and (C) an alkali-soluble resin, wherein the alkali-soluble resin (C) comprises an alkali-soluble resin (C) having a partial structure represented by the following general formula (1), and the photosensitive resin composition further comprises (E) a chain transfer agent. (in the formula (1), R¹Represents a C1-4 valent hydrocarbon group optionally having a substituent, and represents a bonding position. )

Description

Photosensitive resin composition for forming organic electroluminescent element partition wall, organic electroluminescent element, image display device, and illumination

Technical Field

The present invention relates to a photosensitive resin composition for forming partition walls of an organic electroluminescent element, and more particularly to a partition wall formed from a photosensitive resin composition for forming partition walls of an organic electroluminescent element, an organic electroluminescent element provided with the partition wall, and an image display device and an illumination device comprising the organic electroluminescent element.

Background

Conventionally, organic electroluminescent devices included in organic electroluminescent displays, organic electroluminescent illuminations, and the like are manufactured by forming partition walls (dams) on a substrate and then laminating various functional layers in regions surrounded by the partition walls. As a method for easily forming such partition walls, a method of forming the partition walls by photolithography using a photosensitive resin composition is known.

In addition, as a method of laminating various functional layers in the region surrounded by the partition walls, there is known a method of preparing ink including a material constituting the functional layers first and then injecting the prepared ink into the region surrounded by the partition walls. In this method, since a predetermined amount of ink can be easily and accurately injected into a predetermined portion, an ink jet method is often used.

Further, when the functional layer is formed using ink, it is sometimes required to impart ink repellency to the partition walls for the purpose of preventing adhesion of ink to the partition walls, preventing mixing of ink injected between adjacent regions, and the like. In recent years, partition walls have been required to have various properties in addition to ink repellency, and various photosensitive resin compositions have been developed. For example, patent document 1 describes the following: by using a specific alkali-soluble resin, a specific liquid repellent and a specific surfactant, it is possible to cope with a high-resolution image without causing disconnection of the electrodes.

On the other hand, patent document 2 describes the following: by using a resin obtained by adding (meth) acrylic acid to a bisphenol a type epoxy resin, further adding succinic anhydride, and further adding a bisphenol a type epoxy resin, a coating film having excellent heat-resistant coloring properties can be obtained.

Documents of the prior art

Patent document

Patent document 1: japanese laid-open patent publication No. 2010-061093

Patent document 2: japanese laid-open patent application No. 2010-150397

Disclosure of Invention

Problems to be solved by the invention

In recent years, in order to improve the driving life of the element, it is necessary to reduce the amount of outgassing generated by the partition wall when the element emits light after the partition wall is formed. In addition, in order to suppress a decrease in luminance due to the overlap between the lower portion of the partition wall and the light emitting portion and a decrease in light emission characteristics due to the contact portion between the partition wall and the light emitting portion, and to ensure coating adaptability in forming the light emitting portion by an ink jet method, it is necessary to increase the taper angle of the partition wall.

The present inventors have studied and found that it is difficult to sufficiently reduce the amount of outgas generated when a light-emitting element is operated, by using the photosensitive resin composition for forming partition walls described in patent document 1. Also, the taper angle of the obtained partition wall is small.

Patent document 2 does not disclose the partition wall, and the present inventors have conducted studies to apply the photosensitive resin composition described in patent document 2 to the partition wall, and as a result, have found that the taper angle of the obtained partition wall is small when the photosensitive resin composition is used.

Accordingly, an object of the present invention is to provide a photosensitive resin composition for forming partition walls of an organic electroluminescent element which is less in outgas generation amount during operation of the light-emitting element, high in reliability, and large in taper angle.

Further, the present invention aims to provide a partition wall formed using the photosensitive resin composition for forming a partition wall of an organic electroluminescent element, an organic electroluminescent element provided with the partition wall, an image display device and an illumination device including the organic electroluminescent element.

Means for solving the problems

As a result of intensive studies, the present inventors have found that the above problems can be solved by using a resin having a specific partial structure as an alkali-soluble resin and further using a chain transfer agent, and have completed the present invention.

That is, the gist of the present invention is as follows.

A photosensitive resin composition for forming an organic electroluminescent element partition wall, comprising (A) an ethylenically unsaturated compound, (B) a photopolymerization initiator, and (C) an alkali-soluble resin, wherein the alkali-soluble resin (C) contains an alkali-soluble resin (C) having a partial structure represented by the following general formula (1), and the photosensitive resin composition further contains (E) a chain transfer agent.

[ chemical formula 1]

(in the formula (1), R¹Represents an optionally substituted 2-valent hydrocarbon group having 1 to 4 carbon atoms, and represents a bonding position. )

<2> the photosensitive resin composition for forming partition walls of organic electroluminescent elements <1>, wherein the alkali-soluble resin (c) is a resin having an ethylenically unsaturated group.

<3> the photosensitive resin composition for forming partition walls of organic electroluminescent elements <1> or <2>, wherein the alkali-soluble resin (c) contains (c1) an epoxy (meth) acrylate resin.

<4> the photosensitive resin composition for forming an organic electroluminescent element partition wall of <3>, wherein the epoxy (meth) acrylate resin (c1) contains at least one selected from the group consisting of: an epoxy (meth) acrylate resin containing a repeating unit structure represented by the following formula (i), an epoxy (meth) acrylate resin containing a partial structure represented by the following formula (ii), and an epoxy (meth) acrylate resin containing a partial structure represented by the following formula (iii).

[ chemical formula 2]

(in the formula (i), R^aRepresents a hydrogen atom or a methyl group, R^bRepresents a 2-valent hydrocarbon group optionally having a substituent, the benzene ring in the formula (i) is optionally further substituted with an optional substituent, and represents a bonding position. )

[ chemical formula 3]

(in the formula (ii), R^cEach independently represents a hydrogen atom or a methyl group. R is^dRepresents a 2-valent hydrocarbon group having a cyclic hydrocarbon group as a side chain, and represents a bonding position. )

[ chemical formula 4]

(in the formula (iii), R^eRepresents a hydrogen atom or a methyl group, γ represents a single bond, -CO-, an alkylene group optionally having a substituent, or a 2-valent cyclic hydrocarbon group optionally having a substituent, and the benzene ring in the formula (iii) is optionally further substituted with an optional substituent, and x represents a bonding position. )

<5> the photosensitive resin composition for forming partition walls of organic electroluminescent element <3> or <4>, wherein the epoxy (meth) acrylate resin (c1) is obtained by adding an acid or ester compound having an ethylenically unsaturated bond to an epoxy resin and further adding a polybasic acid or an anhydride thereof.

<6> the photosensitive resin composition for forming a partition wall of an organic electroluminescent element as described in any one of <1> to <5>, which further comprises (D) a liquid repellent.

<7> the photosensitive resin composition for forming partition walls of organic electroluminescent element <6>, wherein the liquid repellent (D) contains a liquid repellent having a crosslinking group.

<8> the photosensitive resin composition for forming partition walls of organic electroluminescent elements <1> to <7>, which further contains an ultraviolet absorber.

<9> the photosensitive resin composition for forming an organic electroluminescent element partition wall described in any one of <1> to <8>, wherein the acid value of the photosensitive resin composition for forming an organic electroluminescent element partition wall is 20mgKOH/g or more based on the total solid content.

<10> a partition wall formed of the photosensitive resin composition for forming a partition wall between organic electroluminescent elements <1> to <9 >.

<11> an organic electroluminescent element comprising the partition wall <10 >.

<12> an image display device comprising the organic electroluminescent element <11 >.

<13> an illumination device comprising the organic electroluminescent element <11 >.

ADVANTAGEOUS EFFECTS OF INVENTION

The present invention can provide a photosensitive resin composition for forming partition walls of an organic electroluminescent element which is less in outgas generation amount during operation of the light-emitting element, has high reliability, and has a large taper angle.

Drawings

Fig. 1 is an explanatory view of a method for evaluating a taper angle of a partition wall.

Description of the symbols

1: partition wall

2: ITO film

3: glass substrate

T: tangent to the hypotenuse adjoining the interface S

H: height of partition wall

S: interface between spacer and ITO film

Detailed Description

The present invention will be described in detail below. The following description is an example of the embodiment of the present invention, and the present invention is not limited to these examples within the scope not exceeding the gist thereof.

In the present invention, "(meth) acrylic acid" means "acrylic acid and/or methacrylic acid", "meth) acrylate" means "acrylate and/or methacrylate", and "total solid content" means all components excluding the solvent in the photosensitive resin composition for forming a spacer for an organic electroluminescent element. In the present invention, the numerical range represented by "to" represents a range including numerical values described before and after "to" as a lower limit value and an upper limit value.

In the present invention, the term "(co) polymer" includes both a single polymer (homopolymer) and a copolymer (copolymer), and the terms "(acid) anhydride)" and "… acid (anhydride)" include both an acid and its acid anhydride.

In the present invention, "polybasic acid (anhydride)" means "polybasic acid and/or polybasic anhydride".

In the present invention, the weight average molecular weight refers to a weight average molecular weight (Mw) calculated by polystyrene conversion based on GPC (gel permeation chromatography).

In the present invention, the partition wall material refers to a dam material and a wall material, and similarly, the partition wall refers to a dam and a wall.

In the present invention, the light-emitting portion means a portion that emits light when electric energy is applied.

In the present invention, "mass" and "weight" are synonymous.

In the present invention, a × "in the chemical formula represents a bonding position.

In the present invention, "large taper angle" is synonymous with "high taper angle", and "small taper angle" is synonymous with "low taper angle".

[1] Photosensitive resin composition for forming organic electroluminescent element spacer

The photosensitive resin composition for forming a spacer of an organic electroluminescent element according to embodiment 1 of the present invention comprises (a) an ethylenically unsaturated compound, (B) a photopolymerization initiator, and (C) an alkali-soluble resin, wherein the alkali-soluble resin (C) contains an alkali-soluble resin (C) having a partial structure represented by general formula (1) described later, and the photosensitive resin composition further contains (E) a chain transfer agent. Other components may be further contained as necessary, and for example, (D) a liquid repellent agent and an ultraviolet absorber may be contained.

The photosensitive resin composition for forming a spacer of an organic electroluminescent element according to embodiment 2 of the present invention comprises (a) an ethylenically unsaturated compound, (B) a photopolymerization initiator, and (C) an alkali-soluble resin, wherein the ethylenically unsaturated compound (a) contains (a1) an ethylenically unsaturated compound having an acid group, and the content of the ethylenically unsaturated compound (a1) having an acid group in the total solid content is 30% by mass or less. Other components may be further contained as necessary, and for example, (D) a liquid repellent, (E) a chain transfer agent, and an ultraviolet absorber may be contained.

Hereinafter, the "photosensitive resin composition for forming an organic electroluminescent element partition wall" of the present invention refers to both the photosensitive resin composition for forming an organic electroluminescent element partition wall according to embodiment 1 and the photosensitive resin composition for forming an organic electroluminescent element partition wall according to embodiment 2, unless otherwise specified.

In the present invention, the partition walls are, for example, portions for partitioning the functional layer (organic layer, light emitting portion) in the active-drive-type organic electroluminescent element, and are used for forming pixels including the functional layer and the partition walls by discharging ink, which is a material for constituting the functional layer, to the partitioned regions (pixel regions) and drying the ink.

[1-1] Components and compositions of photosensitive resin compositions for Forming spacer walls of organic electroluminescent elements

The components and composition of the photosensitive resin composition for forming organic electroluminescent element partition walls according to the present invention will be described.

The photosensitive resin composition for forming a spacer wall of an organic electroluminescent element according to embodiment 1 of the present invention (hereinafter, also simply referred to as "photosensitive resin composition of embodiment 1") contains (a) an ethylenically unsaturated compound, (B) a photopolymerization initiator, and (C) an alkali-soluble resin, and further contains (E) a chain transfer agent, and usually further contains a solvent. The photosensitive resin composition for forming partition walls between organic electroluminescent elements of embodiment 1 of the present invention is preferably used for forming partition walls having liquid repellency, and from such a viewpoint, (D) a liquid repellent is preferably contained, and as the components (a) to (C) and (E), a component exhibiting an action as a liquid repellent may be used.

The photosensitive resin composition for forming a spacer wall of an organic electroluminescent element according to embodiment 2 of the present invention (hereinafter, also simply referred to as "photosensitive resin composition of embodiment 2") contains (a) an ethylenically unsaturated compound, (B) a photopolymerization initiator, and (C) an alkali-soluble resin, wherein the ethylenically unsaturated compound (a) contains (a1) an ethylenically unsaturated compound having an acid group, and the content of the ethylenically unsaturated compound (a1) having an acid group in the total solid content is 30% by mass or less, and usually further contains a solvent. The photosensitive resin composition for forming partition walls of an organic electroluminescent element of embodiment 2 of the present invention is preferably used for forming partition walls having liquid repellency, and from such a viewpoint, (D) a liquid repellent is preferably contained, and as the components (a) to (C), a component exhibiting an action as a liquid repellent may be used.

[1-1-1] (A) component; ethylenically unsaturated compounds

The photosensitive resin composition for forming a spacer of an organic electroluminescent element of embodiment 1 of the present invention contains (A) an ethylenically unsaturated compound. It is considered that by containing (a) the ethylenically unsaturated compound, high sensitivity can be obtained.

The ethylenically unsaturated compound used herein is a compound having 1 or more ethylenically unsaturated bonds in the molecule, but is preferably a compound having 2 or more ethylenically unsaturated bonds in the molecule from the viewpoint of the ability to expand polymerizability, crosslinkability, and a difference in solubility of a developer between an exposed portion and a non-exposed portion accompanying the same, and is more preferably an unsaturated bond derived from a (meth) acryloyloxy group, that is, a (meth) acrylate compound.

In the photosensitive resin composition for forming partition walls of an organic electroluminescent element of the present invention according to embodiment 1, a polyfunctional ethylenic monomer having 2 or more ethylenic unsaturated bonds in 1 molecule is particularly preferably used. The number of the ethylenically unsaturated groups of the polyfunctional ethylenic monomer is not particularly limited, but is preferably 2 or more, more preferably 3 or more, further preferably 4 or more, and particularly preferably 5 or more, and is preferably 15 or less, more preferably 10 or less, further preferably 8 or less, and particularly preferably 7 or less. When the amount is equal to or more than the lower limit, the polymerizability tends to be improved and high sensitivity tends to be obtained, and when the amount is equal to or less than the upper limit, the developability tends to be more favorable.

Specific examples of the ethylenically unsaturated compound include: esters of aliphatic polyols with unsaturated carboxylic acids; esters of aromatic polyhydroxy compounds with unsaturated carboxylic acids; esters obtained by esterification of a polyhydric hydroxyl compound such as an aliphatic polyhydric compound or an aromatic polyhydric compound with an unsaturated carboxylic acid or a polybasic carboxylic acid.

Examples of the ester of the aliphatic polyhydric compound and the unsaturated carboxylic acid include: ethylene glycol diacrylate, triethylene glycol diacrylate, trimethylolpropane triacrylate, trimethylolethane triacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, glycerol acrylate, and other aliphatic polyol acrylates, methacrylates obtained by replacing the acrylate of the above-exemplified compounds with methacrylate, itaconate esters similarly replaced with itaconate esters, crotonate esters replaced with crotonate esters, and maleate esters replaced with maleate esters.

As the ester of an aromatic polyhydroxy compound and an unsaturated carboxylic acid, there may be mentioned: acrylic acid esters and methacrylic acid esters of aromatic polyhydroxy compounds such as hydroquinone diacrylate, hydroquinone dimethacrylate, resorcinol diacrylate, resorcinol dimethacrylate and pyrogallol triacrylate.

The ester obtained by esterification of a polyhydric hydroxyl compound such as an aliphatic polyhydric compound or an aromatic polyhydric compound with an unsaturated carboxylic acid or a polybasic carboxylic acid is not necessarily a single compound, and typical examples thereof include: condensates of acrylic acid, phthalic acid and ethylene glycol, condensates of acrylic acid, maleic acid and diethylene glycol, condensates of methacrylic acid, terephthalic acid and pentaerythritol, condensates of acrylic acid, adipic acid, butanediol and glycerol, and the like.

Further, as examples of the polyfunctional olefinic monomer used in the photosensitive resin composition for forming a spacer wall of an organic electroluminescent element of embodiment 1 of the present invention, urethane (meth) acrylates obtained by reacting a polyisocyanate compound with a hydroxyl group-containing (meth) acrylate or a polyol and a hydroxyl group-containing (meth) acrylate; epoxy acrylates such as addition reaction products of a polyhydric epoxy compound with hydroxy (meth) acrylate or (meth) acrylic acid; acrylamides such as ethylene bisacrylamide; allyl esters such as diallyl phthalate; vinyl group-containing compounds such as divinyl phthalate are useful.

Examples of the urethane (meth) acrylates include: DPHA-40H, UX-5000, UX-5002D-P20, UX-5003D, UX-5005 (manufactured by Nippon Kagaku Co., Ltd.), U-2PPA, U-6LPA, U-10PA, U-33H, UA-53H, UA-32P, UA-1100H (manufactured by Ninghamu chemical Co., Ltd.), UA-306H, UA-510H, UF-8001G (manufactured by Kyokun chemical Co., Ltd.), UV-1700B, UV-7600B, UV-7605B, UV-7630B, UV7640 867640 7640B (manufactured by Nippon synthetic chemical Co., Ltd.), and the like.

Of these, from the viewpoint of an appropriate taper angle and sensitivity, ester (meth) acrylates or urethane (meth) acrylates are preferably used as the ethylenically unsaturated compound (a), and dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, 2-tri (meth) acryloyloxymethyl ethyl phthalic acid, pentaerythritol tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, a dibasic anhydride adduct of dipentaerythritol penta (meth) acrylate, a dibasic anhydride adduct of pentaerythritol tri (meth) acrylate, and the like are more preferably used.

In addition, from the viewpoint of suppressing the generation of residue, the ethylenically unsaturated compound described later as embodiment 2 is also preferably used.

These compounds may be used alone or in combination of two or more.

In the photosensitive resin composition for forming partition walls of an organic electroluminescent element of the present invention according to embodiment 1, the molecular weight of the ethylenically unsaturated compound (a) is not particularly limited, but is preferably 100 or more, more preferably 150 or more, further preferably 200 or more, further preferably 300 or more, particularly preferably 400 or more, most preferably 500 or more, and preferably 1,000 or less, more preferably 700 or less, from the viewpoint of sensitivity, liquid repellency, and taper angle.

The number of carbon atoms of the ethylenically unsaturated compound (a) is not particularly limited, but is preferably 7 or more, more preferably 10 or more, further preferably 15 or more, further preferably 20 or more, particularly preferably 25 or more, and preferably 50 or less, more preferably 40 or less, further preferably 35 or less, and particularly preferably 30 or less, from the viewpoint of sensitivity, liquid repellency, and cone angle.

In addition, from the viewpoints of sensitivity, liquid repellency, and cone angle, ester (meth) acrylates, epoxy (meth) acrylates, and urethane (meth) acrylates are preferable, and among them, from the viewpoints of sensitivity, liquid repellency, and cone angle, trifunctional or higher ester (meth) acrylates such as pentaerythritol tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and dipentaerythritol penta (meth) acrylate, and trifunctional or higher ester (meth) acrylate anhydride adducts such as 2,2, 2-tris (meth) acryloyloxymethylethyl phthalate, and dibasic anhydride adducts of dipentaerythritol penta (meth) acrylate are more preferable.

The content of the ethylenically unsaturated compound (a) in the photosensitive resin composition of the present invention according to embodiment 1 is usually 5% by mass or more, preferably 10% by mass or more, more preferably 20% by mass or more, further preferably 30% by mass or more, particularly preferably 40% by mass or more, and usually 80% by mass or less, preferably 70% by mass or less, more preferably 60% by mass or less, further preferably 55% by mass or less, particularly preferably 50% by mass or less, relative to the total solid content. When the value is equal to or higher than the lower limit, sensitivity and a taper angle at the time of exposure tend to be good, and when the value is equal to or lower than the upper limit, developability tends to be good.

The content of the ethylenically unsaturated compound (a) is usually 15 parts by mass or more, preferably 30 parts by mass or more, more preferably 50 parts by mass or more, further preferably 80 parts by mass or more, and particularly preferably 90 parts by mass or more, and usually 150 parts by mass or less, preferably 130 parts by mass or less, more preferably 120 parts by mass or less, and further preferably 110 parts by mass or less, based on 100 parts by mass of the alkali-soluble resin (C). When the value is equal to or higher than the lower limit, the sensitivity during exposure tends to be good and the taper angle tends to be good, and when the value is equal to or lower than the upper limit, the developability tends to be good.

On the other hand, the photosensitive resin composition for forming a spacer wall of an organic electroluminescent element according to embodiment 2 of the present invention contains (A) an ethylenically unsaturated compound. It is considered that by containing (a) the ethylenically unsaturated compound, high sensitivity can be obtained.

< A1) an ethylenically unsaturated compound having an acid group >

The photosensitive resin composition for forming a spacer of an organic electroluminescent element according to embodiment 2 of the present invention contains (a1) an ethylenically unsaturated compound having an acid group in the ethylenically unsaturated compound (a) and the content of the ethylenically unsaturated compound having an acid group in the (a1) is 30% by mass or less in the total solid content. It is considered that by containing (a1) the ethylenically unsaturated compound having an acid group in this manner, the compound is excellent in solubility in a developer, and therefore, generation of residue in the pixel portion (light-emitting portion) can be suppressed, and the inkjet application characteristics can be improved. Further, it is considered that when the content ratio of the compound is not more than the above upper limit value, the occurrence of degassing derived from an acid group contained in the compound can be reduced, and the occurrence of degassing from the partition wall after formation can be sufficiently suppressed.

The ethylenically unsaturated compound means a compound having 1 or more ethylenically unsaturated bonds in the molecule. The number of ethylenically unsaturated bonds in 1 molecule of the ethylenically unsaturated compound having an acid group (a1) is not particularly limited as long as it is 1 or more, but is preferably 2 or more, more preferably 3 or more, further preferably 4 or more, particularly preferably 5 or more, and usually 15 or less, preferably 12 or less, more preferably 10 or less, and further preferably 8 or less, from the viewpoint of being able to expand the difference in polymerizability, crosslinkability, and the developer solubility of exposed portions and unexposed portions accompanying the same. When the content is not less than the lower limit, the polymerizability is improved to obtain high sensitivity, the curability is improved, and the amount of outgas generation is reduced along with the improvement, and when the content is not more than the upper limit, the developability tends to be more favorable.

The number of acid groups in 1 molecule of the ethylenically unsaturated compound having an acid group (a1) is not particularly limited as long as it is 1 or more, but is preferably 4 or less, more preferably 2 or less, and still more preferably 1 from the viewpoint of curability. When the content is less than the above upper limit, the residual film ratio tends to be improved.

The type of the acid group contained in the ethylenically unsaturated compound having an acid group (a1) is not particularly limited, and examples thereof include a carboxyl group, a phosphoric acid group, and a sulfonic acid group, and a carboxyl group is preferable from the viewpoint of developability. When 2 or more acid groups are present, the acid groups may be the same or different.

(A1) The molecular weight of the ethylenically unsaturated compound having an acid group is not particularly limited, but is preferably 100 or more, more preferably 200 or more, further preferably 300 or more, particularly preferably 350 or more, and is preferably 1,000 or less, more preferably 800 or less, further preferably 700 or less. When the lower limit value or more is exceeded, the residual film ratio tends to be improved, and when the upper limit value or less is exceeded, the residual film tends to be reduced.

(A1) The chemical structure of the ethylenically unsaturated compound having an acid group is not particularly limited, and from the viewpoint of developability, for example, a compound represented by the following general formula (a1) is preferable.

[ chemical formula 5]

In the above formula (a1), R^a1Represents a hydrogen atom or a methyl group, R^a2、R^a3、R^a5And R^a6Each independently represents an alkylene group optionally having a substituent.

R^a4Represents a linking group having a valence of n + 1.

R^a7Represents an alkylene group optionally having a substituent, an alkenylene group optionally having a substituent or a 2-valent aromatic ring group optionally having a substituent.

l and m each independently represent an integer of 0 to 12.

n represents an integer of 1 or more.

(R^a2、R^a3、R^a5And R^a6)

In the above general formula (a1), R^a2、R^a3、R^a5And R^a6Each independently represents an alkylene group optionally having a substituent.

The alkylene group may be linear, branched or cyclic, or a combination thereof. The number of carbon atoms is not particularly limited, but is usually 1 or more, and is usually 4 or less, preferably 2 or less. When the content is not more than the above upper limit, the residual film ratio tends to be improved.

Specific examples of the alkylene group include: methylene, ethylene, propylene, butylene, cyclohexylene, and the like, and methylene or ethylene is preferable, and methylene is more preferable, from the viewpoint of curability.

Examples of the substituent optionally contained in the alkylene group include an alkoxy group, a halogen atom (-F, -Cl, -Br, -I), a hydroxyl group, and a carboxyl group, and the substituent is preferably unsubstituted from the viewpoint of curability.

(R^a4)

In the above general formula (a1), R^a4Represents a linking group having a valence of n + 1. The chemical structure of the n + 1-valent linking group is not particularly limited, and an n + 1-valent hydrocarbon group optionally having a substituent may be mentioned. The hydrocarbon group may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group, and is preferably an aliphatic hydrocarbon group from the viewpoint of developability. The carbon-carbon single bond in the hydrocarbon group may be interrupted by at least 1 selected from the group consisting of-O-, -CO-and-NH-.

Specific examples of the n + 1-valent linking group include the following groups.

[ chemical formula 6]

(R^a7)

In the above general formula (a1), R^a7Represents an alkylene group optionally having a substituent, an alkenylene group optionally having a substituent or a 2-valent aromatic ring group optionally having a substituent.

R^a7The alkylene group in (b) may be linear, branched or cyclic, or a combination thereof. The number of carbon atoms is not particularly limited, and is usually 1 or more, preferably 2 or more, and usually 8 or less, preferably 6 or less, more preferably 4 or less, and further preferably 3 or less. When the lower limit value is not less than the above-described lower limit value, the residual film ratio tends to be improved, and when the upper limit value is not more than the above-described upper limit value, the residue tends to be reduced, and the amount of outgas generation tends to be reduced.

Specific examples of the alkylene group include: methylene, ethylene, propylene, hexylene, cyclohexylene and the like, and from the viewpoint of developability, methylene or ethylene is preferred, and ethylene is more preferred.

R^a7The alkenylene group in (b) may be a linear chain, a branched chain, a cyclic chain, or a combination thereof. The number of carbon atoms is not particularly limited, but is usually 2 or more, preferably 4 or more, and usually 8 or less, preferably 6 or less. When the lower limit value is not less than the above-described lower limit value, the residual film ratio tends to be improved, and when the upper limit value is not more than the above-described upper limit value, the residual film ratio tends to be reduced.

Specific examples of alkenylene groups include: vinylene, propenylene, butenylene, cyclohexenylene, and the like, and from the viewpoint of developability and curability, vinylene or cyclohexenylene is preferred, and vinylene is more preferred.

Examples of the substituent optionally contained in the alkenylene group include an alkoxy group, a halogen atom (-F, -Cl, -Br, -I), a hydroxyl group, and a carboxyl group, and the substituent is preferably unsubstituted from the viewpoint of curability.

As R^a7As the 2-valent aromatic ring group in (1), a 2-valent aromatic ring group and a 2-valent aromatic heterocyclic group are exemplified. The number of carbon atoms is usually 4 or more, preferably 5 or more, more preferably 6 or more, and preferably 40 or less, more preferably 30 or less, further preferably 20 or less, further preferably 15 or less, and particularly preferably 10 or less. When the content is not less than the lower limit, the residual film ratio tends to be improved, and when the content is not more than the upper limit, the residual film ratio tends to be reduced.

The aromatic hydrocarbon ring in the 2-valent aromatic hydrocarbon ring group may be a single ring or a condensed ring. As the 2-valent aromatic hydrocarbon ring group, for example: a group having 2 free valences of a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a perylene ring, a tetracene ring, a pyrene ring, a benzopyrene ring, a benzophenanthrene ring, an acenaphthene ring, a fluoranthene ring, a fluorene ring, or the like.

The aromatic heterocyclic ring in the 2-valent aromatic heterocyclic group may be a monocyclic ring or a condensed ring. Examples of the 2-valent aromatic heterocyclic group include: furan, benzofuran, thiophene, benzothiophene, pyrrole, pyrazole, imidazole, or imidazole rings having 2 free valences,

A diazole ring, an indole ring, a carbazole ring, a pyrroloimidazole ring, a pyrrolopyrazole ring, a pyrrolopyrrole ring, a thienopyrrole ring, a thienothiophene ring, a furopyrrole ring, a furofuran ring, a thienofuran ring, a benzisoxazole ring, a benzisothiazole ring, a benzimidazole ring, a pyridine ring, a pyrazine ring, a pyridazine ring, a pyrimidine ring, a triazine ring, a quinoline ring, an isoquinoline ring, a cinnoline ring, a quinoxaline ring, a phenanthridine ring, a benzimidazole ring, a pyridine ring, a pyrazine ring, a pyrimidine ring, a triazine ring, a quinoline ring, an isoquinoline ring, a cinnoline ring, a quinoxaline ring, a phenanthridine ring, a benzimidazole ring, a pyridine ring, a thiophene ring, a pyridine ring, a triazine ring, a derivative compound, a derivative compound, a derivative or a derivative compound or a derivative or derivative thereof, or a derivative compound or a derivative thereof,

A pyridine ring, a quinazoline ring, a quinazolinone ring, an azulene ring, and the like.

Of these, benzene rings or naphthalene rings having 2 free valences are preferable, and benzene rings having 2 free valences are more preferable from the viewpoint of curability.

Examples of the substituent optionally contained in the 2-valent aromatic ring group include an alkyl group, an alkoxy group, a halogen atom (-F, -Cl, -Br, -I), a hydroxyl group, and a carboxyl group. Among these, from the viewpoint of curability, the resin is preferably unsubstituted.

Among these, R is R from the viewpoint of securing developability and reducing the amount of outgas generation^a7Preferred is an alkylene group optionally having a substituent, more preferred is an unsubstituted alkylene group, and further preferred is an ethylene group.

(l and m)

In the general formula (a1), l and m each independently represent an integer of 0 to 12. From the viewpoint of developability, it is preferably 1 or more, more preferably 2 or more, and from the viewpoint of curability, it is preferably 8 or less, more preferably 6 or less, further preferably 4 or less, and particularly preferably 2 or less. On the other hand, from the viewpoint of reducing the amount of outgas generated, 0 is preferred.

(n)

In the general formula (a1), n represents an integer of 1 or more. n is preferably 2 or more, more preferably 3 or more, further preferably 4 or more, particularly preferably 5 or more, and further preferably 6 or less. When the lower limit value is not less than the above lower limit value, the amount of outgas generation tends to decrease as the residual film ratio increases and the curability increases, and when the upper limit value is not more than the above upper limit value, the amount of residue tends to decrease.

Examples of the (a1) ethylenically unsaturated compound having an acid group include: esters obtained by esterification of a polyhydric hydroxyl compound such as an aliphatic polyhydric compound or an aromatic polyhydric compound with an unsaturated carboxylic acid and a polybasic carboxylic acid are not necessarily single compounds, and typical examples thereof include: condensates of acrylic acid, phthalic acid, and pentaerythritol, condensates of acrylic acid, succinic acid, and pentaerythritol, and condensates of acrylic acid, succinic acid, and dipentaerythritol.

In the photosensitive resin composition for forming partition walls of an organic electroluminescent element according to embodiment 2 of the present invention, the content of the ethylenically unsaturated compound having an acid group (a1) is not particularly limited as long as it is 30% by mass or less of the total solid content, but is preferably 27% by mass or less, more preferably 25% by mass or less, further preferably 22% by mass or less, still further preferably 20% by mass or less, particularly preferably 15% by mass or less, and further preferably 1% by mass or more, more preferably 5% by mass or more, and still further preferably 10% by mass or more. When the amount of outgas generation is less than the upper limit, the amount of outgas generation tends to decrease, and when the amount is more than the lower limit, the ink jet coating suitability tends to improve.

The content of the ethylenically unsaturated compound having an acid group (a1) in the ethylenically unsaturated compound (a) is not particularly limited, but is preferably 50% by mass or less, more preferably 45% by mass or less, further preferably 40% by mass or less, further preferably 35% by mass or less, particularly preferably 30% by mass or less, and further preferably 1% by mass or more, more preferably 10% by mass or more, and further preferably 25% by mass or more. When the amount of outgas generation is less than the upper limit, the amount of outgas generation tends to decrease, and when the amount is more than the lower limit, the ink jet coating suitability tends to improve.

< (A2) an ethylenically unsaturated compound having no acid group

In the photosensitive resin composition for forming a spacer for an organic electroluminescent element of the present invention according to embodiment 2, (a) the ethylenically unsaturated compound (a) may contain (a2) an ethylenically unsaturated compound having no acid group in addition to (a1) the ethylenically unsaturated compound having an acid group. (A2) The ethylenically unsaturated compound having no acid group means an ethylenically unsaturated compound other than the ethylenically unsaturated compound having an acid group (A1) in the ethylenically unsaturated compound (A). By containing (a2) the ethylenically unsaturated compound having no acid group, curability is improved, the minimum exposure amount necessary for liquid repellency to be produced is reduced, and the amount of outgas generation tends to be reduced.

(A2) The number of the ethylenically unsaturated bonds in 1 molecule of the ethylenically unsaturated compound having no acid group is not particularly limited as long as it is 1 or more, but is preferably 2 or more, more preferably 3 or more, further preferably 4 or more, further preferably 5 or more, particularly preferably 6 or more, and in addition, usually 15 or less, preferably 12 or less, more preferably 10 or less, further preferably 8 or less, from the viewpoint of being able to expand the difference in polymerizability, crosslinkability, and the developer solubility of the exposed portion and the unexposed portion accompanying the same. When the amount is equal to or more than the lower limit, the polymerization property is improved to obtain high sensitivity, the curability is improved, and the amount of outgas generation is reduced along with the improvement, and when the amount is equal to or less than the upper limit, the developability tends to be more favorable.

(A2) The molecular weight of the ethylenically unsaturated compound having no acid group is not particularly limited, but is preferably 200 or more, more preferably 250 or more, and even more preferably 300 or more, and is preferably 1,000 or less, more preferably 800 or less, and even more preferably 600 or less. When the content is not less than the lower limit, the residual film ratio tends to be improved, and when the content is not more than the upper limit, the residual film ratio tends to be reduced.

The ethylenically unsaturated compound having no acid group (a2) is preferably a compound having a (meth) acryloyloxy group, that is, a (meth) acrylate compound, in terms of the ability to expand polymerizability, crosslinkability, and a difference in developer solubility between an exposed portion and a non-exposed portion associated therewith.

Specific examples of the ethylenically unsaturated compound having no acid group (a2) include: esters of aliphatic polyhydroxy compounds with unsaturated carboxylic acids; esters of aromatic polyhydroxy compounds with unsaturated carboxylic acids, and the like.

Examples of the ester of the aliphatic polyhydroxy compound and the unsaturated carboxylic acid include: ethylene glycol diacrylate, triethylene glycol diacrylate, trimethylolpropane triacrylate, trimethylolethane triacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, glycerol acrylate, and other aliphatic polyol acrylates, methacrylates obtained by replacing the acrylate of these exemplified compounds with methacrylate, itaconate esters similarly replaced with itaconate esters, crotonate esters replaced with crotonate esters, and maleate esters replaced with maleate esters.

Urethane (meth) acrylates obtained by reacting a polyisocyanate compound with a hydroxyl group-containing (meth) acrylate or a polyol and a hydroxyl group-containing (meth) acrylate; epoxy acrylates such as addition reaction products of a polyhydric epoxy compound with hydroxy (meth) acrylate or (meth) acrylic acid; acrylamides such as ethylene bisacrylamide; allyl esters such as diallyl phthalate; vinyl group-containing compounds such as divinyl phthalate and the like are useful.

Examples of the urethane (meth) acrylates include: DPHA-40H, UX-5000, UX-5002D-P20, UX-5003D, UX-5005 (manufactured by Nippon Kagaku Co., Ltd.), U-2PPA, U-6LPA, U-10PA, U-33H, UA-53H, UA-32P, UA-1100H (manufactured by Ninghamu chemical Co., Ltd.), UA-306H, UA-510H, UF-8001G (manufactured by Kakko Kagaku Co., Ltd.), UV-1700B, UV-7600B, UV-7605B, UV-7630B, UV7640B (manufactured by Nippon synthetic chemical Co., Ltd.), and the like.

Among these, from the viewpoint of curability, ester (meth) acrylates or urethane (meth) acrylates are preferably used as the ethylenically unsaturated compound having no acid group (a2), and dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, pentaerythritol tetra (meth) acrylate, and pentaerythritol tri (meth) acrylate are more preferably used.

These compounds may be used alone or in combination of two or more.

In the photosensitive resin composition for forming partition walls of an organic electroluminescent element according to embodiment 2 of the present invention, the content of the ethylenically unsaturated compound having no acid group (a2) is not particularly limited, but is preferably 50% by mass or less, more preferably 45% by mass or less, further preferably 40% by mass or less, and further preferably 20% by mass or more, more preferably 25% by mass or more, further preferably 30% by mass or more, and particularly preferably 35% by mass or more of the total solid content. When the amount is not more than the upper limit, the ink jet coating suitability tends to be improved, and when the amount is not more than the lower limit, the amount of outgas generation tends to be reduced.

The content of the ethylenically unsaturated compound having no acid group (a2) in the ethylenically unsaturated compound (a) is not particularly limited, but is preferably 90% by mass or less, more preferably 80% by mass or less, even more preferably 75% by mass or less, and is preferably 50% by mass or more, more preferably 55% by mass or more, even more preferably 60% by mass or more, even more preferably 65% by mass or more, and particularly preferably 70% by mass or more. When the upper limit value or less is set as above, the ink jet coating suitability tends to be improved, and when the lower limit value or more is set as above, the amount of outgas generation tends to be reduced.

[1-1-2] (B) component: photopolymerization initiator

The photosensitive resin composition for forming organic electroluminescent element partition walls of the present invention contains (B) a photopolymerization initiator. (B) The photopolymerization initiator is not particularly limited as long as it is a compound capable of polymerizing the ethylenically unsaturated bond of the ethylenically unsaturated compound (a) by actinic rays, and a known photopolymerization initiator can be used.

In the photosensitive resin composition of the present invention, as the photopolymerization initiator (B), a photopolymerization initiator generally used in this field can be used. Examples of such photopolymerization initiators include: hexaarylbisimidazole-based photopolymerization initiator, acylphosphine oxide-based photopolymerization initiator, oxime-based photopolymerization initiator, acetophenone-based photopolymerization initiator, benzophenone-based photopolymerization initiator, hydroxybenzene-based photopolymerization initiator, thioxanthone-based photopolymerization initiator, anthraquinone-based photopolymerization initiator, ketal-based photopolymerization initiator, titanocene-based photopolymerization initiator, halogenated hydrocarbon derivative-based photopolymerization initiator, organoborate-based photopolymerization initiator, photopolymerization initiator for photopolymerization, and photopolymerization initiator for photopolymerization,

A salt-type photopolymerization initiator, a sulfone compound-type photopolymerization initiator, a carbamic acid derivative-type photopolymerization initiator, a sulfonamide-type photopolymerization initiator, and a triarylcarbinol-type photopolymerization initiator.

The hexaarylbisimidazole-based photopolymerization initiator is preferably a hexaarylbisimidazole-based compound represented by the following general formula (1-1) and/or the following general formula (1-2) from the viewpoint of absorbance, sensitivity, and compatibility with the absorption wavelength of an ultraviolet absorber.

[ chemical formula 7]

In the above formula, R¹¹～R¹³Each independently represents an alkyl group having 1 to 4 carbon atoms which may have a substituent, an alkoxy group having 1 to 4 carbon atoms which may have a substituent, or a halogen atom, and m, n, and l each independently represent an integer of 0 to 5.

R¹¹～R¹³The number of carbon atoms of the alkyl group (b) is not particularly limited as long as it is in the range of 1 to 4, and is preferably 3 or less, more preferably 2 or less, from the viewpoint of sensitivity. The alkyl group may be linear or cyclic. Specific examples of the alkyl group include methyl, ethyl, propyl and isopropyl groups, and among these, methyl and ethyl groups are preferable. As R¹¹～R¹³As the substituent optionally having the alkyl group having 1 to 4 carbon atoms, a group having a nonmetallic atom group of 1 valence other than hydrogen can be used, and preferable examples thereof include a halogen atom (-F, -Br, -Cl, -I), a hydroxyl group and an alkoxy group.

In addition, R¹¹～R¹³The number of carbon atoms of the alkoxy group(s) is not particularly limited as long as it is within a range of 1 to 4, but is preferably 3 or less, more preferably 2 or less, from the viewpoint of sensitivity. The alkyl moiety of the alkoxy group may be linear or cyclic. Specific examples of the alkoxy group include methoxy group, ethoxy group, propoxy group, isopropoxy group and butoxy group, and among these, methoxy group and ethoxy group are preferable. As R¹¹～R¹³The substituent optionally contained in the alkoxy group having 1 to 4 carbon atoms in (b) includes an alkyl group and an alkoxy group, and is preferably an alkyl group.

In addition, as R¹¹～R¹³Examples of the halogen atom of (b) include a chlorine atom, an iodine atom, a bromine atom and a fluorine atom, among which, from the viewpoint of ease of synthesis, a chlorine atom or a fluorine atom is preferable,more preferably a chlorine atom.

Among these, R is R from the viewpoint of sensitivity and ease of synthesis¹¹～R¹³Each independently is preferably a halogen atom, more preferably a chlorine atom.

m, n and l each independently represent an integer of 0 to 5, and from the viewpoint of ease of synthesis, at least 1 of m, n and l is preferably an integer of 1 or more, and more preferably any 1 of m, n and l is 1 and the remaining 2 are 0.

Examples of the hexaarylbisimidazoles of the general formula (1-1) and/or the general formula (1-2) include: 2,2 '-bis (o-chlorophenyl) -4,5, 4', 5 '-tetraphenyl biimidazole, 2' -bis (o-methylphenyl) -4,5,4 ', 5' -tetraphenyl biimidazole, 2 '-bis (o-chlorophenyl) -4, 4', 5,5 '-tetrakis (o, p-dichlorophenyl) biimidazole, 2' -bis (o, p-dichlorophenyl) -4,4 ', 5, 5' -tetrakis (o, p-dichlorophenyl) biimidazole, 2 '-bis (o-chlorophenyl) -4, 4', 5,5 '-tetrakis (p-fluorophenyl) biimidazole, 2' -bis (o-chlorophenyl) -4,4 ', 5, 5' -tetrakis (o, p-dibromophenyl) biimidazole, 2,2 '-bis (o-bromophenyl) -4, 4', 5,5 '-tetrakis (o, p-dichlorophenyl) biimidazole, 2' -bis (o-chlorophenyl) -4,4 ', 5, 5' -tetrakis (p-chloronaphthyl) biimidazole, and the like. Among these compounds, preferred are hexaphenylbiimidazole compounds, more preferred are compounds in which the ortho position of the benzene ring bonded to the 2,2 ' -position of the imidazole ring is substituted with a methyl group, a methoxy group or a halogen atom, and preferred are compounds in which the benzene ring bonded to the 4,4 ', 5,5 ' -position of the imidazole ring is unsubstituted or substituted with a halogen atom or a methoxy group.

As the photopolymerization initiator (B), either one of the hexaarylbisimidazole compound represented by the general formula (1-1) and the hexaarylbisimidazole compound represented by the general formula (1-2) may be used, or both may be used in combination. When used in combination, the ratio is not particularly limited. In the examples, b-1 used had a structure satisfying the general formula (1-1).

Further, as the acylphosphine oxide-based photopolymerization initiator, preferred are: 2,4, 6-trimethylbenzoyldiphenylphosphine oxide, bis (2,4, 6-trimethylbenzoyl) phenylphosphine oxide, and the like.

Examples of the oxime photopolymerization initiator include: oxime ester compounds described in, for example, JP-A-2004-534797, JP-A-2000-80068, JP-A-2006-36750, JP-A-2008-179611, JP-A-2012-526185, and JP-A-2012-519191. Among them, from the viewpoint of sensitivity, preferred are: N-acetoxy-N- { 4-acetoxyimino-4- [ 9-ethyl-6- (o-methylbenzoyl) -9H-carbazol-3-yl ] butan-2-yl } acetamide, N-acetoxy-N- {3- (acetoxyimino) -3- [ 9-ethyl-6- (1-naphthoyl) -9H-carbazol-3-yl ] -1-methylpropyl } acetamide, methyl 4-acetoxyimino-5- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] -5-oxopentanoate, And OXE-01, OXE-02, OXE-03 (manufactured by BASF Co., Ltd.), TR-PBG-304, TR-PBG-305 (manufactured by Kyowa Kagaku Co., Ltd.), NCI-831, NCI-930 (manufactured by ADEKA Co., Ltd.), and the like, which are expressed by product names.

Examples of the acetophenone-based photopolymerization initiator include: 2, 2-diethoxyacetophenone, 2-dimethoxy-2-phenylacetophenone, 1-hydroxycyclohexylphenyl ketone, 1-hydroxy-1- (p-dodecylphenyl) ketone, 1-hydroxy-1-methylethyl (p-isopropylphenyl) ketone, 1-trichloromethyl (p-butylphenyl) ketone, α -hydroxy-2-methylphenylacetone, 2-methyl-1- [4- (methylthio) phenyl ] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one, 2-hydroxy-1- (p-dodecylphenyl) propanone, 2-hydroxy-1-morpholinophenyl) butan-1-one, 2-hydroxy-1- (4-morpholinophenyl) butan-1-one, 2-hydroxy-1-methyl-1- (p-dodecylphenyl) propanone, 2-methyl-1-methyl-1-morpholinyl-1-morpholinyl-1-one, 2-morpholinyl-phenyl-1-methyl-one, 2-methyl-1-methyl-one, 2-methyl-1-methyl-1-ethyl-one, 2-methyl-1-methyl-ethyl-1-methyl-ethyl, 2-ethyl-methyl-ethyl-1-2-ethyl-1-2-1-2-methyl-1-methyl-1-methyl-1-methyl-phenyl-2-methyl-1-methyl-ethyl-methyl-ethyl-1-methyl-1-methyl-1-2-methyl-1-methyl-1-methyl-1-methyl-, Ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 4-diethylaminoacetophenone, 4-dimethylaminopropiophenone, 2-ethylhexyl 1, 4-dimethylaminobenzoate, 2, 5-bis (4-diethylaminobenzylidene) cyclohexanone, 4- (diethylamino) chalcone, and the like.

Examples of the benzophenone photopolymerization initiator include: benzophenone, 2-methyl benzophenone, 3-methyl benzophenone, 4-methyl benzophenone, 2-carboxyl benzophenone, 2-chlorine benzophenone, 4-bromine benzophenone, Michler's ketone etc..

Examples of the hydroxybenzene photopolymerization initiator include: 2-hydroxy-4-n-octyloxybenzophenone, 2-hydroxy-4-benzylbenzophenone, 2- (2-hydroxy-5-methylphenyl) benzotriazole, 4-di-t-butylphenyl-3, 5-di-t-butyl-4-hydroxybenzoate and the like.

Examples of the thioxanthone photopolymerization initiator include: thioxanthone, 2-ethylthioxanthone, 2-isopropylthioxanthone, 2, 4-dimethylthioxanthone, 2, 4-diethylthioxanthone, 2, 4-diisopropylthioxanthone, 2-chlorothioxanthone, and the like.

Examples of the anthraquinone-based photopolymerization initiator include 2-methylanthraquinone, and examples of the ketal-based photopolymerization initiator include benzildimethylketal.

Examples of the titanocene-based photopolymerization initiator include: bis (cyclopentadienyl) titanium dichloride, diphenylbis (cyclopentadienyl) titanium, bis (2, 4-difluorophenyl) bis (cyclopentadienyl) titanium, bis (2, 6-difluorophenyl) bis (cyclopentadienyl) titanium, bis (2,4, 6-trifluorophenyl) bis (cyclopentadienyl) titanium, bis (2,3,5, 6-tetrafluorophenyl) bis (cyclopentadienyl) titanium, bis (2,3,4,5, 6-pentafluorophenyl) bis (cyclopentadienyl) titanium, bis (2, 6-difluorophenyl) bis (methylcyclopentadienyl) titanium, bis (2,3,4,5, 6-pentafluorophenyl) bis (methylcyclopentadienyl) titanium, bis [2, 6-difluoro-3- (1-pyrrolyl) phenyl ] bis (cyclopentadienyl) titanium, and the like. Among these, from the viewpoint of sensitivity, a titanium compound having a bis (cyclopentadienyl) structure and a bisphenyl structure is preferable, and a compound in which the ortho position of the bisphenyl ring is substituted with a halogen atom is particularly preferable.

Examples of the halogenated hydrocarbon derivative photopolymerization initiator include halomethylated s-triazine derivatives, and examples thereof include: 2,4, 6-tris (monochloromethyl) s-triazine, 2,4, 6-tris (dichloromethyl) s-triazine, 2,4, 6-tris (trichloromethyl) s-triazine, 2-methyl-4, 6-bis (trichloromethyl) s-triazine, 2-n-propyl-4, 6-bis (trichloromethyl) s-triazine, 2- (. alpha.,. beta. -trichloroethyl) -4, 6-bis (trichloromethyl) s-triazine, 2-phenyl-4, 6-bis (trichloromethyl) s-triazine, 2- (p-methoxyphenyl) -4, 6-bis (trichloromethyl) s-triazine, 2- (3, 4-epoxyphenyl) -4, 6-bis (trichloromethyl) s-triazine, 2- (p-chlorophenyl) -4, 6-bis (trichloromethyl) s-triazine, 2- [1- (p-methoxyphenyl) -2, 4-butadienyl ] -4, 6-bis (trichloromethyl) s-triazine, 2-styryl-4, 6-bis (trichloromethyl) s-triazine, 2- (p-methoxystyryl) -4, 6-bis (trichloromethyl) s-triazine, 2- (p-methoxy-m-hydroxystyryl) -4, 6-bis (trichloromethyl) s-triazine, 2- (p-isopropoxystyryl) -4, 6-bis (trichloromethyl) s-triazine, 2- (p-tolyl) -4, 6-bis (trichloromethyl) s-triazine, 2- (p-methoxynaphthyl) -4, 6-bis (trichloromethyl) s-triazine, Halomethylated s-triazine derivatives such as 2- (p-ethoxynaphthyl) -4, 6-bis (trichloromethyl) s-triazine, 2- (p-ethoxycarbonylnaphthyl) -4, 6-bis (trichloromethyl) s-triazine, 2-phenylthio-4, 6-bis (trichloromethyl) s-triazine, 2-benzylthio-4, 6-bis (trichloromethyl) s-triazine, 2,4, 6-tris (dibromomethyl) s-triazine, 2,4, 6-tris (tribromomethyl) s-triazine, 2-methyl-4, 6-bis (tribromomethyl) s-triazine, 2-methoxy-4, 6-bis (tribromomethyl) s-triazine, 2- (4-methoxyphenyl) -4, 6-bis (trichloromethyl) s-triazine, among them, bis (trihalomethyl) s-triazines are preferable from the viewpoint of sensitivity.

Examples of the organoborate type photopolymerization initiator include: organic boron-ammonium complex, organic boron

Complex, organoboron sulfonium complex, organoboron oxonium complex, organoboron iodonium

Complexes, organoboron transition metal coordination complexes, and the like, the organoboron anions thereof are preferably, for example: n-butyltriphenylboron anion, n-butyltris (2,4, 6-trimethylphenyl) boron anion, n-butyltris (p-methoxyphenyl) boron anion, n-butyltris (p-fluorophenyl) boron anion, n-butyltris (m-fluorophenyl) boron anion, n-butyltris (3-fluoro-4-methylphenyl) boron anion, n-butyltris (2, 6-difluorophenyl) boron anion, n-butyltris (2,4, 6-trifluorophenyl) boron anion, n-butyltris (2,3,4,5, 6-pentafluorophenyl) boron anion, n-butyltris (p-chlorophenyl) boron anion, n-butyltris (2, 6-difluoro-3-pyrrolylphenyl) boron anion and the like alkanesThe triphenylboron anion is preferably an ammonium cation, or a mixture thereof as the counter cation from the viewpoint of sensitivity,

Cation, sulfonium cation, iodine

Cations and the like

The compound is particularly preferably an organic ammonium cation such as tetraalkylammonium from the viewpoint of sensitivity.

As

Examples of the salt-type photopolymerization initiator include: ammonium salts such as tetramethylammonium bromide and tetraethylammonium bromide, and diphenyliodine

Hexafluoroarsenate, diphenyl iodide

Tetrafluoroborate and diphenyl iodide

P-toluenesulfonate salt and diphenyl iodide

Camphor sulfonate, dicyclohexyl iodide

Hexafluoroarsenate, dicyclohexyliodide

Tetrafluoroborate, dicyclohexyliodide

P-toluenesulfonic acidSalt, dicyclohexyliodide

Iodine such as camphorsulfonate

Sulfonium salts such as phosphonium salts, triphenylsulfonium hexafluoroarsenate, triphenylsulfonium tetrafluoroborate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium camphorsulfonate, tricyclohexylsulfonium hexafluoroarsenate, tricyclohexylsulfonium tetrafluoroborate, tricyclohexylsulfonium p-toluenesulfonate, and tricyclohexylsulfonium camphorsulfonate.

Examples of the sulfone compound-based photopolymerization initiator include: bis (sulfonyl) methane compounds such as bis (phenylsulfonyl) methane, bis (p-hydroxyphenylsulfonyl) methane, bis (p-methoxyphenylsulfonyl) methane, bis (. alpha. -naphthylsulfonyl) methane, bis (. beta. -naphthylsulfonyl) methane, bis (cyclohexylsulfonyl) methane, bis (t-butylsulfonyl) methane, phenylsulfonyl (cyclohexylsulfonyl) methane, carbonyl (phenylsulfonyl) methane, naphthylcarbonyl (phenylsulfonyl) methane, phenylcarbonyl (naphthylsulfonyl) methane, cyclohexylcarbonyl (phenylsulfonyl) methane, t-butylcarbonyl (phenylsulfonyl) methane, phenylcarbonyl (cyclohexylsulfonyl) methane, carbonyl (sulfonyl) methane compounds such as phenylcarbonyl (t-butylcarbonyl) methane, bis (phenylsulfonyl) diazomethane, bis (p-hydroxyphenylsulfonyl) diazomethane, bis (α -naphthylsulfonyl) methane, bis (β -naphthylsulfonyl) methane, bis (cyclohexylsulfonyl) methane, and the like, Carbonyl (sulfonyl) diazomethane compounds such as bis (p-methoxyphenylsulfonyl) diazomethane, bis (α -naphthylsulfonyl) diazomethane, bis (β -naphthylsulfonyl) diazomethane, bis (cyclohexylsulfonyl) diazomethane, bis (tert-butylsulfonyl) diazomethane, phenylsulfonyl (cyclohexylsulfonyl) diazomethane, bis (sulfonyl) diazomethane, phenylcarbonyl (phenylsulfonyl) diazomethane, naphthylcarbonyl (phenylsulfonyl) diazomethane, phenylcarbonyl (naphthylsulfonyl) diazomethane, cyclohexylcarbonyl (phenylsulfonyl) diazomethane, tert-butylcarbonyl (phenylsulfonyl) diazomethane, phenylcarbonyl (cyclohexylsulfonyl) diazomethane, phenylcarbonyl (tert-butylcarbonyl) diazomethane, and the like.

Examples of the urethane derivative photopolymerization initiator include: benzoylcyclohexylcarbamate, 2-nitrobenzylcyclohexylcarbamate, 3, 5-dimethoxybenzylcyclohexylcarbamate, 3-nitrophenylcyclohexylcarbamate, and the like.

Examples of the sulfonamide photopolymerization initiator include: n-cyclohexyl-4-methylphenylsulfonamide, N-cyclohexyl-2-naphthylsulfonamide and the like, and examples of the triarylcarbinol-based photopolymerization initiator include: triphenylmethanol, tris (4-chlorophenyl) methanol, and the like.

The photosensitive resin composition may contain one of these photopolymerization initiators alone, or may contain two or more of them. Among these photopolymerization initiators, hexaarylbiimidazole-based compounds are particularly preferable because of high absorbance, high surface curability, high liquid repellency, and large cone angle.

The content of the photopolymerization initiator (B) in the photosensitive resin composition of the present invention is usually 0.01 mass% or more, preferably 0.1 mass% or more, more preferably 0.5 mass% or more, further preferably 1 mass% or more, and particularly preferably 1.5 mass% or more, and usually 25 mass% or less, preferably 10 mass% or less, more preferably 8 mass% or less, further preferably 5 mass% or less, and particularly preferably 3 mass% or less, with respect to the total solid content of the photosensitive resin composition. When the amount is not less than the lower limit, a coating film can be formed during development without causing film shrinkage and sufficient liquid repellency tends to be produced, and when the amount is not more than the upper limit, a desired pattern shape tends to be easily formed.

In addition, as the blending ratio of the photopolymerization initiator (B) to the ethylenically unsaturated compound (a) in the photosensitive resin composition of the present invention, the photopolymerization initiator (B) is preferably 1 part by mass or more, more preferably 2 parts by mass or more, and still more preferably 3 parts by mass or more, and further preferably 200 parts by mass or less, more preferably 100 parts by mass or less, further preferably 50 parts by mass or less, still more preferably 20 parts by mass or less, particularly preferably 10 parts by mass or less, and most preferably 5 parts by mass or less, with respect to 100 parts by mass of the ethylenically unsaturated compound (a). When the lower limit value is not less than the above-described lower limit value, there is a tendency that appropriate sensitivity can be obtained, and when the upper limit value is not more than the above-described upper limit value, there is a tendency that a desired pattern shape is easily formed.

In addition, a sensitizer may be used in combination with the photopolymerization initiator (B). The sensitivity is improved by the sensitizer, and the light transmittance into the photosensitive resin composition is reduced, so that the taper angle tends to increase.

As the sensitizer, one commonly used in this field can be used. The sensitizer has a characteristic of effectively promoting a reactive radical polymerization reaction by transferring energy obtained by absorption to a photopolymerization initiator or by generating acceptance of electrons with the photopolymerization initiator.

Examples of such a sensitizer include: unsaturated ketones typified by chalcone derivatives and dibenzylideneacetone, 1, 2-diketones typified by benzil and camphorquinone, benzoin compounds, fluorene compounds, naphthoquinone compounds, anthraquinone compounds, xanthene compounds, thioxanthene compounds, xanthone compounds, thioxanthone compounds, coumarin compounds, coumarone compounds, cyanine compounds, merocyanine compounds, oxonol derivatives and other polymethine pigments, acridine compounds, azine compounds, thiazine compounds, acridine compounds, dihydroazulene compounds, and the like,

Oxazine compound, indoline compound, azulene compound and azulene

Compounds, squarylium compounds, porphyrin compounds, tetraphenylporphyrin compounds, triarylmethane compounds, tetraphenylporphyrin compounds, tetrapyrazino-tetraazaporphyrin compounds, phthalocyanine compounds, tetraazaporphyrin compounds, and tetraquinoxalino-tetraazaporphyrin compoundsNaphthalocyanine compound, subphthalocyanine compound and pyran

Compound of the class, thiopyran

Compounds, porphyrins, annulenes, spiropyrans, and spiros

Oxazine compounds, thiospiropyran compounds, metal aromatic hydrocarbon complexes, organic ruthenium complexes, benzophenone compounds, and the like.

These sensitizers may be used singly or in combination of two or more.

Among these, thioxanthone compounds and benzophenone compounds are preferable from the viewpoint of improving sensitivity and increasing the cone angle.

Examples of the thioxanthone compound include: thioxanthone, 2-methylthioxanthone, 4-methylthioxanthone, 2, 4-dimethylthioxanthone, 2-ethylthioxanthone, 4-ethylthioxanthone, 2, 4-diethylthioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2, 4-diisopropylthioxanthone, 2-chlorothioxanthone, 4-chlorothioxanthone, 2, 4-dichlorothioxanthone, and the like. Among these compounds, 2, 4-diethylthioxanthone is preferable from the viewpoint of improving sensitivity and increasing the cone angle.

Examples of the benzophenone compound include: benzophenone, 4 ' -bis (dimethylamino) benzophenone, 4 ' -bis (diethylamino) benzophenone, 4 ' -bis (ethylmethylamino) benzophenone, and the like. Among these compounds, 4' -bis (diethylamino) benzophenone is preferable from the viewpoint of improving sensitivity and increasing the cone angle.

The content of the sensitizer in the photosensitive resin composition is usually 0.1% by mass or more, preferably 0.3% by mass or more, more preferably 0.5% by mass or more, further preferably 0.8% by mass or more, further preferably 1% by mass or more, particularly preferably 1.2% by mass or more, and is usually 10% by mass or less, preferably 7% by mass or less, more preferably 5% by mass or less, further preferably 3% by mass or less, relative to the total solid content of the photosensitive resin composition. When the lower limit value is not less than the above-mentioned lower limit value, sensitivity is likely to be improved and the taper angle tends to be increased, and when the upper limit value is not more than the above-mentioned upper limit value, a desired pattern tends to be easily formed.

[1-1-3] (E) component: chain transfer agent

The photosensitive resin composition for forming a spacer of an organic electroluminescent element of the invention according to embodiment 1 contains (E) a chain transfer agent. The inclusion of the chain transfer agent (E) tends to increase the taper angle because the deactivation of radicals in the vicinity of the surface due to oxygen inhibition or the like is improved and the surface curability is improved.

In addition, when the liquid repellent is contained, the surface curability is improved to suppress the outflow of the liquid repellent, and the liquid repellent tends to be easily fixed to a surface member and the contact angle tends to be increased.

In the photosensitive resin composition for forming partition walls of an organic electroluminescent element of the present invention of embodiment 2, the chain transfer agent (E) is not essential, but it is preferable to contain the chain transfer agent (E) from the viewpoint of increasing the taper angle.

The chain transfer agent (E) includes a mercapto group-containing compound, carbon tetrachloride and the like, and the mercapto group-containing compound is more preferably used because the chain transfer effect tends to be high. The mercapto group-containing compound tends to have improved surface curability because it has a small S — H bond energy and is likely to undergo bond cleavage and a chain transfer reaction.

The chain transfer agent (E) is preferably a mercapto compound having an aromatic ring or an aliphatic mercapto compound, from the viewpoint of cone angle and surface curability.

As the mercapto group-containing compound having an aromatic ring, compounds represented by the following general formula (1-3) are preferably used from the viewpoint of cone angle.

[ chemical formula 8]

In the formula (1-3), Z represents-O-, -S-or-NH-, R⁶¹、R⁶²、R⁶³And R⁶⁴Each independently represents a hydrogen atom or a 1-valent substituent.

Of these, Z is preferably-S-or-NH-, and more preferably-NH-, from the viewpoint of the taper angle.

In addition, from the viewpoint of taper angle, R ⁶¹、R⁶²、R⁶³And R⁶⁴Each independently preferably a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, and more preferably a hydrogen atom.

Specific examples thereof include 2-mercaptobenzothiazole, 2-mercaptobenzimidazole and 2-mercaptobenz

Mercapto compounds having an aromatic ring such as oxazole, 3-mercapto-1, 2, 4-triazole, 2-mercapto-4 (3H) -quinazoline, β -mercaptonaphthalene, and 1, 4-dimethylmercaptobenzene, and 2-mercaptobenzothiazole and 2-mercaptobenzimidazole are preferable from the viewpoint of the cone angle.

On the other hand, as the aliphatic mercapto group-containing compound, from the viewpoint of surface curability, hexanedithiol, decanedithiol, or a compound represented by the following general formula (1-4) can be preferably used.

[ chemical formula 9]

In the formula (1-4), m represents an integer of 0-4, n represents an integer of 2-4, R⁷¹And R⁷²Each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and X represents an n-valent group.

In the general formula (1-4), m is preferably 1 or 2 from the viewpoint of ease of synthesis. In addition, n is preferably 3 or 4, and more preferably 4, from the viewpoint of surface curability.

In addition, as R⁷¹And R⁷²The alkyl group of (2) is preferably an alkyl group having 1 to 3 carbon atoms from the viewpoint of surface curability. From the viewpoint of surface curability, R is preferred ⁷¹And R⁷²At least one of them, e.g. R⁷²Is a hydrogen atom, in which case R is preferably⁷¹Is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.

When n is 2, X is preferably an alkylene group having 1 to 6 carbon atoms which optionally has an ether bond and/or a branched portion, from the viewpoint of surface curability. Among them, an alkylene group having 1 to 6 carbon atoms is more preferable, and an alkylene group having 4 carbon atoms is even more preferable, from the viewpoint of surface curability and ease of synthesis.

When n is 3, X is preferably a structure represented by the following general formula (1-5) or (1-6) from the viewpoint of surface curability and ease of synthesis.

[ chemical formula 10]

In the formula (1-5), R⁷³Represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a hydroxymethyl group. At R⁷³Among them, ethyl is preferable from the viewpoint of the taper angle.

[ chemical formula 11]

In the formula (1-6), R⁷⁴Represents an alkylene group having 1 to 4 carbon atoms. At R⁷⁴Among them, ethylene is preferable from the viewpoint of the taper angle.

On the other hand, when n is 4, X is preferably a structure represented by the following general formula (1-7).

[ chemical formula 12]

Specific examples thereof include: butanediol bis (3-mercaptopropionate), butanediol bis (mercaptoacetate), ethylene glycol bis (3-mercaptopropionate), ethylene glycol bis (mercaptoacetate), trimethylolpropane tris (3-mercaptopropionate), trimethylolpropane tris (mercaptoacetate), trihydroxyethyltris (mercaptopropionate), pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tris (3-mercaptopropionate), butanediol bis (3-mercaptobutyrate), ethylene glycol bis (3-mercaptobutyrate), trimethylolpropane tris (3-mercaptobutyrate), pentaerythritol tetrakis (3-mercaptobutyrate), pentaerythritol tris (3-mercaptobutyrate), 1,3, 5-tris (3-mercaptobutoxyethyl) -1,3, 5-triazine-2, 4,6(1H,3H,5H) -trione, and the like.

Among them, more preferred are: trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tris (3-mercaptopropionate), trimethylolpropane tris (3-mercaptobutyrate), pentaerythritol tetrakis (3-mercaptobutyrate), pentaerythritol tris (3-mercaptobutyrate), 1,3, 5-tris (3-mercaptobutoxyethyl) -1,3, 5-triazine-2, 4,6(1H,3H,5H) -trione, more preferably pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptobutyrate).

Of these, one of the various compounds may be used alone, or two or more of them may be used in combination.

Among these, from the viewpoint of increasing the taper angle, it is preferable to use a compound selected from the group consisting of 2-mercaptobenzothiazole, 2-mercaptobenzimidazole and 2-mercaptobenz

One or more of azoles and a photopolymerization initiator are used in combination as a photopolymerization initiator system. For example, 2-mercaptobenzothiazole, 2-mercaptobenzimidazole, or a combination of 2-mercaptobenzothiazole and 2-mercaptobenzimidazole may be used.

In addition, from the viewpoint of surface curability, it is preferable to use at least one selected from pentaerythritol tetrakis (3-mercaptopropionate) and pentaerythritol tetrakis (3-mercaptobutyrate).

Further, particularly from the viewpoint that the taper angle can be increased even in the partition wall having a narrow line width, it is preferable to use a thiol-group-containing compound having an aromatic ring in combination with an aliphatic thiol-group-containing compound. This is because, in order to form partition walls having a small line width, the use of a mask having a narrow opening width reduces the illuminance per unit area by diffraction during exposure, and thus the influence of oxygen inhibition tends to be more likely to be exerted and the surface curability tends to be reduced than in the case where the line width is large.

In particular, when a hexaarylbisimidazole-based photopolymerization initiator is used as the photopolymerization initiator (B), it is preferable to use a combination of a mercapto group-containing compound having an aromatic ring and an aliphatic mercapto group-containing compound. On the other hand, when an acetophenone-based photopolymerization initiator is used, sufficient effects tend to be obtained even when an aliphatic mercapto group-containing compound is used alone.

For example, it is preferable to use a compound selected from the group consisting of 2-mercaptobenzothiazole, 2-mercaptobenzimidazole and 2-mercaptobenzo

One or more kinds of azoles, one or more kinds selected from pentaerythritol tetrakis (3-mercaptopropionate) and pentaerythritol tetrakis (3-mercaptobutyrate), and a photopolymerization initiator are used in combination.

The content of the chain transfer agent (E) in the photosensitive resin composition of the present invention is usually 0.01% by mass or more, preferably 0.025% by mass or more, more preferably 0.05% by mass or more, further preferably 0.1% by mass or more, particularly preferably 1% by mass or more, and usually 5% by mass or less, preferably 4% by mass or less, more preferably 3% by mass or less, based on the total solid content of the photosensitive resin composition. When the lower limit value is not less than the above-mentioned lower limit value, the taper angle tends to be increased, and the surface curability tends to be improved, and when the upper limit value is not more than the above-mentioned upper limit value, a desired pattern tends to be easily formed.

In addition, when the mercapto group-containing compound having an aromatic ring and the mercapto group-containing compound of an aliphatic series are used in combination as the (E) chain transfer agent, the content ratio of these compounds is usually not less than 10 parts by mass, preferably not less than 50 parts by mass, more preferably not less than 80 parts by mass, and usually not more than 400 parts by mass, preferably not more than 300 parts by mass, more preferably not more than 200 parts by mass, and further preferably not more than 150 parts by mass, relative to 100 parts by mass of the mercapto group-containing compound having an aromatic ring. When the value is equal to or higher than the lower limit, the taper angle tends to be large, and when the value is equal to or lower than the upper limit, the surface curability tends to be high, and the contact angle tends to be high.

The blending ratio of the chain transfer agent (E) to the photopolymerization initiator (B) in the photosensitive resin composition is preferably 10 parts by mass or more, more preferably 25 parts by mass or more, further preferably 50 parts by mass or more, and particularly preferably 80 parts by mass or more, and further preferably 500 parts by mass or less, more preferably 400 parts by mass or less, further preferably 300 parts by mass or less, further preferably 200 parts by mass or less, and particularly preferably 150 parts by mass or less, relative to 100 parts by mass of the photopolymerization initiator (B). When the lower limit value is not less than the above-described lower limit value, the taper angle tends to be increased, and the surface curability tends to be improved.

[1-1-4] (C) component: alkali soluble resin

The photosensitive resin composition for forming organic electroluminescent element partition walls of the present invention contains (C) an alkali-soluble resin. In the present invention, the alkali-soluble resin (C) is not particularly limited as long as it is a resin that can be developed in a developer, but since the developer is preferably an alkali developer, the alkali-soluble resin (C) is used in the present invention.

Examples of the alkali-soluble resin (C) include various resins containing a carboxyl group or a hydroxyl group. Among them, an alkali-soluble resin having a carboxyl group is preferable, and an alkali-soluble resin having an ethylenically unsaturated group is more preferable, because a partition wall having an appropriate taper angle can be obtained, and outflow of a liquid repellent due to thermal fusion of the surface of the partition wall can be suppressed at the time of post baking, and liquid repellency can be maintained.

(alkali-soluble resin (c) having a partial structure represented by the general formula (1))

In the photosensitive resin composition for forming partition walls of an organic electroluminescent element of the present invention according to embodiment 1, the alkali-soluble resin (C) contains an alkali-soluble resin (C) having a partial structure represented by the following general formula (1) (hereinafter, also simply referred to as "resin (C)").

The resin (C) is also preferably a resin having an ethylenically unsaturated group, similarly to the alkali-soluble resin (C).

It is considered that by using the alkali-soluble resin having a partial structure represented by the general formula (1), that is, a partial structure containing an acid component having a small number of carbon atoms and being easily thermally decomposed, most of the acid component is removed in a gaseous state in thermal curing at the time of forming the partition walls, so that the amount of outgas generated at the time of driving the organic electroluminescent element can be reduced, and the reliability can be improved.

[ chemical formula 13]

In the above formula (1), R¹Represents a C1-4 valent hydrocarbon group optionally having a substituent, and represents a bonding position.

(R¹)

In the above general formula (1), R¹Represents an optionally substituted C1-4 valent hydrocarbon group. As the 2-valent hydrocarbon group, an alkylene group and an alkenylene group are exemplified.

The alkylene group may be linear or branched, but is preferably linear from the viewpoint of developing solubility. The number of carbon atoms of the alkylene group is preferably 2 or more, and preferably 3 or less. When the lower limit value is not less than the above-mentioned lower limit value, the residual film ratio tends to be improved, and when the upper limit value is not more than the above-mentioned upper limit value, the amount of outgas generation at the time of light emission of the device tends to be reduced.

Specific examples of the alkylene group include: the methylene group, ethylene group, propylene group, and butylene group are preferably a methylene group or an ethylene group, and more preferably an ethylene group, from the viewpoint of reducing the amount of outgas generated.

The alkenylene group may be linear or branched, but is preferably linear from the viewpoint of developing solubility. The number of carbon atoms of the alkenylene group is preferably 2 or more, and preferably 3 or less. When the lower limit value is not less than the above-mentioned lower limit value, the residual film ratio tends to be improved, and when the upper limit value is not more than the above-mentioned upper limit value, the amount of outgas generation at the time of light emission of the device tends to be reduced.

Specific examples of alkenylene groups include: vinylidene, propenylene and butenylene groups are preferably vinylidene groups from the viewpoint of reducing the amount of outgas generated.

The substituent optionally contained in the 2-valent hydrocarbon group having 1 to 4 carbon atoms is not particularly limited, and examples thereof include a halogen atom, an alkoxy group, a benzoyl group, and a hydroxyl group, and it is preferably unsubstituted from the viewpoint of ease of synthesis.

Of these, R is preferred from the viewpoint of reducing the amount of outgas generated¹Is a C1-4 alkylene group having a valence of 2, more preferably a methylene group or an ethylene group, and still more preferably an ethylene group.

The alkali-soluble resin (c) is not particularly limited as long as it has a partial structure represented by the above general formula (1), and the specific structure thereof is not particularly limited, but from the viewpoint of developing solubility, (c1) epoxy (meth) acrylate resin and/or (c2) acrylic copolymer resin are preferably contained, and from the viewpoint of reducing the amount of outgas generated, (c1) epoxy (meth) acrylate resin is more preferably contained.

The epoxy (meth) acrylate resin (c1) will be described in detail below.

[ (c1) epoxy (meth) acrylate resin ]

(c1) The epoxy (meth) acrylate resin is obtained by adding an acid or ester compound having an ethylenically unsaturated bond to an epoxy resin and further adding a polybasic acid or an acid anhydride thereof. For example, a resin obtained by ring-opening addition of a carboxyl group of an unsaturated monocarboxylic acid to an epoxy group of an epoxy resin to add an ethylenically unsaturated bond to the epoxy resin via an ester bond (-COO-) and simultaneously adding a hydroxyl group generated at this time to a carboxyl group of one of a polybasic acid and an acid anhydride thereof is exemplified. Further, there can be mentioned a resin obtained by adding a polyhydric alcohol simultaneously with the addition of a polybasic acid or an acid anhydride thereof. Further, a resin obtained by further reacting a carboxyl group of the resin obtained in the above reaction with a compound having a reactive functional group is also included in the above (c1) epoxy (meth) acrylate resin.

As described above, (c1) the epoxy (meth) acrylate resin is not limited to a "(meth) acrylate" resin having substantially no epoxy group in chemical structure, but is conventionally named because an epoxy compound (epoxy resin) is used as a raw material and a "(meth) acrylate" is a typical example.

Here, the name of the epoxy resin also includes a raw material compound before forming a resin by heat curing, and the epoxy resin can be appropriately selected from known epoxy resins and used. In addition, as the epoxy resin, a compound obtained by reacting a phenolic compound with epichlorohydrin may be used. The phenolic compound is preferably a 2-or more-membered compound having a phenolic hydroxyl group, and may be a monomer or a polymer.

Specific examples thereof include: bisphenol a-type epoxy resin, bisphenol F-type epoxy resin, bisphenol S-type epoxy resin, phenol novolac epoxy resin, cresol novolac epoxy resin, biphenol-aldehyde epoxy resin, trisphenol epoxy resin, epoxy resin obtained by polymerizing phenol with dicyclopentadiene, dihydroxyfluorene-type epoxy resin, dihydroxyalkyleneoxyfluorene-type epoxy resin, diglycidyl ether of 9, 9-bis (4 '-hydroxyphenyl) fluorene, diglycidyl ether of 1, 1-bis (4' -hydroxyphenyl) adamantane, and the like, and a compound having an aromatic ring in the main chain can be preferably used.

Among them, from the viewpoint of high cured film strength, bisphenol a type epoxy resins, phenol novolac epoxy resins, cresol novolac epoxy resins, polymerized epoxy resins of phenol and dicyclopentadiene, diglycidyl etherate of 9, 9-bis (4' -hydroxyphenyl) fluorene, and the like are preferable, and bisphenol a type epoxy resins are more preferable.

As the acid having an ethylenically unsaturated bond, an ethylenically unsaturated monocarboxylic acid is preferable, and there may be exemplified: (meth) acrylic acid, crotonic acid, maleic acid, fumaric acid, citraconic acid, and the like, and pentaerythritol tri (meth) acrylate succinic anhydride adducts, pentaerythritol tri (meth) acrylate tetrahydrophthalic anhydride adducts, dipentaerythritol penta (meth) acrylate succinic anhydride adducts, dipentaerythritol penta (meth) acrylate phthalic anhydride adducts, dipentaerythritol penta (meth) acrylate tetrahydrophthalic anhydride adducts, reaction products of (meth) acrylic acid and epsilon-caprolactone, and the like. Among them, (meth) acrylic acid is preferable from the viewpoint of sensitivity.

Examples of the polybasic acid or anhydride thereof include: succinic acid, maleic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, 3-methyltetrahydrophthalic acid, 4-methyltetrahydrophthalic acid, 3-ethyltetrahydrophthalic acid, 4-ethyltetrahydrophthalic acid, hexahydrophthalic acid, 3-methylhexahydrophthalic acid, 4-methylhexahydrophthalic acid, 3-ethylhexahydrophthalic acid, 4-ethylhexahydrophthalic acid, trimellitic acid, pyromellitic acid, benzophenone tetracarboxylic acid, biphenyl tetracarboxylic acid, and acid anhydrides thereof. These polybasic acids or anhydrides thereof may be used alone or in combination of two or more. Among these, succinic anhydride, maleic anhydride, and itaconic anhydride are preferable, and succinic anhydride is more preferable, from the viewpoint of introducing the partial structure represented by the above general formula (1) into a resin.

When a polybasic acid or an anhydride thereof is added, the use of a polyhydric alcohol tends to increase the molecular weight of the epoxy (meth) acrylate resin (c1), introduce branches into the molecule, and balance the molecular weight and viscosity. Further, the introduction rate of an acid group into a molecule tends to be increased, and a balance between sensitivity, adhesion, and the like tends to be easily obtained.

The polyol is preferably one or two or more polyols selected from trimethylolpropane, ditrimethylolpropane, pentaerythritol, dipentaerythritol, trimethylolethane, and 1,2, 3-propanetriol, for example.

(c1) The acid value of the epoxy (meth) acrylate resin is not particularly limited, and is preferably 10mgKOH/g or more, more preferably 20mgKOH/g or more, further preferably 40mgKOH/g or more, further preferably 60mgKOH/g or more, and particularly preferably 80mgKOH/g or more, and is preferably 200mgKOH/g or less, more preferably 180mgKOH/g or less, further preferably 150mgKOH/g or less, further preferably 120mgKOH/g or less, and particularly preferably 100mgKOH/g or less. When the upper limit value is not less than the lower limit value, the amount of outgas generated in the light emission of the device tends to be reduced.

(c1) The weight average molecular weight (Mw) of the epoxy (meth) acrylate resin is not particularly limited, and is usually 1,000 or more, preferably 2,000 or more, more preferably 3,000 or more, further preferably 4,000 or more, further preferably 5,000 or more, particularly preferably 6,000 or more, and most preferably 7,000 or more, and is usually 30,000 or less, preferably 20,000 or less, more preferably 15,000 or less, and further preferably 10,000 or less. When the content is not less than the lower limit, the amount of outgas generated during light emission of the device tends to decrease, and when the content is not more than the upper limit, the content of residue tends to decrease.

(C) The content of the (c1) epoxy (meth) acrylate resin contained in the alkali-soluble resin is not particularly limited, but is preferably 30% by mass or more, more preferably 50% by mass or more, further preferably 70% by mass or more, further preferably 80% by mass or more, particularly preferably 90% by mass or more, and usually 100% by mass or less. When the content is not less than the lower limit, the amount of outgas generation tends to decrease.

(c1) The epoxy (meth) acrylate resin can be synthesized by a conventionally known method. Specifically, the following method may be employed: the epoxy resin is dissolved in an organic solvent, the acid or ester compound having an ethylenically unsaturated bond is added in the presence of a catalyst and a thermal polymerization inhibitor to cause an addition reaction, and a polybasic acid or an anhydride thereof is further added to continue the reaction.

Here, as the organic solvent used for the reaction, there may be mentioned: one or more organic solvents selected from methyl ethyl ketone, cyclohexanone, diethylene glycol ethyl ether acetate, propylene glycol monomethyl ether acetate, etc.

Further, as the catalyst, there may be mentioned: one or more of tertiary amines such as triethylamine, benzyldimethylamine and tribenzylamine, quaternary ammonium salts such as tetramethylammonium chloride, methyltriethylammonium chloride, tetraethylammonium chloride, tetrabutylammonium chloride and trimethylbenzylammonium chloride, phosphorus compounds such as triphenylphosphine, and antimony compounds such as triphenylantimony.

Further, the thermal polymerization inhibitor may be one or more of hydroquinone, hydroquinone monomethyl ether, and methyl hydroquinone.

The acid or ester compound having an ethylenically unsaturated bond may be used in an amount of usually 0.7 to 1.3 chemical equivalents, preferably 0.9 to 1.1 chemical equivalents, relative to 1 chemical equivalent of the epoxy group of the epoxy resin. The temperature during the addition reaction may be generally 60 to 150 ℃, preferably 80 to 120 ℃. The amount of the polybasic acid or the anhydride thereof to be used may be usually 0.1 to 1.2 stoichiometric equivalents, preferably 0.2 to 1.1 stoichiometric equivalents, based on 1 stoichiometric equivalent of the hydroxyl group produced in the addition reaction.

(c1) The epoxy (meth) acrylate resin may contain a partial structure other than the partial structure represented by the above general formula (1), and preferably contains at least one selected from the following group from the viewpoint of reducing the amount of outgas generated in the light emission of the device: an epoxy (meth) acrylate resin containing a repeating unit structure represented by the following formula (i), an epoxy (meth) acrylate resin containing a partial structure represented by the following formula (ii), and an epoxy (meth) acrylate resin containing a partial structure represented by the following formula (iii).

From the viewpoint of reducing the amount of outgas generated in the light emission of the device, (c1) the epoxy (meth) acrylate resin is preferably an epoxy (meth) acrylate resin (c1-1) containing a repeating unit represented by the following formula (i). One reason for this is that the steel sheet is hard to decompose by heat because it has a rigid main skeleton.

[ chemical formula 14]

In the formula (i), R^aRepresents a hydrogen atom or a methyl group, R^bRepresents a 2-valent hydrocarbon group optionally having a substituent, the benzene ring in the formula (i) is optionally further substituted with an optional substituent, and represents a bonding position.

(R^b)

In the above formula (i), R^bRepresents a 2-valent hydrocarbon group optionally having a substituent.

As the 2-valent hydrocarbon group, there may be mentioned: a 2-valent aliphatic group, a 2-valent aromatic group, and a group in which 1 or more 2-valent aliphatic groups and 1 or more 2-valent aromatic groups are linked.

Examples of the 2-valent aliphatic group include linear, branched and cyclic groups. Among these, a linear group is preferable from the viewpoint of developing solubility, and a cyclic 2-valent aliphatic group is preferable from the viewpoint of reducing permeation of the developing solution into the exposed portion. The number of carbon atoms is usually 1 or more, preferably 3 or more, more preferably 6 or more, and preferably 20 or less, more preferably 15 or less, and further preferably 10 or less. When the amount is not less than the lower limit, the development adhesion tends to be improved, and when the amount is not more than the upper limit, the amount of residue tends to be reduced.

Specific examples of the 2-valent linear aliphatic group include: methylene, ethylene, n-propylene, n-butylene, n-hexylene, n-heptylene, and the like. Among these, methylene is preferable from the viewpoint of reducing the residue.

Specific examples of the 2-valent branched aliphatic group include: the linear aliphatic group having a valence of 2 described above has a structure having a side chain such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, or a tert-butyl group.

The number of rings of the 2-valent cyclic aliphatic group is not particularly limited, and is usually 1 or more, preferably 2 or more, and usually 10 or less, preferably 5 or less. When the lower limit value is not less than the above-mentioned lower limit value, the residual film ratio tends to be improved, and when the upper limit value is not more than the above-mentioned upper limit value, the residual film ratio tends to be reduced. Specific examples of the 2-valent cyclic aliphatic group include: a group obtained by removing 2 hydrogen atoms from a ring such as a cyclohexane ring, a cycloheptane ring, a cyclodecane ring, a cyclododecane ring, a norbornane ring, an isoborneol ring, an adamantane ring or a cyclododecane ring. Among these groups, from the viewpoint of development adhesion, a group obtained by removing 2 hydrogen atoms from the adamantane ring is preferable.

As the substituent optionally having the 2-valent aliphatic group, there may be mentioned: alkoxy groups having 1 to 5 carbon atoms such as methoxy and ethoxy; a hydroxyl group; a nitro group; a cyano group; carboxyl groups, and the like. Among these, from the viewpoint of ease of synthesis, the compound is preferably unsubstituted.

Examples of the 2-valent aromatic ring group include a 2-valent aromatic ring group and a 2-valent aromatic heterocyclic group. The number of carbon atoms is usually 4 or more, preferably 5 or more, more preferably 6 or more, and preferably 20 or less, more preferably 15 or less, further preferably 10 or less. When the amount is equal to or more than the lower limit, the development adhesion tends to be improved, and when the amount is equal to or less than the upper limit, the amount of residue tends to be reduced.

The aromatic hydrocarbon ring in the 2-valent aromatic hydrocarbon ring group may be a single ring or a condensed ring. As the 2-valent aromatic hydrocarbon ring group, for example: a group having 2 free valences of a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a perylene ring, a tetracene ring, a pyrene ring, a benzopyrene ring, an azulene ring, a benzophenanthrene ring, an acenaphthylene ring, a fluoranthene ring, a fluorene ring, or the like.

The aromatic heterocyclic group in the aromatic heterocyclic group may be a monocyclic ring or a fused ring. Examples of the 2-valent aromatic heterocyclic group include: furan, benzofuran, thiophene, benzothiophene, pyrrole, pyrazole, imidazole, or imidazole rings having 2 free valences,

A diazole ring, an indole ring, a carbazole ring, a pyrroloimidazole ring, a pyrrolopyrazole ring, a pyrrolopyrrole ring, a thienopyrrole ring, a thienothiophene ring, a furopyrrole ring, a furofuran ring, a thienofuran ring, a benzisoxazole ring

An azole ring, a benzisothiazole ring, a benzimidazole ring, a pyridine ring, a pyrazine ring, a pyridazine ring, a pyrimidine ring, a triazine ring, a quinoline ring, an isoquinoline ring, a cinnoline ring, a quinoxaline ring, a phenanthridine ring, a benzimidazole ring, a triazine ring, a derivative thereof, or a derivative thereof,

A pyridine ring, a quinazoline ring, a quinazolinone ring, an azulene ring, and the like. Of these, from the viewpoint of photocurability, a benzene ring or a naphthalene ring having 2 free valences is preferable, and a benzene ring having 2 free valences is more preferable.

Examples of the substituent optionally having a 2-valent aromatic ring group include a hydroxyl group, a methyl group, a methoxy group, an ethyl group, an ethoxy group, a propyl group, and a propoxy group. Among these, non-substitution is preferable from the viewpoint of curability.

Examples of the group in which 1 or more 2-valent aliphatic groups and 1 or more 2-valent aromatic ring groups are linked include groups in which 1 or more of the 2-valent aliphatic groups and 1 or more of the 2-valent aromatic ring groups are linked.

The number of the 2-valent aliphatic group is not particularly limited, and is usually 1 or more, preferably 2 or more, and usually 10 or less, preferably 5 or less, more preferably 3 or less. When the amount is not less than the lower limit, development adhesion tends to be improved, and when the amount is not more than the upper limit, residue tends to be reduced.

The number of the 2-valent aromatic ring groups is not particularly limited, and is usually 1 or more, preferably 2 or more, and usually 10 or less, preferably 5 or less, more preferably 3 or less. When the amount is not less than the lower limit, development adhesion tends to be improved, and when the amount is not more than the upper limit, residue tends to be reduced.

Specific examples of the group in which 1 or more 2-valent aliphatic groups and 1 or more 2-valent aromatic ring groups are linked include: groups represented by the following formulae (i-A) to (i-E), and the like. Among these groups, from the viewpoint of rigidity of the skeleton and hydrophobization of the film, a group represented by the following formula (i-a) is preferable.

[ chemical formula 15]

As described above, the benzene ring in the formula (i) is optionally further substituted with an optional substituent. Examples of the substituent include: hydroxyl, methyl, methoxy, ethyl, ethoxy, propyl, propoxy, and the like. The number of the substituents is not particularly limited, and may be 1 or 2 or more.

Among these, from the viewpoint of curability, the compound is preferably unsubstituted.

From the viewpoint of developing solubility, the repeating unit structure represented by the above formula (i) is preferably a repeating unit structure represented by the following formula (i-1). The formula of the repeating unit structure represented by the formula (i-1) includes a partial structure represented by the above general formula (1).

[ chemical formula 16]

In the formula (i-1), R^aAnd R^bAnd R in the above formula (i)^aAnd R^bSynonymously. R¹And R in the above formula (1)¹Synonymously, indicates the bonding position, and the phenyl ring in formula (i-1) is optionally further substituted with any substituent.

The epoxy (meth) acrylate resin (c1-1) may have one or more repeating unit structures represented by the above formula (i-1) contained in 1 molecule.

The number of the repeating unit structure represented by the above formula (i) contained in 1 molecule of the epoxy (meth) acrylate resin (c1-1) is not particularly limited, but is preferably 1 or more, more preferably 2 or more, further preferably 3 or more, and further preferably 10 or less, further preferably 8 or less. When the amount is equal to or more than the lower limit, the development adhesion tends to be improved, and when the amount is equal to or less than the upper limit, the amount of residue tends to be reduced.

The number of the repeating unit structure represented by the above formula (i-1) contained in 1 molecule of the epoxy (meth) acrylate resin (c1-1) is not particularly limited, but is preferably 1 or more, more preferably 2 or more, further preferably 3 or more, and further preferably 10 or less, further preferably 8 or less. When the amount is equal to or more than the lower limit, the development adhesion tends to be improved, and when the amount is equal to or less than the upper limit, the amount of residue tends to be reduced.

Specific examples of the epoxy (meth) acrylate resin (c1-1) are shown below.

[ chemical formula 17]

[ chemical formula 18]

[ chemical formula 19]

[ chemical formula 20]

On the other hand, from the viewpoint of development adhesion, the (c1) epoxy (meth) acrylate resin is preferably an epoxy (meth) acrylate resin (c1-2) containing a partial structure represented by the following formula (ii).

[ chemical formula 21]

In the formula (ii), R^cEach independently represents a hydrogen atom or a methyl group, R^dRepresents a 2-valent hydrocarbon group having a cyclic hydrocarbon group as a side chain, and represents a bonding position.

(R^d)

In the above formula (ii), R^dRepresents a 2-valent hydrocarbon group having a cyclic hydrocarbon group as a side chain.

Examples of the cyclic hydrocarbon group include an aliphatic ring group and an aromatic ring group.

The number of rings of the aliphatic ring group is not particularly limited, and is usually 1 or more, preferably 2 or more, and usually 10 or less, preferably 5 or less, and more preferably 3 or less. When the amount is equal to or more than the lower limit, the development adhesion tends to be improved, and when the amount is equal to or less than the upper limit, the amount of residue tends to be reduced.

The aliphatic ring group has usually 4 or more, preferably 6 or more, more preferably 8 or more, and preferably 40 or less, more preferably 30 or less, further preferably 20 or less, and particularly preferably 15 or less carbon atoms. When the amount is equal to or more than the lower limit, the development adhesion tends to be improved, and when the amount is equal to or less than the upper limit, the amount of residue tends to be reduced.

Specific examples of the aliphatic ring in the aliphatic ring group include: cyclohexane ring, cycloheptane ring, cyclodecane ring, cyclododecane ring, norbornane ring, isobornyl ring, adamantane ring, cyclododecane ring and the like. Among these, an adamantane ring is preferable from the viewpoint of development adhesion.

On the other hand, the number of rings of the aromatic ring group is not particularly limited, and is usually 1 or more, preferably 2 or more, more preferably 3 or more, and is usually 10 or less, preferably 5 or less, more preferably 4 or less. When the amount is not less than the lower limit, the amount of residue tends to decrease, and when the amount is not more than the upper limit, the development adhesion tends to be improved.

Examples of the aromatic ring group include an aromatic ring group and an aromatic heterocyclic group. The number of carbon atoms of the aromatic ring group is usually 4 or more, preferably 6 or more, more preferably 8 or more, further preferably 10 or more, and particularly preferably 12 or more, and preferably 40 or less, more preferably 30 or less, further preferably 20 or less, and particularly preferably 15 or less. When the amount is not less than the lower limit, the amount of residue tends to decrease, and when the amount is not more than the upper limit, the development adhesion tends to improve.

Specific examples of the aromatic ring in the aromatic ring group include: benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, tetracene ring, pyrene ring, benzopyrene ring,

A ring, a benzophenanthrene ring, an acenaphthylene ring, a fluoranthene ring, a fluorene ring, etc. Among these, the fluorene ring is preferable from the viewpoint of pattern characteristics.

In addition, the 2-valent hydrocarbon group in the 2-valent hydrocarbon group having a cyclic hydrocarbon group as a side chain is not particularly limited, and examples thereof include: a 2-valent aliphatic group, a 2-valent aromatic group, and a group in which 1 or more 2-valent aliphatic groups and 1 or more 2-valent aromatic groups are linked.

Examples of the 2-valent aliphatic group include linear, branched, and cyclic groups. Of these, a linear 2-valent aliphatic group is preferable from the viewpoint of developing solubility, and a cyclic 2-valent aliphatic group is preferable from the viewpoint of reducing permeation of the developing solution into exposed portions. The number of carbon atoms is usually 1 or more, preferably 3 or more, more preferably 6 or more, and preferably 25 or less, more preferably 20 or less, and further preferably 15 or less. When the amount is equal to or more than the lower limit, the development adhesion tends to be improved, and when the amount is equal to or less than the upper limit, the amount of residue tends to be reduced.

Specific examples of the 2-valent linear aliphatic group include: methylene, ethylene, n-propylene, n-butylene, n-hexylene, n-heptylene, and the like. Among these, methylene is preferred from the viewpoint of residue.

Specific examples of the 2-valent branched aliphatic group include: the aforementioned 2-valent linear aliphatic group has a structure of a side chain such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, or the like.

The number of rings of the 2-valent cyclic aliphatic group is not particularly limited, and is usually 1 or more, preferably 2 or more, and usually 10 or less, preferably 5 or less, and more preferably 3 or less. When the amount is equal to or more than the lower limit, the development adhesion tends to be improved, and when the amount is equal to or less than the upper limit, the amount of residue tends to be reduced.

Specific examples of the 2-valent cyclic aliphatic group include: a group obtained by removing 2 hydrogen atoms from a ring such as a cyclohexane ring, a cycloheptane ring, a cyclodecane ring, a cyclododecane ring, a norbornane ring, an isoborneol ring, an adamantane ring or a cyclododecane ring. Among these, from the viewpoint of development adhesion, a group obtained by removing 2 hydrogen atoms from an adamantane ring is preferable.

As the substituent optionally having the 2-valent aliphatic group, there may be mentioned: alkoxy groups having 1 to 5 carbon atoms such as methoxy group and ethoxy group; a hydroxyl group; a nitro group; a cyano group; carboxyl groups, and the like. Among these, from the viewpoint of ease of synthesis, the compound is preferably unsubstituted.

Examples of the 2-valent aromatic ring group include a 2-valent aromatic ring group and a 2-valent aromatic heterocyclic group. The number of carbon atoms is usually 4 or more, preferably 5 or more, more preferably 6 or more, and preferably 30 or less, more preferably 20 or less, and further preferably 15 or less. When the amount is equal to or more than the lower limit, the development adhesion tends to be improved, and when the amount is equal to or less than the upper limit, the amount of residue tends to be reduced.

As in 2-valent aromatic hydrocarbon ring groupsThe aromatic hydrocarbon ring may be a single ring or a condensed ring. As the 2-valent aromatic hydrocarbon ring group, for example: benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, tetracene ring, pyrene ring, benzopyrene ring, perylene,

A ring, a benzophenanthrene ring, an acenaphthene ring, an anthryl ring, a fluorene ring, etc.

The aromatic heterocyclic group in the aromatic heterocyclic group may be a monocyclic ring or a fused ring. Examples of the 2-valent aromatic heterocyclic group include: furan, benzofuran, thiophene, benzothiophene, pyrrole, pyrazole, imidazole, or imidazole ring having 2 free valences,

An azole ring, a benzisothiazole ring, a benzimidazole ring, a pyridine ring, a pyrazine ring, a pyridazine ring, a pyrimidine ring, a triazine ring, a quinoline ring, an isoquinoline ring, a cinnoline ring, a quinoxaline ring, a phenanthridine ring, a benzimidazole ring, a pyridine ring, a pyrimidine ring, a triazine ring, a quinoline ring, a benzimidazole ring, a pyridine ring, a compound, a,

A pyridine ring, a quinazoline ring, a quinazolinone ring, an azulene ring, etc. Of these, from the viewpoint of photocurability, a benzene ring or a naphthalene ring having 2 free valences is preferable, and a benzene ring having 2 free valences is more preferable.

As the substituent optionally having a 2-valent aromatic ring group, there can be mentioned: hydroxyl, methyl, methoxy, ethyl, ethoxy, propyl, propoxy, and the like. Among these, from the viewpoint of curability, the resin is preferably unsubstituted.

Examples of the group in which 1 or more of the 2-valent aliphatic groups and 1 or more of the 2-valent aromatic ring groups are linked include: a group in which 1 or more of the aforementioned 2-valent aliphatic groups are linked to 1 or more of the aforementioned 2-valent aromatic ring groups.

The number of the 2-valent aliphatic group is not particularly limited, but is usually 1 or more, preferably 2 or more, and usually 10 or less, preferably 5 or less, and more preferably 3 or less. When the amount is not less than the lower limit, development adhesion tends to be improved, and when the amount is not more than the upper limit, residue tends to be reduced.

The number of the 2-valent aromatic ring groups is not particularly limited, and is usually 1 or more, preferably 2 or more, and usually 10 or less, preferably 5 or less, more preferably 3 or less. When the amount is not less than the lower limit, the development adhesion tends to be improved, and when the amount is not more than the upper limit, the amount of residue tends to be reduced.

Specific examples of the group in which 1 or more 2-valent aliphatic groups and 1 or more 2-valent aromatic ring groups are linked include: and groups represented by the above formulae (i-A) to (i-E). Among these groups, the group represented by the above formula (i-C) is preferable from the viewpoint of reducing the residue.

The bonding form of the cyclic hydrocarbon group as the side chain to these 2-valent hydrocarbon groups is not particularly limited, and examples thereof include: the side chain is substituted with an aliphatic group or 1 hydrogen atom of an aromatic ring group, or a cyclic hydrocarbon group having 1 carbon atom of the aliphatic group as a side chain.

In addition, the partial structure represented by the above formula (ii) is preferably a partial structure represented by the following formula (ii-1) from the viewpoint of development adhesion.

[ chemical formula 22]

In the formula (ii-1), R^cSynonymous with the above formula (ii), R^αRepresents an optionally substituted 1-valent cyclic hydrocarbon group, n is an integer of 1 or more, and is represented by the formula (ii-1)The benzene ring of (a) is optionally further substituted with an optional substituent.

(R^α)

In the above formula (ii-1), R^αRepresents a 1-valent cyclic hydrocarbon group optionally having a substituent.

The number of rings of the aliphatic ring group is not particularly limited, and is usually 1 or more, preferably 2 or more, and usually 6 or less, preferably 4 or less, and more preferably 3 or less. When the amount is equal to or more than the lower limit, the development adhesion tends to be improved, and when the amount is equal to or less than the upper limit, the amount of residue tends to be reduced.

Specific examples of the aliphatic ring in the aliphatic ring group include: cyclohexane ring, cycloheptane ring, cyclodecane ring, cyclododecane ring, norbornane ring, isobornyl ring, adamantane ring, cyclododecane ring, and the like. Among these, an adamantane ring is preferable from the viewpoint of development adhesion.

On the other hand, the number of rings of the aromatic ring group is not particularly limited, but is usually 1 or more, preferably 2 or more, more preferably 3 or more, and is usually 10 or less, preferably 5 or less. When the amount is not less than the lower limit, the development adhesion tends to be improved, and when the amount is not more than the upper limit, the amount of residue tends to be reduced.

Examples of the aromatic ring group include an aromatic hydrocarbon ring group and an aromatic heterocyclic group. The number of carbon atoms of the aromatic ring group is usually 4 or more, preferably 5 or more, more preferably 6 or more, and preferably 30 or less, more preferably 20 or less, and further preferably 15 or less. When the amount is not less than the lower limit, the development adhesion tends to be improved, and when the amount is not more than the upper limit, the amount of residue tends to be reduced.

Specific examples of the aromatic ring in the aromatic ring group include: benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, fluorene ring, etc. Among these, the fluorene ring is preferable from the viewpoint of development adhesion.

Examples of the substituent optionally contained in the cyclic hydrocarbon group include: an alkyl group having 1 to 5 carbon atoms such as a hydroxyl group, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, a pentyl group, an isopentyl group, etc.; alkoxy groups having 1 to 5 carbon atoms such as methoxy and ethoxy; a hydroxyl group; a nitro group; a cyano group; carboxyl groups, and the like. Among these, from the viewpoint of ease of synthesis, the compound is preferably unsubstituted.

n represents an integer of 1 or more, preferably 2 or more, and preferably 3 or less. When the amount is equal to or more than the lower limit, the development adhesion tends to be improved, and when the amount is equal to or less than the upper limit, the amount of residue tends to be reduced.

Among these, R is from the viewpoint of a strong film curability and electrical characteristics^αPreferably a 1-valent aliphatic ring group, more preferably an adamantyl group.

As described above, the benzene ring in the formula (ii-1) is optionally further substituted with an optional substituent. Examples of the substituent include: hydroxyl, methyl, methoxy, ethyl, ethoxy, propyl, propoxy, and the like. The number of the substituents is not particularly limited, and may be 1 or 2 or more. Among these, from the viewpoint of curability, the resin is preferably unsubstituted.

Specific examples of the partial structure represented by the above formula (ii-1) are shown below.

[ chemical formula 23]

[ chemical formula 24]

[ chemical formula 25]

[ chemical formula 26]

[ chemical formula 27]

In addition, the partial structure represented by the above formula (ii) is preferably a partial structure represented by the following formula (ii-2) from the viewpoint of development adhesion.

[ chemical formula 28]

In the formula (ii-2), R^cSynonymous with the above formula (ii), R^βRepresents a 2-valent cyclic hydrocarbon group optionally having a substituent, and the benzene ring in the formula (ii-2) is optionally further substituted with an optional substituent.

(R^β)

In the above formula (ii-2), R^βRepresents a 2-valent cyclic hydrocarbon group optionally having a substituent.

The number of rings of the aliphatic ring group is not particularly limited, and is usually 1 or more, preferably 2 or more, and usually 10 or less, preferably 5 or less. When the amount is not less than the lower limit, the development adhesion tends to be improved, and when the amount is not more than the upper limit, the amount of residue tends to be reduced.

The aliphatic ring group has usually 4 or more, preferably 6 or more, more preferably 8 or more, and preferably 40 or less, more preferably 35 or less, and still more preferably 30 or less carbon atoms. When the amount is equal to or more than the lower limit, the development adhesion tends to be improved, and when the amount is equal to or less than the upper limit, the amount of residue tends to be reduced.

Specific examples of the alicyclic ring in the alicyclic ring group include: cyclohexane ring, cycloheptane ring, cyclodecane ring, cyclododecane ring, norbornane ring, isobornyl ring, adamantane ring, cyclododecane ring and the like. Among these, an adamantane ring is preferable from the viewpoint of development adhesion.

On the other hand, the number of rings of the aromatic ring group is not particularly limited, and is usually 1 or more, preferably 2 or more, more preferably 3 or more, and is usually 10 or less, preferably 5 or less. When the amount is not less than the lower limit, the development adhesion tends to be improved, and when the amount is not more than the upper limit, the amount of residue tends to be reduced.

Examples of the aromatic ring group include an aromatic ring group and an aromatic heterocyclic group. The number of carbon atoms of the aromatic ring group is usually 4 or more, preferably 6 or more, more preferably 8 or more, further preferably 10 or more, and preferably 40 or less, more preferably 30 or less, further preferably 20 or less, particularly preferably 15 or less. When the amount is not less than the lower limit, the development adhesion tends to be improved, and when the amount is not more than the upper limit, the amount of residue tends to be reduced.

Examples of the substituent optionally contained in the cyclic hydrocarbon group include: an alkyl group having 1 to 5 carbon atoms such as a hydroxyl group, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, a pentyl group, an isopentyl group, etc.; alkoxy groups having 1 to 5 carbon atoms such as methoxy and ethoxy; a hydroxyl group; a nitro group; a cyano group; carboxyl group and the like. Among these, from the viewpoint of ease of synthesis, the compound is preferably unsubstituted.

Among these, R is R from the viewpoint of curability^βPreferably a 2-valent aliphatic ring group, more preferably a 2-valent adamantyl ring group.

On the other hand, from the viewpoint of development adhesion, R^βPreferably a 2-valent aromatic ring group, more preferably a 2-valent fluorene ring group.

As described above, the benzene ring in the formula (ii-2) is optionally further substituted with an optional substituent. Examples of the substituent include: hydroxyl, methyl, methoxy, ethyl, ethoxy, propyl, propoxy, and the like. The number of the substituent is not particularly limited, and may be 1 or 2 or more. Among these, from the viewpoint of curability, the resin is preferably unsubstituted.

Specific examples of the partial structure represented by the above formula (ii-2) are shown below.

[ chemical formula 29]

[ chemical formula 30]

[ chemical formula 31]

[ chemical formula 32]

On the other hand, the partial structure represented by the above formula (ii) is preferably a partial structure represented by the following formula (ii-3) from the viewpoint of curability. The partial structure represented by the formula (ii-3) includes the partial structure represented by the above general formula (1).

[ chemical formula 33]

In the formula (ii-3), R^cAnd R^dSynonymous with the above formula (ii), R¹The same meaning as in the above formula (1).

The partial structure represented by the above formula (ii-3) contained in 1 molecule of the epoxy (meth) acrylate resin (c1-2) may be one kind or two or more kinds.

The number of the partial structures represented by the above formula (ii) contained in 1 molecule of the epoxy (meth) acrylate resin (c1-2) is not particularly limited, but is preferably 1 or more, more preferably 3 or more, and is preferably 20 or less, more preferably 15 or less, and still more preferably 10 or less. When the amount is not less than the lower limit, the development adhesion tends to be improved, and when the amount is not more than the upper limit, the amount of residue tends to be reduced.

On the other hand, from the viewpoint of reducing the amount of outgas generated during light emission of the device, the epoxy (meth) acrylate resin (c1) is preferably an epoxy (meth) acrylate resin (c1-3) containing a partial structure represented by the following formula (iii).

[ chemical formula 34]

In the formula (iii), R^eRepresents a hydrogen atom or a methyl group, γ represents a single bond, -CO-, an alkylene group optionally having a substituent, or a 2-valent cyclic hydrocarbon group optionally having a substituent, and the benzene ring in the formula (iii) is optionally further substituted with an optional substituent, and represents a bonding position.

(γ)

In the above formula (iii), γ represents a single bond, -CO-, an alkylene group optionally having a substituent, or a 2-valent cyclic hydrocarbon group optionally having a substituent.

The alkylene group may be linear or branched, and is preferably linear from the viewpoint of developing solubility, and is preferably branched from the viewpoint of developing adhesion. The number of carbon atoms is not particularly limited, but is usually 1 or more, preferably 2 or more, and is usually 6 or less, preferably 4 or less. When the amount is not less than the lower limit, development adhesion tends to be improved, and when the amount is not more than the upper limit, residue tends to be reduced.

Specific examples of the alkylene group include: methylene, ethylene, propylene, butylene, hexylene, and heptylene are preferably ethylene or propylene, and more preferably propylene, from the viewpoint of satisfying both development adhesion and development solubility.

Examples of the substituent optionally contained in the alkylene group include: alkoxy groups having 1 to 5 carbon atoms such as methoxy group and ethoxy group; a hydroxyl group; a nitro group; a cyano group; carboxyl group and the like. Among these, non-substitution is preferable from the viewpoint of ease of synthesis.

The 2-valent cyclic hydrocarbon group may include a 2-valent aliphatic ring group and a 2-valent aromatic ring group.

The number of rings included in the aliphatic ring group is not particularly limited, and is usually 1 or more, preferably 2 or more, and usually 10 or less, preferably 5 or less. When the amount is not less than the lower limit, development adhesion tends to be improved, and when the amount is not more than the upper limit, residue tends to be reduced.

Among these, γ is preferably an alkylene group optionally having a substituent, and more preferably dimethylmethylene, from the viewpoint of reducing the residue.

As mentioned above, the phenyl ring in formula (iii) is optionally further substituted with an optional substituent. Examples of the substituent include: hydroxyl, methyl, methoxy, ethyl, ethoxy, propyl, propoxy, and the like. The number of the substituents is not particularly limited, and may be 1 or 2 or more. Among these, from the viewpoint of curability, the resin is preferably unsubstituted.

On the other hand, from the viewpoint of developing solubility, the partial structure represented by the above formula (iii) is preferably a partial structure represented by the following formula (iii-1). The partial structure represented by the formula (iii-1) includes a partial structure represented by the above general formula (1).

[ chemical formula 35]

In the formula (iii-1), R^eAnd γ is the same as in the above formula (iii), R¹And R in the above formula (1)¹Synonymously, indicates the bonding position. The benzene ring in the formula (iii-1) is optionally further substituted with an optional substituent.

The number of the repeating unit structure represented by the above formula (iii) contained in 1 molecule of the epoxy (meth) acrylate resin (c1-3) is not particularly limited, but is preferably 1 or more, more preferably 5 or more, further preferably 10 or more, and further preferably 18 or less, further preferably 15 or less. When the amount is not less than the lower limit, the development adhesion tends to be improved, and when the amount is not more than the upper limit, the amount of residue tends to be reduced.

The number of the repeating unit structure represented by the above formula (iii-1) contained in 1 molecule of the epoxy (meth) acrylate resin (c1-3) is not particularly limited, but is preferably 1 or more, more preferably 3 or more, further preferably 5 or more, and further preferably 18 or less, further preferably 15 or less. When the amount is equal to or more than the lower limit, the development adhesion tends to be improved, and when the amount is equal to or less than the upper limit, the amount of residue tends to be reduced.

Specific examples of the epoxy (meth) acrylate resin (c1-3) are shown below.

[ chemical formula 36]

[ chemical formula 37]

[ (c2) acrylic copolymer resin ]

The acrylic copolymer resin (c2) will be described in detail below. (c2) The acrylic copolymer resin is not particularly limited as long as it has a partial structure represented by the above general formula (1), but from the viewpoint of curability, an acrylic copolymer resin having an ethylenically unsaturated group in a side chain is preferable.

(c2) The partial structure containing a side chain having an ethylenically unsaturated group contained in the acrylic copolymer resin is not particularly limited, but from the viewpoint of developing solubility, for example, a partial structure represented by the following general formula (I) is preferable.

[ chemical formula 38]

In the formula (I), R^ARepresents a hydrogen atom or a methyl group, R^BRepresents an optionally substituted alkenyl group or a group represented by the following general formula (II), and represents a bonding site.

[ chemical formula 39]

In the formula (II), R^CRepresents an alkenyl group optionally having a substituent. α represents an alkylene group optionally having a substituent, an arylene group optionally having a substituent, or an alkenylene group optionally having a substituent, and represents a bonding position to a carbonyl carbon.

(R^B)

In the above formula (I), R^BRepresents an optionally substituted alkenyl group or a group represented by the above general formula (II).

As R^BExamples of the alkenyl group in (1) include straight-chain, branched or cyclic alkenyl groups. The number of carbon atoms is preferably 2 or more, and is preferably 20 or less, more preferably 16 or less, further preferably 12 or less, further preferably 8 or less, particularly preferably 6 or less, and most preferably 4 or less. When the amount is not less than the lower limit, the development adhesion tends to be improved, and when the amount is not more than the upper limit, the curability tends to be improved.

Specific examples of the alkenyl group include: ethenyl, propenyl, butenyl, cyclohexenyl, and the like. Among these, from the viewpoint of curability, an ethylene group or an propylene group is preferable, and a vinyl group is more preferable.

Further, as the substituent optionally having an alkenyl group, there may be mentioned: alkyl, alkenyl, alkynyl, hydroxyl, carboxyl, chloro, bromo, fluoro, alkoxy, hydroxyalkyl, thiol, sulfonic acid, and the like. Among these groups, an alkyl group or an alkenyl group is preferable, and an alkyl group is more preferable, from the viewpoint of developability. When the substituent group has 2 or more, the substituent groups may be linked to each other to form a ring.

Of these groups, as R^BFrom the viewpoints of developability and curability, a vinyl group or an acryl group is preferable, and a vinyl group is more preferable.

(R^C)

In the above formula (II), R^CRepresents an alkenyl group optionally having a substituent.

As R^CExamples of the alkenyl group in (1) include straight-chain, branched or cyclic alkenyl groups. The number of carbon atoms is preferably 2 or more, and is preferably 20 or less, more preferably 16 or less, further preferably 12 or less, further preferably 8 or less, particularly preferably 6 or less, and most preferably 4 or less. When the amount is not less than the lower limit, the development adhesion tends to be improved, and when the amount is not more than the upper limit, the curability tends to be improved.

Specific examples of the alkenyl group include: ethenyl, propenyl, butenyl, cyclohexenyl, and the like. Among these alkenyl groups, from the viewpoint of curability, an ethylene group or an propylene group is preferable, and an ethylene group is more preferable.

Further, as the substituent optionally having an alkenyl group, there may be mentioned: alkyl, alkenyl, alkynyl, hydroxyl, carboxyl, chloro, bromo, fluoro, alkoxy, hydroxyalkyl, thiol, sulfonic acid, and the like. Among these groups, an alkyl group or an alkenyl group is preferable, and an alkyl group is more preferable, from the viewpoint of developability. When 2 or more substituents are present, the substituents may be linked to each other to form a ring.

Like this, R^CRepresents an alkenyl group optionally having a substituent, and among these groups, from the viewpoint of developability, an ethenyl group or a propenyl group is preferable, and an ethenyl group is more preferable.

(α)

In the above formula (II), α represents an alkylene group optionally having a substituent, an arylene group optionally having a substituent, or an alkenylene group optionally having a substituent.

Examples of the alkylene group in α include a linear, branched or cyclic alkylene group. The number of carbon atoms is preferably 1 or more, more preferably 2 or more, and further preferably 22 or less, more preferably 20 or less, further preferably 18 or less, further preferably 16 or less, particularly preferably 14 or less, and most preferably 12 or less. When the lower limit value is not less than the above-mentioned lower limit value, the adhesiveness tends to be improved, and when the upper limit value is not more than the above-mentioned upper limit value, the curability tends to be improved.

Specific examples of the alkylene group include: methylene, ethylene, propylene, cyclohexylene, methylcyclohexylene, bicyclo [2.2.1] heptanyl, methylbicyclo [2.2.1] heptanyl, and the like. Among these alkylene groups, ethylene, cyclohexylene, and methylcyclohexylene are preferable, and ethylene is more preferable, from the viewpoint of curability.

Further, as the substituent optionally having the alkylene group, there may be mentioned: alkenyl, alkynyl, hydroxy, carboxyl, chloro, bromo, fluoro, alkoxy, hydroxyalkyl, thiol, thio, and the like. Among these groups, an alkenyl group is preferable from the viewpoint of development adhesion. When 2 or more substituents are present, the substituents may be linked to each other to form a ring.

Further, as the arylene group in α, a 2-valent aromatic hydrocarbon ring group and a 2-valent aromatic heterocyclic ring group are exemplified. The number of carbon atoms is preferably 6 or more, and also preferably 24 or less, more preferably 22 or less, further preferably 20 or less, still more preferably 18 or less, particularly preferably 16 or less, and most preferably 14 or less. When the amount is equal to or more than the lower limit, the development adhesion tends to be improved, and when the amount is equal to or less than the upper limit, the amount of residue tends to be reduced.

The aromatic hydrocarbon ring in the aromatic hydrocarbon ring group may be a single ring or a condensed ring, and examples thereof include: benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, tetracene ring, pyrene ring, benzopyrene ring, azulene ring, benzophenanthrene ring, acenaphthene ring, fluoranthene ring, fluorene ring, etc.

The aromatic heterocyclic group in the aromatic heterocyclic group may be a monocyclic ring or a fused ring, and examples thereof include: furan ring, benzofuran ring, thiophene ring, benzothiophene ring, pyrrole ring, pyrazole ring, imidazole ring, or a salt thereof,

An azole ring, a benzisothiazole ring, a benzimidazole ring, a pyridine ring, a pyrazine ring, a pyridazine ring, a pyrimidine ring, a triazine ring, a quinoline ring, an isoquinoline ring, a cinnoline ring, a quinoxaline ring, a phenanthridine ring, a benzimidazole ring, a pyridine ring, a pyrazine ring, a pyrimidine ring, a triazine ring, a quinoline ring, an isoquinoline ring, a cinnoline ring, a quinoxaline ring, a phenanthridine ring, a benzimidazole ring, a pyridine ring, a pyrimidine ring, a triazine ring, a quinoline ring, a pyrimidine ring, a phenanthridine ring, a pyridine ring, a compound,

pyridine ring, quinazoline ring, azulene ring, etc. Among these aromatic heterocycles, a benzene ring or a naphthalene ring is preferable, and a benzene ring is more preferable, from the viewpoint of developability.

Further, as the substituent optionally having an arylene group, there may be mentioned: alkyl, alkenyl, alkynyl, hydroxyl, carboxyl, chloro, bromo, fluoro, alkoxy, hydroxyalkyl, thiol, sulfonic acid, and the like. Of these, from the viewpoint of developability, a hydroxyl group or a carboxyl group is preferable, and a carboxyl group is more preferable. When the compound has 2 or more substituents, the substituents may be linked to each other to form a ring.

Specific examples of the substituted arylene group include carboxyphenyl ring group and the like.

Examples of the alkenylene group in α include a linear, branched or cyclic alkenylene group. The number of carbon atoms is preferably 2 or more, and is preferably 22 or less, more preferably 20 or less, further preferably 18 or less, further preferably 16 or less, particularly preferably 14 or less, and most preferably 12 or less. When the amount is not less than the lower limit, the development adhesion tends to be improved, and when the amount is not more than the upper limit, the amount of residue tends to be reduced.

Specific examples of alkenylene groups include: vinylene, propenylene, cyclohexenylene, methylvinylene, and the like. Among these groups, from the viewpoint of developability, a vinylene group and a cyclohexenylene group are preferable, and a vinylene group is more preferable.

Further, as the substituent optionally having an alkenylene group, there may be mentioned: alkyl, alkenyl, alkynyl, hydroxy, carboxy, chloro, bromo, fluoro, alkoxy, hydroxyalkyl, thiol, thio, and the like. Among these groups, an alkyl group or an alkenyl group is preferable, and an alkyl group is more preferable, from the viewpoint of developability. When 2 or more substituents are present, the substituents may be linked to each other to form a ring.

In this manner, α represents an alkylene group optionally having a substituent, an arylene group optionally having a substituent, or an alkenylene group optionally having a substituent, and among these groups, an alkylene group or an alkenylene group is preferable, and an alkylene group is more preferable, from the viewpoint of developability.

In addition, the repeating unit structure represented by the above formula (I) is preferably a repeating unit structure represented by the following formula (I-1) from the viewpoint of developability. The formula of the repeating unit structure represented by the formula (I-1) includes a partial structure represented by the above general formula (1).

[ chemical formula 40]

In the formula (I-1), R^AAnd R^BAnd R in the above formula (I)^AAnd R^BSynonymously. R¹And R in the above formula (1)¹Synonymously.

From the viewpoint of sensitivity, the repeating unit structure represented by the above formula (I) is preferably a repeating unit structure represented by the following formula (I-2).

[ chemical formula 41]

In the formula (I-2), R^AAnd R^BAnd R in the above formula (I)^AAnd R^BSynonymously.

(c2) The content ratio of the partial structure represented by the above general formula (I) contained in the acrylic copolymer resin is not particularly limited, but is preferably 5 mol% or more, more preferably 20 mol% or more, further preferably 30 mol% or more, further preferably 50 mol% or more, particularly preferably 70 mol% or more, most preferably 80 mol% or more, and further preferably 99 mol% or less, more preferably 97 mol% or less, and further preferably 95 mol% or less. When the amount is not less than the lower limit, the amount of residue tends to decrease, and when the amount is not more than the upper limit, the development adhesion tends to improve.

(c2) The content ratio of the partial structure represented by the above general formula (I-1) contained in the acrylic copolymer resin is not particularly limited, but is preferably 1 mol% or more, more preferably 5 mol% or more, further preferably 10 mol% or more, further preferably 15 mol% or more, particularly preferably 20 mol% or more, and further preferably 99 mol% or less, more preferably 60 mol% or less, further preferably 40 mol% or less, and particularly preferably 30 mol% or less. When the amount is not less than the lower limit, sensitivity tends to be improved and residue tends to be reduced, and when the amount is not more than the upper limit, development adhesion tends to be improved.

(c2) The content ratio of the partial structure represented by the above general formula (I-2) contained in the acrylic copolymer resin is not particularly limited, but is preferably 5 mol% or more, more preferably 10 mol% or more, further preferably 20 mol% or more, further preferably 30 mol% or more, particularly preferably 40 mol% or more, most preferably 50 mol% or more, and further preferably 99 mol% or less, more preferably 90 mol% or less, further preferably 80 mol% or less, and particularly preferably 70 mol% or less. When the lower limit value is not less than the above-described lower limit value, the sensitivity tends to be improved, and when the upper limit value is not more than the above-described upper limit value, the developability tends to be improved.

(partial structure represented by the general formula (I'))

When the acrylic copolymer resin (c2) contains a partial structure represented by the above general formula (I), the other partial structures that may be contained are not particularly limited, but from the viewpoint of development adhesion, it is preferable to contain a partial structure represented by the following general formula (I'), for example.

[ chemical formula 42]

In the above formula (I'), R^DRepresents a hydrogen atom or a methyl group, R^ERepresents an alkyl group optionally having a substituent, an aryl group optionally having a substituent, or an alkenyl group optionally having a substituent.

(R^E)

In the above formula (I'), R^ERepresents an alkyl group optionally having a substituent, an aryl group optionally having a substituent, or an alkenyl group optionally having a substituent.

As R^EExamples of the alkyl group in (1) include linear, branched or cyclic alkyl groups. The number of carbon atoms is preferably 1 or more, more preferably 3 or more, further preferably 5 or more, and further preferably 20 or less, more preferably 18 or less, further preferably 16 or less, further preferably 14 or less, and particularly preferably 12 or less. When the amount is not less than the lower limit, the film strength tends to be improved and the development adhesion tends to be improved, and when the amount is not more than the upper limit, the amount of residue tends to be reduced.

Specific examples of the alkyl group include: methyl, ethyl, cyclohexyl, dicyclopentyl, dodecyl and the like. Among these groups, from the viewpoint of membrane strength, dicyclopentyl or dodecyl is preferable, and dicyclopentyl is more preferable.

Further, as the substituent optionally contained in the alkyl group, there may be mentioned: methoxy group, ethoxy group, chloro group, bromo group, fluoro group, hydroxy group, amino group, epoxy group, oligoethylene glycol group, phenyl group, carboxyl group, acryloyl group, methacryloyl group, etc., and from the viewpoint of developability, hydroxy group and oligoethylene glycol group are preferable.

As R^EAs the aryl group in (1), there may be mentioned a 1-valent aromatic hydrocarbon ring group and a 1-valent aromatic heterocyclic group. The number of carbon atoms is preferably 6 or more, and also preferably 24 or less, more preferably 22 or less, further preferably 20 or less, and particularly preferably 18 or less. When the amount is not less than the lower limit, the development adhesion tends to be improved, and when the amount is not more than the upper limit, the amount of residue tends to be reduced.

An azole ring, a benzisothiazole ring, a benzimidazole ring, a pyridine ring, a pyrazine ring, a pyridazine ring, a pyrimidine ring, a triazine ring, a quinoline ring, an isoquinoline ring, a cinnoline ring, an quinoxaline ring, a phenanthridine ring, a benzimidazole ring, a triazine ring, a quinoline ring, a quinoxaline ring, a phenanthridine ring, a benzimidazole ring, a pyridine ring, a pyrazine ring, a pyrimidine ring, a triazine ring, a quinoline ring, a quinoxaline ring, a phenanthrene ring, a compound, a,

Pyridine ring, quinazoline ring, azulene ring, etc. Of these, benzene rings or naphthalene rings are preferable, and benzene rings are more preferable from the viewpoint of curability.

Further, as the substituent optionally having an aryl group, there may be mentioned: methyl group, ethyl group, propyl group, methoxy group, ethoxy group, chloro group, bromo group, fluoro group, hydroxy group, amino group, epoxy group, oligoethylene glycol group, phenyl group, carboxyl group and the like, and from the viewpoint of developability, a hydroxy group or an oligoethylene glycol group is preferable.

As R^EExamples of the alkenyl group in (1) include a linear, branched or cyclic alkenyl group. The number of carbon atoms is preferably 2 or more, and is preferably 22 or less, more preferably 20 or less, further preferably 18 or less, further preferably 16 or less, and particularly preferably 14 or less. When the amount is not less than the lower limit, the development adhesion tends to be improved, and when the amount is not more than the upper limit, the amount of residue tends to be reduced.

Further, as the substituent optionally having an alkenyl group, there may be mentioned: methyl group, ethyl group, propyl group, methoxy group, ethoxy group, chloro group, bromo group, fluoro group, hydroxy group, amino group, epoxy group, oligoethylene glycol group, phenyl group, carboxyl group and the like, and from the viewpoint of developability, a hydroxy group or an oligoethylene glycol group is preferable.

Like this, R^ERepresents an alkyl group optionally having a substituent, an aryl group optionally having a substituent, or an alkenyl group optionally having a substituent, and among these groups, an alkyl group or an alkenyl group is preferable, and an alkyl group is more preferable, from the viewpoint of developability.

(c2) The content ratio of the partial structure represented by the above general formula (I') contained in the acrylic copolymer resin is not particularly limited, but is preferably 0.5 mol% or more, more preferably 1 mol% or more, further preferably 1.5 mol% or more, particularly preferably 2 mol% or more, and is preferably 90 mol% or less, more preferably 70 mol% or less, further preferably 50 mol% or less, further preferably 30 mol% or less, and particularly preferably 10 mol% or less. When the amount is not less than the lower limit, the development adhesion tends to be improved, and when the amount is not more than the upper limit, the amount of residue tends to be reduced.

(partial Structure represented by the general formula (I))

When the acrylic copolymer resin (c2) contains a partial structure represented by the above general formula (I), it is preferable that the acrylic copolymer resin (c2) contains a partial structure represented by the following general formula (I ") as another partial structure that may be contained, from the viewpoint of heat resistance and film strength.

[ chemical formula 43]

In the above formula (I'), R^FRepresents a hydrogen atom or a methyl group, R^GRepresents an alkyl group optionally having a substituent, an alkenyl group optionally having a substituent, a hydroxyl group, a carboxyl group, a halogen atom, an alkoxy group optionally having a substituent, a thiol group, or an alkylthio group optionally having a substituent. t represents an integer of 0 to 5.

(R^G)

In the above formula (I'), R^GRepresents an alkyl group optionally having a substituent, an alkenyl group optionally having a substituent, a hydroxyl group, a carboxyl group, a halogen atom, an alkoxy group optionally having a substituent, a thiol group, or an alkylthio group optionally having a substituent.

As R^GExamples of the alkyl group in (1) include linear, branched or cyclic alkyl groups. The number of carbon atoms is preferably 1 or more, more preferably 3 or more, further preferably 5 or more, and further preferably 20 or less, more preferably 18 or less, further preferably 16 or less, further preferably 14 or less, and particularly preferably 12 or less. When the amount is equal to or more than the lower limit, the development adhesion tends to be improved, and when the amount is equal to or less than the upper limit, the amount of residue tends to be reduced.

Specific examples of the alkyl group include: methyl, ethyl, cyclohexyl, dicyclopentyl, dodecyl and the like. Among these groups, from the viewpoint of development adhesion, dicyclopentyl or dodecyl group is preferable, and dicyclopentyl is more preferable.

As R^GExamples of the alkenyl group in (1) include straight-chain, branched or cyclic alkenyl groups. The number of carbon atoms is preferably 2 or more, and is preferably 22 or less, more preferably 20 or less, further preferably 18 or less, further preferably 16 or less, and particularly preferably 14 or less. When the amount is not less than the lower limit, the development adhesion tends to be improved, and when the amount is not more than the upper limit, the amount of residue tends to be reduced.

Specific examples of the alkenyl group include: ethenyl, propenyl, butenyl, cyclohexenyl, and the like. Among these groups, from the viewpoint of curability, an ethylene group or an propylene group is preferable, and an ethylene group is more preferable.

Further, as the substituent optionally having an alkenyl group, there may be mentioned: methyl group, ethyl group, propyl group, methoxy group, ethoxy group, chloro group, bromo group, fluoro group, hydroxyl group, amino group, epoxy group, oligoethylene glycol group, phenyl group, carboxyl group, and the like, and from the viewpoint of developability, a hydroxyl group or oligoethylene glycol group is preferable.

As R^GThe halogen atom in (b) includes a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and among these halogen atoms, a fluorine atom is preferable from the viewpoint of liquid repellency.

As R^GExamples of the alkoxy group in (1) include linear, branched or cyclic alkoxy groups. The number of carbon atoms is preferably 1 or more, and is preferably 20 or less, more preferably 18 or less, further preferably 16 or less, further preferably 14 or less, and particularly preferably 12 or less. When the amount is not less than the lower limit, the development adhesion tends to be improved, and when the amount is not more than the upper limit, the amount of residue tends to be reduced.

Further, as the substituent optionally having an alkoxy group, there may be mentioned: methoxy group, ethoxy group, chloro group, bromo group, fluoro group, hydroxy group, amino group, epoxy group, oligoethylene glycol group, phenyl group, carboxyl group, acryloyl group, methacryloyl group, and the like, and from the viewpoint of developability, a hydroxy group and an oligoethylene glycol group are preferable.

As R^GThe alkylthio group in (1) may be a straight-chain, branched or cyclic alkylthio group. The number of carbon atoms is preferably 1 or more, and is preferably 20 or less, more preferably 18 or less, further preferably 16 or less, further preferably 14 or less, and particularly preferably 12 or less. When the amount is not less than the lower limit, the development adhesion tends to be improved, and when the amount is not more than the upper limit, the amount of residue tends to be reduced.

Specific examples of the alkylthio group include: methylthio, ethylthio, propylthio, butylthio, and the like. Among these groups, a methylthio group or an ethylthio group is preferable from the viewpoint of developability.

In addition, as the substituent optionally having an alkyl group in the alkylthio group, there can be mentioned: methoxy group, ethoxy group, chloro group, bromo group, fluoro group, hydroxy group, amino group, epoxy group, oligoethylene glycol group, phenyl group, carboxyl group, acryloyl group, methacryloyl group, etc., and from the viewpoint of developability, hydroxy group and oligoethylene glycol group are preferable.

Like this, R^GRepresents an optionally substituted alkyl group, an optionally substituted alkenyl group, a hydroxyl group, a carboxyl group, a halogen atom, an alkoxy group, a hydroxyalkyl group, a thiol group, or an optionally substituted alkylthio group, and among these groups, from the viewpoint of developability, a hydroxyl group or a carboxyl group is preferable, and a carboxyl group is more preferable.

(t)

In the formula (I'), t represents an integer of 0 to 5. From the viewpoint of developability, t is preferably 2 or less, more preferably 1 or less, and still more preferably 0.

(c2) The content ratio of the partial structure represented by the above general formula (I ") contained in the acrylic copolymer resin is not particularly limited, and is preferably 1 mol% or more, more preferably 2 mol% or more, further preferably 3 mol% or more, particularly preferably 5 mol% or more, and further preferably 90 mol% or less, more preferably 70 mol% or less, further preferably 50 mol% or less, further preferably 30 mol% or less, particularly preferably 20 mol% or less, and most preferably 10 mol% or less. When the amount is not less than the lower limit, development adhesion tends to be improved, and when the amount is not more than the upper limit, residue tends to be reduced.

(partial structure shown by general formula (I'))

When the acrylic copolymer resin (c2) contains a partial structure represented by the above general formula (I), the partial structure represented by the following general formula (I' ") is preferable from the viewpoint of developability as the other partial structure that may be contained.

[ chemical formula 44]

The above formula (I) " ') wherein R^HRepresents a hydrogen atom or a methyl group.

(c2) The content ratio of the partial structure represented by the general formula (I' ") contained in the acrylic copolymer resin is not particularly limited, but is preferably 5 mol% or more, more preferably 10 mol% or more, further preferably 30 mol% or more, and further preferably 90 mol% or less, more preferably 80 mol% or less, further preferably 70 mol% or less, and particularly preferably 50 mol% or less. When the amount is not less than the lower limit, the amount of residue tends to decrease, and when the amount is not more than the upper limit, the development adhesion tends to improve. On the other hand, from the viewpoint of reducing the amount of outgas generated, it is preferably 0 mol%, that is, it is preferable that the partial structure represented by the above general formula (I' ") is not included.

(c2) The acid value of the acrylic copolymer resin is not particularly limited, but is preferably 5mgKOH/g or more, more preferably 10mgKOH/g or more, further preferably 30mgKOH/g or more, further preferably 40mgKOH/g or more, particularly preferably 50mgKOH/g or more, and further preferably 100mgKOH/g or less, more preferably 90mgKOH/g or less, further preferably 70mgKOH/g or less, and further preferably 60mgKOH/g or less. When the amount is equal to or more than the lower limit, the amount of the residue tends to be reduced, and when the amount is equal to or less than the upper limit, the development adhesion tends to be improved.

(c2) The weight average molecular weight (Mw) of the acrylic copolymer resin is not particularly limited, but is preferably 1,000 or more, more preferably 2,000 or more, further preferably 3,000 or more, still more preferably 4,000 or more, and particularly preferably 5,000 or more, and is usually 30,000 or less, preferably 20,000 or less, more preferably 15,000 or less, and further preferably 10,000 or less. Particularly preferably 7,000 or less. When the amount is not less than the lower limit, development adhesion tends to be improved, and when the amount is not more than the upper limit, residue tends to be reduced.

(C) The content ratio of the acrylic copolymer resin (c2) contained in the alkali-soluble resin is not particularly limited, but is preferably 5% by mass or more, more preferably 10% by mass or more, further preferably 15% by mass or more, and particularly preferably 20% by mass or more, and is preferably 100% by mass or less, more preferably 80% by mass or less, and further preferably 50% by mass or less, from the viewpoint of developability. When the amount is not less than the lower limit, the developing solubility tends to be good, and when the amount is not more than the upper limit, the taper angle tends to be large.

(C) The alkali-soluble resin may contain either (c1) the epoxy (meth) acrylate resin or (c2) the acrylic copolymer resin alone or both. Further, resins other than (c1) and (c2) may be contained. For example, the liquid repellency can be imparted to (C) the alkali-soluble resin itself by the alkali-soluble resin containing a functional group containing a fluorine atom.

The content ratio of the alkali-soluble resin (C) in the photosensitive resin composition of the invention of embodiment 1 is: the content is usually 5% by mass or more, preferably 10% by mass or more, more preferably 20% by mass or more, further preferably 30% by mass or more, and particularly preferably 40% by mass or more, and usually 90% by mass or less, preferably 70% by mass or less, more preferably 60% by mass or less, and particularly preferably 50% by mass or less, based on the total solid content. When the lower limit value is not less than the above-mentioned lower limit value, the developability tends to be improved, and when the upper limit value is not more than the above-mentioned upper limit value, the amount of outgas generation at the time of light emission of the element tends to be reduced.

The content ratio of the ethylenically unsaturated compound (a) and the alkali-soluble resin (C) in the total solid content is: the content is usually 5% by mass or more, preferably 10% by mass or more, more preferably 30% by mass or more, further preferably 50% by mass or more, further preferably 70% by mass or more, particularly preferably 80% by mass or more, and most preferably 85% by mass or more, and is usually 99% by mass or less, preferably 97% by mass or less, and more preferably 95% by mass or less, based on the total solid content. When the lower limit value is not less than the above-mentioned lower limit value, curability tends to be improved, and when the upper limit value is not more than the above-mentioned upper limit value, an amount of outgas generation at the time of light emission of the element tends to be reduced.

The blending ratio of the alkali-soluble resin (C) to the ethylenically unsaturated compound (a) in the photosensitive resin composition is preferably 50 parts by mass or more, more preferably 60 parts by mass or more, further preferably 70 parts by mass or more, and particularly preferably 80 parts by mass or more, and further preferably 400 parts by mass or less, more preferably 300 parts by mass or less, further preferably 200 parts by mass or less, and particularly preferably 100 parts by mass or less, with respect to 100 parts by mass of the ethylenically unsaturated compound (a). When the amount is not less than the lower limit, development adhesion tends to be improved, and when the amount is not more than the upper limit, curing tends to be improved.

On the other hand, the alkali-soluble resin (C) used in the photosensitive resin composition for forming a partition wall of an organic electroluminescent element according to embodiment 2 of the present invention will be described in detail below, as well as the carboxyl group-containing (co) polymer (C-1), the carboxyl group-containing (co) polymer (C-2) having an ethylenically unsaturated group in the side chain, and the carboxyl group-and ethylenically unsaturated group-containing resin (C-3).

[1-1-4-a ] (C-1) carboxyl group-containing (co) polymer

[1-1-4-a-1] carboxyl group-containing (co) Polymer (1)

Typical examples of the carboxyl group-containing (co) polymer include: unsaturated carboxylic acids such as (meth) acrylic acid, crotonic acid, isocrotonic acid, maleic anhydride, itaconic acid, and citraconic acid, and styrenes such as styrene, α -methylstyrene, and hydroxystyrene, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, dodecyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, adamantyl (meth) acrylate, isobornyl (meth) acrylate, hydroxymethyl (meth) acrylate, hydroxyethyl (meth) acrylate, glycidyl (meth) acrylate, benzyl (meth) acrylate, N-dimethylaminoethyl (meth) acrylate, and mixtures thereof, Copolymers of (meth) acrylates such as N- (meth) acrylmorpholine, (meth) acrylonitriles such as (meth) acrylonitrile, (meth) acrylamide, N-methylol (meth) acrylamide, N-dimethyl (meth) acrylamide, and (meth) acrylamides such as N, N-dimethylaminoethyl (meth) acrylamide, and vinyl compounds such as vinyl acetate.

Among these, from the viewpoint of sensitivity, (meth) acrylate- (meth) acrylic acid copolymer and styrene- (meth) acrylate- (meth) acrylic acid copolymer are preferable. Further, in the (meth) acrylate- (meth) acrylic acid copolymer, a copolymer of 5 to 80 mol% of (meth) acrylate and 20 to 95 mol% of (meth) acrylic acid is more preferable, and a copolymer of 10 to 70 mol% of (meth) acrylate and 30 to 90 mol% of (meth) acrylic acid is particularly preferable. Further, in the styrene- (meth) acrylate- (meth) acrylic acid copolymer, a copolymer of 3 to 60 mol% of styrene, 10 to 70 mol% of (meth) acrylate, and 10 to 60 mol% of (meth) acrylic acid is more preferable, and a copolymer of 5 to 50 mol% of styrene, 20 to 60 mol% of (meth) acrylate, and 15 to 55 mol% of (meth) acrylic acid is particularly preferable.

[1-1-4-a-2] carboxyl group-containing (co) Polymer (2)

Further, there may be mentioned copolymers obtained by copolymerizing the above-mentioned styrene, (meth) acrylate esters, (meth) acrylonitrile, (meth) acrylamide, vinyl compounds and the like with a compound obtained by adding a polybasic acid (anhydride) to a hydroxyalkyl (meth) acrylate, instead of the above-mentioned unsaturated carboxylic acid.

Examples of the hydroxyalkyl (meth) acrylate include hydroxymethyl (meth) acrylate, hydroxyethyl (meth) acrylate, hydroxybutyl (meth) acrylate, and the like, and examples of the polybasic acid (anhydride) include succinic acid (anhydride), adipic acid (anhydride), phthalic acid (anhydride), tetrahydrophthalic acid (anhydride), hexahydrophthalic acid (anhydride), maleic acid (anhydride), and the like, and examples of the reaction compound of the two include: [2- (meth) acryloylethyl ] succinate, [2- (meth) acryloylethyl ] adipate, [2- (meth) acryloylethyl ] phthalate, [2- (meth) acryloylethyl ] hexahydrophthalate, [2- (meth) acryloylethyl ] maleate, [2- (meth) acryloylpropyl ] succinate, [2- (meth) acryloylpropyl ] adipate, [2- (meth) acryloylpropyl ] phthalate, [2- (meth) acryloylpropyl ] hexahydrophthalate, [2- (meth) acryloylpropyl ] maleate, [2- (meth) acryloylpropyl ] succinate, [2- (meth) acryloylbutyl ] adipate, 2- (meth) acryloylbutyl phthalate, 2- (meth) acryloylbutyl hexahydrophthalate, 2- (meth) acryloylbutyl maleate and the like.

The carboxyl group-containing (co) polymer preferably has an acid value of 50 to 500mgKOH/g from the viewpoint of developing solubility, and a weight average molecular weight (Mw) in terms of polystyrene of 1,000 to 300,000 from the viewpoint of developing solubility.

[1-1-4-b ] (C-2) carboxyl group-containing (co) polymer having ethylenic unsaturated group in side chain

[1-1-4-b-1] copolymers of unsaturated carboxylic acids and two or more compounds having ethylenically unsaturated groups

Examples of the carboxyl group-containing (co) polymer having an ethylenically unsaturated group in a side chain thereof include: a compound having two or more ethylenically unsaturated groups such as allyl (meth) acrylate, 3-allyloxy-2-hydroxypropyl (meth) acrylate, cinnamyl (meth) acrylate, crotyl (meth) acrylate, methallyl (meth) acrylate, and N, N-diallyl (meth) acrylamide, a compound having two or more ethylenically unsaturated groups such as vinyl (meth) acrylate, 1-chloroethyl (meth) acrylate, 2-phenylethyl (meth) acrylate, 1-propenyl (meth) acrylate, vinyl crotonate, and vinyl (meth) acrylamide, and an unsaturated carboxylic acid such as (meth) acrylic acid, or further an unsaturated carboxylic acid ester are added so that the proportion of the compound having an ethylenically unsaturated group in the whole is 10 to 90 mol%, Preferably about 30 to 80 mol% of the copolymer.

The acid value of the copolymer of the unsaturated carboxylic acid and the compound having two or more ethylenically unsaturated groups is preferably 30 to 250mgKOH/g from the viewpoint of developing solubility, and the weight average molecular weight (Mw) thereof is preferably 1,000 to 300,000 from the viewpoint of developing solubility.

[1-1-4-b-2] carboxyl group-containing (co) polymer modified with epoxy group-containing unsaturated compound

Further, as the carboxyl group-containing (co) polymer having an ethylenically unsaturated group in a side chain, there may be exemplified: and a modified carboxyl group-containing (co) polymer obtained by reacting an epoxy group-containing unsaturated compound with a carboxyl group-containing (co) polymer and modifying the resulting product by adding a part of the carboxyl groups of the carboxyl group-containing (co) polymer to the epoxy groups of the epoxy group-containing unsaturated compound.

The carboxyl group-containing (co) polymer is preferably a (meth) acrylate- (meth) acrylic acid copolymer, a styrene- (meth) acrylate- (meth) acrylic acid copolymer, or the like of the above-described carboxyl group-containing (co) polymer, from the viewpoint of sensitivity.

Examples of the epoxy group-containing unsaturated compound include: aliphatic epoxy group-containing unsaturated compounds such as allyl glycidyl ether, glycidyl (meth) acrylate, α -ethyl glycidyl (meth) acrylate, glycidyl crotonate, glycidyl isocrotonate, crotonyl glycidyl ether, monoalkyl monoglycidyl itaconate, monoalkyl monoglycidyl fumarate and monoalkyl monoglycidyl maleate, and alicyclic epoxy group-containing unsaturated compounds such as 3, 4-epoxycyclohexylmethyl (meth) acrylate, 2, 3-epoxycyclopentylmethyl (meth) acrylate and 7, 8-epoxy [ tricyclo [5.2.1.0] dec-2-yl ] oxyethyl (meth) acrylate.

Wherein the epoxy group-containing unsaturated compound is obtained by reacting 5 to 90 mol%, preferably about 30 to 70 mol%, of the carboxyl group-containing (co) polymer with the epoxy group-containing unsaturated compound. The reaction can be carried out by a known method.

The acid value of the epoxy group-containing unsaturated compound-modified carboxyl group-containing (co) polymer is preferably 30 to 250mgKOH/g from the viewpoint of developability, and the weight average molecular weight (Mw) thereof is preferably 1,000 to 300,000 from the viewpoint of developability.

[1-1-4-b-3] unsaturated carboxylic acid-modified epoxy group-and carboxyl group-containing (co) polymer

Further, as the carboxyl group-containing (co) polymer having an ethylenically unsaturated group in a side chain, there may be exemplified: a modified epoxy group-containing (co) polymer obtained by copolymerizing an unsaturated carboxylic acid such as (meth) acrylic acid with the above-mentioned aliphatic epoxy group-containing unsaturated compound or alicyclic epoxy group-containing unsaturated compound, or further with an unsaturated carboxylic acid ester, styrene or the like so that the proportion of the former carboxyl group-containing unsaturated compound in the whole is 10 to 90 mol%, preferably about 30 to 80 mol%, and reacting the obtained copolymer with an unsaturated carboxylic acid such as (meth) acrylic acid to modify the carboxyl group of the unsaturated carboxylic acid by addition to the epoxy group of the copolymer.

The acid value of the unsaturated carboxylic acid-modified epoxy group and the carboxyl group-containing (co) polymer is preferably 30 to 250mgKOH/g from the viewpoint of developability, and the weight average molecular weight (Mw) thereof is preferably 1,000 to 300,000 from the viewpoint of developability.

[1-1-4-b-4] acid-modified epoxy group-containing (co) Polymer

Further, examples of the carboxyl group-containing (co) polymer having an ethylenically unsaturated group in a side chain thereof include: an acid-modified epoxy group-containing (co) polymer obtained by adding an ethylenically unsaturated monocarboxylic acid to at least a part of the epoxy groups of a copolymer of an epoxy group-containing (meth) acrylate and an ethylenically unsaturated compound and further adding a polybasic acid (anhydride) to at least a part of the hydroxyl groups generated by the addition.

Specific examples thereof include: an acid-modified epoxy group-containing (co) polymer obtained by adding an ethylenically unsaturated monocarboxylic acid to a copolymer containing 5 to 99 mol% of an epoxy group-containing (meth) acrylate such as glycidyl (meth) acrylate and an ethylenically unsaturated compound such as a (meth) acrylate, usually 2 to 95 mol%, usually 10 to 100 mol% of the epoxy groups contained in the copolymer, and further adding a polybasic acid (anhydride) to a hydroxyl group formed during the addition, usually 10 to 100 mol%.

The copolymerization ratio of the epoxy group-containing (meth) acrylate in the copolymer is not particularly limited, and is usually 5 mol% or more, preferably 20 mol% or more, more preferably 40 mol% or more, further preferably 60 mol% or more, further preferably 80 mol% or more, particularly preferably 90 mol% or more, and usually 99 mol% or less, preferably 98 mol% or less, more preferably 95 mol% or less. When the amount is not less than the lower limit, high sensitivity tends to be obtained, and when the amount is not more than the upper limit, adequate developer solubility tends to be obtained.

On the other hand, the copolymerization ratio of the ethylenically unsaturated compound in the above copolymer is not particularly limited, but is usually 1 mol% or more, preferably 3 mol% or more, more preferably 5 mol% or more, and is usually 90 mol% or less, preferably 70 mol% or less, more preferably 50 mol% or less, further preferably 30 mol% or less, and particularly preferably 10 mol% or less. When the content is not less than the lower limit, high sensitivity tends to be obtained, and when the content is not more than the upper limit, adequate developer solubility tends to be obtained.

Examples of epoxy group-containing (meth) acrylates include: aliphatic epoxy group-containing (meth) acrylates such as glycidyl (meth) acrylate and α -ethyl glycidyl (meth) acrylate; alicyclic epoxy group-containing (meth) acrylates such as 3, 4-epoxycyclohexylmethyl (meth) acrylate, 2, 3-epoxycyclopentylmethyl (meth) acrylate, and 7, 8-epoxy [ tricyclo [5.2.1.0] dec-2-yl ] oxyethyl (meth) acrylate.

Here, as the ethylenically unsaturated compound, for example, one or two or more kinds of mono (meth) acrylates having a partial structure represented by the following formula (α) are preferably used.

[ chemical formula 45]

In the formula (. alpha.), R^1d～R^4dEach independently represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, R^5dAnd R^6dEach independently represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. In addition, R^5dAnd R^6dOr may be connected to form a ring. R^5dAnd R^6dThe ring formed by the connection is preferably an aliphatic ring, and may be either saturated or unsaturated, and the number of carbon atoms in the ring is preferably 5 to 6.

R^1d～R^4dThe number of carbon atoms of the alkyl group in (2) is preferably 8 or less, more preferably 5 or less. When the amount is less than the upper limit, appropriate developer solubility tends to be obtained.

Of these, R is, from the viewpoint of solubility^1d～R^4dPreferably a hydrogen atom.

R^5dAnd R^6dThe number of carbon atoms of the alkyl group in (2) is preferably 8 or less, more preferably 5 or less. When the amount is not less than the lower limit, the solubility tends to be adequate, and when the amount is not more than the upper limit, the hydrophilicity tends to be maintained.

Of these, R is preferable from the viewpoint of developing solubility^5dAnd R^6dIs a hydrogen atom, or R^5dAnd R^6dLinked to form an aliphatic ring having 5 to 6 carbon atoms.

In the formula (. alpha.), a mono (meth) acrylate having a structure represented by the following formula (. alpha. -a), (. alpha. -b) or (. alpha. -c) is preferable. By introducing these partial structures, the heat resistance and strength of the mono (meth) acrylate can be enhanced. These mono (meth) acrylates may be used alone, or two or more kinds may be used in combination in any combination and ratio.

[ chemical formula 46]

As the mono (meth) acrylate having the partial structure represented by the above formula (α), various known mono (meth) acrylates can be used, and from the viewpoint of curability, a mono (meth) acrylate represented by the following formula (β) is particularly preferable.

[ chemical formula 47]

In the formula (. beta.), R^9dRepresents a hydrogen atom or a methyl group, R^10dRepresents a partial structure of the above formula (. alpha.).

When the mono (meth) acrylate having the partial structure represented by the formula (α) is contained, the copolymerization ratio thereof is usually 1 mol% or more, preferably 2 mol% or more, and is usually 70 mol% or less, preferably 50 mol% or less, more preferably 30 mol% or less, further preferably 10 mol% or less, and particularly preferably 5 mol% or less. When the content is not less than the lower limit, the film residue ratio tends to be improved, and when the content is not more than the upper limit, the residue tends to be reduced.

On the other hand, as the ethylenically unsaturated compound, ethylenically unsaturated compounds other than the above-mentioned mono (meth) acrylate having a partial structure represented by the formula (α) (hereinafter, also referred to as "other ethylenically unsaturated compounds") may be mentioned, for example: styrenes such as α -, o-, m-, p-alkyl, nitro, cyano, amide and ester derivatives of styrene, dienes such as butadiene, 2, 3-dimethylbutadiene, isoprene and chloroprene, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, pentyl (meth) acrylate, neopentyl (meth) acrylate, isoamyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, dodecyl (meth) acrylate, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, cyclohexyl (meth) acrylate, and the like, Dicyclohexyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, allyl (meth) acrylate, propynyl (meth) acrylate, phenyl (meth) acrylate, naphthyl (meth) acrylate, anthryl (meth) acrylate, anthraquinonyl (meth) acrylate, piperonyl (meth) acrylate, salicyl (meth) acrylate, furyl (meth) acrylate, furfuryl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, pyranyl (meth) acrylate, benzyl (meth) acrylate, phenylethyl (meth) acrylate, methylphenyl (meth) acrylate, 1,1, 1-trifluoroethyl (meth) acrylate, perfluoroethyl (meth) acrylate, perfluoro-n-propyl (meth) acrylate, perfluoro-isopropyl (meth) acrylate, perfluoroisopropyl (meth) acrylate, allyl (meth) acrylate, and the like, (meth) acrylic acid amides such as triphenylmethyl (meth) acrylate, isopropylphenyl (meth) acrylate, 3- (N, N-dimethylamino) propyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, and 2-hydroxypropyl (meth) acrylate, (meth) acrylic acid amide, (meth) acrylic acid N, N-dimethylamide, (meth) acrylic acid N, N-diethylamide, (meth) acrylic acid N, N-dipropylamide, (meth) acrylic acid N, N-diisopropylamide, and (meth) acrylic acid anthranylamide, (meth) acrylic acid anilides, (meth) acrylic acid nitriles, acrolein, vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride, N-vinylpyrrolidone, vinyl pyrrolidone, and mixtures thereof, Vinyl compounds such as vinylpyridine and vinyl acetate, unsaturated dicarboxylic diesters such as citraconic acid diethyl ester, maleic acid diethyl ester, fumaric acid diethyl ester and itaconic acid diethyl ester, monomaleimides such as N-phenylmaleimide, N-cyclohexylmaleimide, N-laurylmaleimide and N- (4-hydroxyphenyl) maleimide, and radical polymerizable compounds such as N- (meth) acryloylphthalimide.

Among these, in order to impart more excellent heat resistance and strength, it is effective to use at least one selected from styrene, benzyl (meth) acrylate and monomaleimide as the other ethylenically unsaturated compound. In this case, from the viewpoint of heat resistance, the copolymerization ratio of at least one selected from the group consisting of styrene, benzyl (meth) acrylate, and monomaleimide is usually 1 mol% or more, preferably 3 mol% or more, and is usually 70 mol% or less, preferably 50 mol% or less, more preferably 30 mol% or less, and still more preferably 10 mol% or less.

As the ethylenically unsaturated monocarboxylic acid to which an epoxy group contained in the copolymer of the epoxy group-containing (meth) acrylate and the ethylenically unsaturated compound is added, known ones can be used, and from the viewpoint of curability, (meth) acrylic acid is preferable. The amount of the ethylenically unsaturated monocarboxylic acid added to the epoxy group contained in the copolymer is usually 10 mol% or more, preferably 30 mol% or more, more preferably 50 mol% or more, further preferably 70 mol% or more, and usually 100 mol% or less of the epoxy group contained in the copolymer. When the addition ratio of the ethylenically unsaturated monocarboxylic acid is not less than the lower limit value, curability tends to be improved. As a method for adding the ethylenically unsaturated monocarboxylic acid to the copolymer, a known method can be used.

The polybasic acid (anhydride) to which the hydroxyl group formed by the addition of the ethylenically unsaturated monocarboxylic acid to the above-mentioned copolymer is added is not particularly limited, and known ones can be used, and examples thereof include: phthalic acid (anhydride), tetrahydrophthalic acid (anhydride), hexahydrophthalic acid (anhydride), succinic acid (anhydride), trimellitic acid (anhydride), and the like. From the viewpoint of reducing the amount of outgas generated, succinic acid (anhydride) is preferable, and from the viewpoint of improving the residual film rate and reducing the residue, tetrahydrophthalic acid (anhydride) is preferable. The polybasic acid (anhydride) may be used alone or in combination of two or more kinds in any combination and ratio. By adding such a component, the copolymer can be rendered alkali-soluble.

The amount of the polybasic acid (anhydride) added is usually 5 mol% or more, preferably 10 mol% or more, of the hydroxyl groups formed when the ethylenically unsaturated monocarboxylic acid is added to the copolymer. The content is usually 100 mol% or less, preferably 90 mol% or less, and more preferably 80 mol% or less. When the amount is not less than the lower limit, developability tends to be imparted, and when the amount is not more than the upper limit, film dissolution due to excessive development tends to be suppressed. As a method for adding a polybasic acid (anhydride) and a hydroxyl group formed when an ethylenically unsaturated monocarboxylic acid is added to the above-mentioned copolymer, a known method can be arbitrarily employed.

The modified product of the epoxy group-containing (co) polymer based on an ethylenically unsaturated monocarboxylic acid and a polybasic acid (anhydride) can be further improved in photosensitivity by adding a part of carboxyl groups formed by the addition of glycidyl (meth) acrylate or a glycidyl ether compound having an ethylenically unsaturated group to the polybasic acid (anhydride). Further, the developability can also be improved by adding a part of the carboxyl groups formed by adding a glycidyl ether compound having no ethylenically unsaturated group to a polybasic acid (anhydride). Further, the two may be added after the addition of the polybasic acid (anhydride).

Examples of the modified product of the epoxy group-containing (co) polymer based on an ethylenically unsaturated monocarboxylic acid and a polybasic acid (anhydride) include resins described in, for example, Japanese patent application laid-open Nos. 8-297366 and 2001-89533.

The weight average molecular weight (Mw) of the acid-modified epoxy group-containing (co) polymer is not particularly limited, and is usually 3,000 or more, preferably 5,000 or more, and is usually 100,000 or less, preferably 50,000 or less, more preferably 30,000 or less, still more preferably 20,000 or less, still more preferably 15,000 or less, and particularly preferably 10,000 or less. When the content is not less than the lower limit, compatibility tends to be improved, and when the content is not more than the upper limit, solubility tends to be ensured. From the viewpoint of curability, the molecular weight distribution [ weight average molecular weight (Mw)/number average molecular weight (Mn) ] is preferably 2.0 to 5.0.

The acid value of the acid-modified epoxy group-containing (co) polymer is not particularly limited, but is preferably 5mgKOH/g or more, more preferably 10mgKOH/g or more, and still more preferably 20mgKOH/g or more, and is preferably 150mgKOH/g or less, more preferably 100mgKOH/g or less, and still more preferably 50mgKOH/g or less. When the content is not less than the lower limit, solubility tends to be ensured, and when the content is not more than the upper limit, film reduction tends to be improved.

[1-1-4-C ] (C-3) carboxyl group-and ethylenically unsaturated group-containing resin

[1-1-4-c-1] acid-modified epoxy resin

Examples of the resin containing a carboxyl group and an ethylenically unsaturated group include: epoxy resins containing carboxyl groups and ethylenically unsaturated groups of a polybasic acid (anhydride) added to an adduct of an ethylenically unsaturated group monocarboxylic acid to an epoxy resin, so-called epoxy (meth) acrylate resins. That is, there is exemplified a resin obtained by ring-opening addition of an epoxy group of an epoxy resin and a carboxyl group of an ethylenically unsaturated monocarboxylic acid to thereby add an ethylenically unsaturated bond to the epoxy resin via an ester bond (-COO-) and, at the same time, addition of one carboxyl group of a polybasic acid (anhydride) and a hydroxyl group generated at that time.

Here, the epoxy resin also includes a raw material compound before forming a resin by thermosetting, and the epoxy resin can be appropriately selected from known epoxy resins and used. Specific examples thereof include: bisphenol a epoxy resins, bisphenol F epoxy resins, bisphenol S epoxy resins, phenol novolac epoxy resins, cresol novolac epoxy resins, biphenol novolac epoxy resins, triphenol epoxy resins, epoxy resins obtained by polymerizing phenol with dicyclopentane, dihydroxyfluorene epoxy resins, dihydroxyalkyleneoxyfluorene epoxy resins, diglycidyl etherate of 9, 9-bis (4 '-hydroxyphenyl) fluorene, diglycidyl etherate of 1, 1-bis (4' -hydroxyphenyl) adamantane, and the like. Among them, bisphenol a epoxy resins, phenol novolac epoxy resins, cresol novolac epoxy resins, polymerized epoxy resins of phenol and dicyclopentadiene, diglycidyl etherate of 9, 9-bis (4' -hydroxyphenyl) fluorene, and the like are preferable, and bisphenol a epoxy resins are more preferable, from the viewpoint of high cured film strength.

Examples of the ethylenically unsaturated monocarboxylic acid include: (meth) acrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, and the like, and pentaerythritol tri (meth) acrylate succinic anhydride adducts, pentaerythritol tri (meth) acrylate tetrahydrophthalic anhydride adducts, dipentaerythritol penta (meth) acrylate succinic anhydride adducts, dipentaerythritol penta (meth) acrylate phthalic anhydride adducts, dipentaerythritol penta (meth) acrylate tetrahydrophthalic anhydride adducts, reaction products of (meth) acrylic acid and epsilon-caprolactone, and the like. Among them, (meth) acrylic acid is preferable from the viewpoint of sensitivity.

Further, examples of the polybasic acid (anhydride) include: succinic acid, maleic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, 3-methyltetrahydrophthalic acid, 4-methyltetrahydrophthalic acid, 3-ethyltetrahydrophthalic acid, 4-ethyltetrahydrophthalic acid, hexahydrophthalic acid, 3-methylhexahydrophthalic acid, 4-methylhexahydrophthalic acid, 3-ethylhexahydrophthalic acid, 4-ethylhexahydrophthalic acid, trimellitic acid, pyromellitic acid, benzophenone tetracarboxylic acid, biphenyl tetracarboxylic acid, anhydrides thereof, and the like. Among them, succinic anhydride, maleic anhydride, tetrahydrophthalic anhydride, or hexahydrophthalic anhydride is preferable, succinic anhydride or tetrahydrophthalic anhydride is more preferable, and succinic anhydride is even more preferable, from the viewpoint of image reproducibility, developability, and reduction in the amount of outgas generated.

The acid value of the acid-modified epoxy resin in the present invention is not particularly limited, but is preferably 10mgKOH/g or more, more preferably 20mgKOH/g or more, further preferably 30mgKOH/g or more, and is preferably 200mgKOH/g or less, more preferably 180mgKOH/g or less, further preferably 150mgKOH/g or less, further preferably 100mgKOH/g or less, and particularly preferably 80mgKOH/g or less. When the content is not less than the lower limit, the adhesion tends to be improved, and when the content is not more than the upper limit, the solubility tends to be improved.

The weight average molecular weight (Mw) of the acid-modified epoxy resin is not particularly limited, but is usually 1,000 or more, preferably 2,000 or more, more preferably 3,000 or more, further preferably 4,000 or more, still more preferably 5,000 or more, and particularly preferably 6,000 or more, and is usually 30,000 or less, preferably 20,000 or less, more preferably 15,000 or less, and further preferably 10,000 or less. When the content is not less than the lower limit, the adhesiveness tends to be improved, and when the content is not more than the upper limit, the solubility tends to be maintained.

The acid-modified epoxy resin can be synthesized by a conventionally known method. Specifically, the following method can be employed: the epoxy resin is dissolved in an organic solvent, the ethylenically unsaturated monocarboxylic acid is added in the presence of a catalyst and a thermal polymerization inhibitor to cause an addition reaction to proceed, and a polybasic acid (anhydride) is further added to continue the reaction.

Examples of the organic solvent used in the reaction include one or more organic solvents such as methyl ethyl ketone, cyclohexanone, diethylene glycol ethyl ether acetate, and propylene glycol monomethyl ether acetate. The catalyst may be one or more of tertiary amines such as triethylamine, benzyldimethylamine and tribenzylamine, quaternary ammonium salts such as tetramethylammonium chloride, methyltriethylammonium chloride, tetraethylammonium chloride, tetrabutylammonium chloride and trimethylbenzylammonium chloride, phosphorus compounds such as triphenylphosphine, antimony compounds such as triphenylantimony, and the like. Further, the thermal polymerization inhibitor may be one or more of hydroquinone, hydroquinone monomethyl ether, and methyl hydroquinone.

The amount of the ethylenically unsaturated monocarboxylic acid used may be generally 0.7 to 1.3 stoichiometric equivalents, preferably 0.9 to 1.1 stoichiometric equivalents, based on 1 stoichiometric equivalent of the epoxy group of the epoxy resin. The temperature during the addition reaction may be usually 60 to 150 ℃, preferably 80 to 120 ℃. The amount of the polybasic acid (anhydride) used may be usually 0.1 to 1.2 stoichiometric equivalents, preferably 0.2 to 1.1 stoichiometric equivalents, based on 1 stoichiometric equivalent of the hydroxyl group formed in the addition reaction.

Specific examples of the acid-modified epoxy resin in the present invention are shown below. The acid-modified epoxy resin may contain one kind of resin, or may contain two or more kinds of resins.

[ chemical formula 48]

In the formula (C1-1), R¹¹¹Each independently represents a hydrogen atom, a halogen atom, an alkyl group or an aryl group, n¹¹¹Represents an integer of 0 to 20.

[ chemical formula 49]

In the formula (C1-2), R¹²¹Each independently represents a hydrogen atom, a halogen atom, an alkyl group or an aryl group, n¹²¹Represents an integer of 0 to 20.

[ chemical formula 50]

In the formula (C1-3), R¹³¹Each independently represents a hydrogen atom, a halogen atom, an alkyl group or an aryl group, m¹³¹And n¹³¹Each independently represents an integer of 0 to 20. In addition, m is ¹³¹And n¹³¹The number of repeating units is not meant to be a block copolymer. Gamma represents a single bond, -CO-, -CH₂-、 -C(CH₃)₂-, a group represented by the following formula (. gamma.), or a group represented by the following formula (. delta.). δ represents a hydrogen atom or a polybasic acid residue.

[ chemical formula 51]

[ chemical formula 52]

[ chemical formula 53]

In the formula (C1-4), R¹⁴¹Each independently represents an alkyl group or a halogen atom, and each independently represents an integer of 0 to 4.

[ chemical formula 54]

[ chemical formula 55]

In the formula (C1-6), R¹⁶¹Each independently represents a hydrogen atom, a halogen atom, an alkyl group or an aryl group, n¹⁶¹Represents an integer of 0 to 20.

In the formulae (C1-1) to (C1-6), A represents a group represented by the following general formula (. epsilon.).

[ chemical formula 56]

In the formula (ε), R¹⁷¹Represents a hydrogen atom or a methyl group, R¹⁷²Represents an alkylene group, m¹⁷¹Represents an integer of 0 to 10. In addition, δ represents a hydrogen atom or a polybasic acid residue.

[1-1-4-c-2] modified phenolic resin

Examples of the resin containing a carboxyl group and an ethylenically unsaturated group include: a phenolic resin containing carboxyl and olefinic unsaturated group, which is obtained by adding polybasic acid (anhydride) to an addition product of an epoxy compound containing olefinic unsaturated group of the phenolic resin. That is, a phenol resin obtained by adding an ethylenically unsaturated bond to a phenol resin via an ester bond (-COO-) by ring-opening addition of a phenolic hydroxyl group of the phenol resin and an epoxy group of an epoxy compound having an ethylenically unsaturated group, and simultaneously adding one carboxyl group of a polybasic acid (anhydride) and a hydroxyl group generated at that time can be cited.

Here, as the phenolic resin, for example: a novolak resin obtained by polycondensing at least 1 kind of phenol such as phenol, o-cresol, m-cresol, p-cresol, 2, 5-xylenol, 3, 5-xylenol, o-ethylphenol, m-ethylphenol, p-ethylphenol, propylphenol, n-butylphenol, t-butylphenol, 1-naphthol, 2-naphthol, 4' -biphenyldiol, bisphenol-A, catechol, resorcinol, hydroquinone, pyrogallol, 1,2, 4-benzenetriol, benzoic acid, 4-hydroxyphenylacetic acid, salicylic acid, phloroglucinol, with an aldehyde such as formaldehyde, paraformaldehyde, acetaldehyde, sec-aldehyde, propionaldehyde, benzaldehyde, salicylaldehyde, furfural or a ketone such as acetone, methyl ethyl ketone, methyl isobutyl ketone, or the like, in the presence of an acid catalyst, and resol resins obtained by polycondensation in the same manner except that an alkali catalyst is used instead of the acid catalyst in the polycondensation. The condensation reaction of the above-mentioned phenols with aldehydes may be carried out in the absence of a solvent or in a solvent.

The weight average molecular weight (Mw) of the novolac resin or resol resin is usually 1,000 to 20,000, preferably 1,000 to 10,000, and more preferably 1,000 to 8,000. When the weight average molecular weight is equal to or higher than the lower limit, the image strength tends to be easily ensured, and when the weight average molecular weight is equal to or lower than the upper limit, the developability tends to be easily ensured.

Further, as the epoxy compound containing an ethylenically unsaturated group, there can be mentioned: glycidyl (meth) acrylate, (3, 4-epoxycyclohexyl) methyl (meth) acrylate, glycidyloxy (poly) alkylene glycol (meth) acrylate, methylglycidyl (meth) acrylate, 1-vinyl-3, 4-epoxycyclohexane and the like. Among these, glycidyl (meth) acrylate and (3, 4-epoxycyclohexyl) methyl (meth) acrylate are particularly preferable.

The reaction of the novolak resin, the resol resin, etc. with the ethylenically unsaturated group-containing epoxy compound can be carried out by a known method. For example, the epoxy compound containing an ethylenically unsaturated group can be added to a novolak resin, a resol resin, or the like by reacting in an organic solvent at a reaction temperature of 50 to 150 ℃ for several hours to several tens of hours using one or more of tertiary amines such as triethylamine and benzylmethylamine, quaternary ammonium salts such as dodecyltrimethylammonium chloride, tetramethylammonium chloride, tetraethylammonium chloride, and benzyltriethylammonium chloride, pyridine, triphenylphosphine, or the like as a catalyst.

The amount of the catalyst used is preferably 0.01 to 10% by mass, and particularly preferably 0.3 to 5% by mass, based on the total amount of the reaction raw material mixture (the novolac resin, the resol resin, and the ethylenically unsaturated group-containing epoxy compound). In order to prevent polymerization during the reaction, a polymerization inhibitor (for example, one or more of methoquinone, hydroquinone, methylhydroquinone, p-methoxyphenol, pyrogallol, t-butylphthalophenol, dibutylhydroxytoluene, phenothiazine, and the like) is preferably used in an amount of 0.01 to 10% by mass, particularly preferably 0.03 to 5% by mass, based on the reaction raw material mixture.

The preferable proportion of the epoxy compound having an ethylenically unsaturated group added to the phenolic hydroxyl group of the novolac resin, the resol resin, or the like is 1 to 99 mol%. The ratio is adjusted by the amount of the ethylenically unsaturated group-containing epoxy compound added relative to the phenolic hydroxyl group.

As the polybasic acid (anhydride), for example, known polybasic acids (anhydrides) can be used, and examples thereof include: dicarboxylic acids such as maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, methylnadic acid, chlorendic acid, methyltetrahydrophthalic acid, 5-norbornene-2, 3-dicarboxylic acid and methyl-5-norbornene-2, 3-dicarboxylic acid, and polycarboxylic acids such as trimellitic acid, pyromellitic acid, benzophenone tetracarboxylic acid and biphenyl tetracarboxylic acid, and anhydrides thereof. Among them, tetrahydrophthalic anhydride or succinic anhydride is preferably used. These polybasic acids (anhydrides) may be used alone or in combination of two or more.

The addition rate of the polybasic acid (anhydride) is usually 10 to 100 mol%, preferably 20 to 100 mol%, more preferably 30 to 100 mol% of the hydroxyl group of the reaction product of the epoxy compound containing an ethylenically unsaturated group such as a novolak resin, a resol resin and the like. When the addition ratio is within the above range, the developing property tends to be easily secured.

[1-1-4-d ] other alkali-soluble resins

In addition, in the case where it is intended to provide partition walls in an organic electric field element of a substrate which is easily deteriorated by an alkali developing solution, and a developing solution using a weakly alkaline alkali compound or a developing solution containing no alkali compound, as the alkali-soluble resin, it is preferable to use: polyvinyl alcohol, a vinyl alcohol copolymer obtained by copolymerizing 0.1 to 40 mol%, preferably 1 to 30 mol%, of a comonomer (preferable example is vinyl acetate) exemplified in the [1-1-4-a-1] carboxyl group-containing (co) polymer (1), or a modified polyvinyl alcohol obtained by introducing 0.1 to 40 mol%, preferably 1 to 30 mol%, of a copolymer exemplified in the [1-1-4-a-1] carboxyl group-containing (co) polymer (1) by an esterification reaction.

Further, in order to form a moderate taper angle and maintain liquid repellency, it is preferable to use: the ethylenically unsaturated monocarboxylic acid (preferably, a reaction product of (meth) acrylic acid and epsilon-caprolactone, etc.) used in the above-mentioned [1-1-4-c-1] acid-modified epoxy resin, a modified polyvinyl alcohol into which 0.1 to 30 mol%, preferably 0.5 to 20 mol%, of a polybasic acid (anhydride) is introduced by an esterification reaction (preferably, tetrahydrophthalic anhydride, etc.), a compound having a (meth) acryloyl (oxy) group or (meth) acrylamide group and an aldehyde group (preferably, 4-acryloyloxy, etc.) described in jp 2008-45047 a, or a compound having a dialkyl group introduced by a formal reaction (preferably, butyraldehyde-containing acetal having 0.1 to 30 mol%, preferably 0.5 to 20 mol%, examples thereof include modified polyvinyl alcohol such as N- (2, 2-dimethoxyethyl) methacrylamide).

Among the above, the alkali-soluble resin (C) is preferably (C-2) a carboxyl group-containing (co) polymer having an ethylenically unsaturated group in a side chain or (C-3) a carboxyl group-and ethylenically unsaturated group-containing resin, more preferably (C-3) a carboxyl group-and ethylenically unsaturated group-containing resin, and still more preferably an acid-modified epoxy resin, from the viewpoints of reduction in degassing yield and curability. In addition, the resin exemplified as the alkali-soluble resin (C) in embodiment 1 may be used.

The weight average molecular weight (Mw) of the alkali-soluble resin (C) is not particularly limited, but is preferably 2,000 or more, more preferably 3,000 or more, further preferably 5,000 or more, and particularly preferably 7,000 or more, and is preferably 50,000 or less, more preferably 30,000 or less, further preferably 20,000 or less, and particularly preferably 10,000 or less. When the amount is not less than the lower limit, the film tends to be inhibited from dissolving due to excessive development, and when the amount is not more than the upper limit, the film tends to exhibit appropriate development solubility.

The acid value of the alkali-soluble resin (C) is not particularly limited, but is preferably not less than 10mgKOH/g, more preferably not less than 20mgKOH/g, and preferably not less than 30mgKOH/g, and is preferably not more than 200mgKOH/g, more preferably not more than 150mgKOH/g, still more preferably not more than 100mgKOH/g, still more preferably not more than 70mgKOH/g, and particularly preferably not more than 50 mgKOH/g. When the content is not less than the lower limit, the residue tends to be suppressed, and when the content is not more than the upper limit, the residual film ratio tends to be high.

The content ratio of the alkali-soluble resin (C) in the photosensitive resin composition of the present invention of embodiment 2 is: the content is usually 5% by mass or more, preferably 10% by mass or more, more preferably 20% by mass or more, further preferably 30% by mass or more, and particularly preferably 40% by mass or more, and usually 90% by mass or less, preferably 70% by mass or less, more preferably 60% by mass or less, and particularly preferably 50% by mass or less, based on the total solid content. When the amount is not less than the lower limit, appropriate solubility and sensitivity in development tend to be obtained, and when the amount is not more than the upper limit, appropriate solubility and sensitivity in development tend to be obtained.

The content ratio of the ethylenically unsaturated compound (a) and the alkali-soluble resin (C) in the total solid content is: the content is usually 5% by mass or more, preferably 10% by mass or more, more preferably 30% by mass or more, further preferably 50% by mass or more, further preferably 70% by mass or more, particularly preferably 80% by mass or more, and most preferably 85% by mass or more, and is usually 99% by mass or less, preferably 97% by mass or less, and more preferably 95% by mass or less, based on the total solid content. When the amount is not less than the lower limit, appropriate solubility and sensitivity in development tend to be obtained, and when the amount is not more than the upper limit, appropriate solubility and sensitivity in development tend to be obtained.

The blending ratio of the alkali-soluble resin (C) to the ethylenically unsaturated compound (a) in the photosensitive resin composition is preferably 50 parts by mass or more, more preferably 60 parts by mass or more, further preferably 70 parts by mass or more, and particularly preferably 80 parts by mass or more, and further preferably 400 parts by mass or less, more preferably 300 parts by mass or less, further preferably 200 parts by mass or less, and particularly preferably 100 parts by mass or less, with respect to 100 parts by mass of the ethylenically unsaturated compound (a). When the amount is equal to or more than the lower limit, the substrate adhesiveness tends to be enhanced, and when the amount is equal to or less than the upper limit, the curability tends to be improved, the liquid repellency tends to be generated, and the minimum exposure amount required tends to be reduced.

[1-1-5] (D) component; liquid repellent

The photosensitive resin composition for forming organic electroluminescent element partition walls of the present invention may contain (D) a liquid repellent. In particular, when an organic electroluminescent element is produced by an ink jet method, it is preferable to contain (D) a liquid repellent which can impart liquid repellency to the surface of the partition wall, and therefore it is considered that the partition wall obtained can prevent color mixing of the light emitting portions (pixels) of the organic layer.

Examples of the liquid repellent include silicone-containing compounds and fluorine-containing compounds, and preferred examples thereof include liquid repellents having a crosslinking group (hereinafter also referred to as "crosslinking group-containing liquid repellents"). The crosslinking group may be an epoxy group or an ethylenically unsaturated group, and is preferably an ethylenically unsaturated group from the viewpoint of suppressing the outflow of the liquid repellent component of the developer.

It is considered that, in the case of using a crosslinking group-containing liquid repellent, the crosslinking reaction on the surface of the formed coating film at the time of exposure can be accelerated, and the liquid repellent hardly flows out in the development treatment, and as a result, the partition walls obtained can be made to exhibit high liquid repellency.

When a fluorine-based compound is used as the liquid repellent, the fluorine-based compound tends to be oriented on the surface of the partition walls, and the function of preventing bleeding of ink and color mixing tends to be exerted. More specifically, there is a tendency that: the group having a fluorine atom can exert the effects of repelling ink, preventing ink bleeding and color mixing caused by the ink passing over the spacer into the adjacent region.

Specific examples of the crosslinking group-containing liquid repellent, particularly the ethylenically unsaturated group-containing fluorine-based compound include: fluorine-containing organic compounds such as perfluoroalkyl sulfonic acid, perfluoroalkyl carboxylic acid, perfluoroalkyl oxyalkylene adduct, perfluoroalkyl trialkylammonium salt, oligomer containing perfluoroalkyl group and hydrophilic group, oligomer containing perfluoroalkyl group and lipophilic group, oligomer containing perfluoroalkyl group, hydrophilic group and novel oil group, urethane containing perfluoroalkyl group and hydrophilic group, perfluoroalkyl ester, perfluoroalkyl phosphate, etc. As commercially available products of these fluorine-containing compounds, "Megafac F116", "Megafac F120", "Megafac F142D", "Megafac F144D", "Megafac F150", "Megafac F160", "Megafac F171", "Megafac F172", "Megafac F173", "Megafac F177", "Megafac F178A", "Megafac F178K", "Megafac F179", "Megafac F183", "Megafac F184", "Megafac F191", "Megafac F812", "Megafac F815", "Megafac F824", "Megafac F833", "Megafac RS 101", "Megafac RS 401", "Megafac RS 105", "Megafac RS 201", "Megafac RS 202", "Megafac RS 301", "Megafac RS 303", "MegaRS 31", "Megafac RS 31-300" Megafac RS402 "and" Megafac RS402 "Megars 402" Megafac RS 300 "23" by DIC RS 300 "DIC RS 31", "Megafac RS 31" DIC RS 31 "or" can be used in DIC of DIC company DIC, Commercially available fluorinated organic compounds such as "Fluorad FC 430", "Fluorad FC 431", "FC-4430", "FC 4432", Asahi Guard AG710 "," Surflon S-382 "," Surflon SC-101 "," Surflon SC-102 "," Surflon SC-103 "," Surflon SC-104 "," Surflon SC-105 "," Surflon SC-106 ", and" Optool DAC-HP ", manufactured by Dajin Kokai Co.

In this manner, when a fluorine-based compound is used as the liquid repellent, the fluorine atom content in the liquid repellent is not particularly limited, but is preferably 1% by mass or more, more preferably 5% by mass or more, and is preferably 50% by mass or less, more preferably 25% by mass or less. When the lower limit value is higher than the above-described lower limit value, the outflow to the pixel portion tends to be suppressed, and when the upper limit value is lower than the above-described upper limit value, the contact angle tends to be high.

The molecular weight of the liquid repellent is not particularly limited, and may be a low molecular weight compound or a high molecular weight substance. The high molecular weight liquid repellent can suppress the flowability of the repellent due to the post-baking and thus can suppress the flow of the repellent from the dam, and therefore, the number average molecular weight of the repellent is preferably 100 or more, more preferably 500 or more, and preferably 100,000 or less, more preferably 10,000 or less.

The content of the liquid repellent (D) in the photosensitive resin composition of the present invention is usually 0.01 mass% or more, preferably 0.1 mass% or more, and usually 1 mass% or less, preferably 0.5 mass% or less, and more preferably 0.3 mass% or less, based on the total solid content. When the amount is equal to or more than the lower limit, the liquid repellency tends to be high, and when the amount is equal to or less than the upper limit, the outflow to the pixel portion tends to be suppressed.

On the other hand, in the photosensitive resin composition for spacer formation of the present invention, a surfactant may be used in addition to the liquid repellent (D), or a surfactant may be used instead of the liquid repellent (D). The surfactant can be used for the purpose of improving the coatability of a coating solution of the photosensitive resin composition for forming partition walls, the developability of a coating film, and the like, and among them, a fluorine-based or silicone-based surfactant is preferable.

In particular, the silicone surfactant is preferable, and the polyether-modified silicone surfactant is more preferable, because it has a function of removing the residue of the photosensitive resin composition from unexposed portions during development and a function of exhibiting wettability.

The fluorine-based surfactant is preferably a compound having a fluoroalkyl group or a fluoroalkylene group at least at any one of the terminal, main chain, and side chain. Specific examples thereof include: 1,1,2, 2-tetrafluorooctyl (1,1,2, 2-tetrafluoropropyl) ether, 1,2, 2-tetrafluorooctylhexyl ether, octaethyleneglycol bis (1,1,2, 2-tetrafluorobutyl) ether, hexaethyleneglycol bis (1,1,2,2,3, 3-hexafluoropentyl) ether, octapropyleneglycol bis (1,1,2, 2-tetrafluorobutyl) ether, hexapropyleneglycol bis (1,1,2,2,3, 3-hexafluoropentyl) ether, sodium perfluorododecylsulfonate, 1,2,2,8,8,9,9,10, 10-decafluorododecane, 1,2,2,3, 3-hexafluorodecane, and the like. Examples of commercially available products of these include: BM-1000 and BM-1100 manufactured by BM Chemie, Megafac F142D, Megafac F172, Megafac F173, Megafac F183, Megafac F470, Megafac F475, FC430 manufactured by 3M Japan, DFX-18 manufactured by Neos, and the like.

Further, examples of the silicone surfactant include: commercially available products such as "DC 3 PA", "SH 7 PA", "DC 11 PA", "SH 21 PA", "SH 28 PA", "SH 29 PA", "8032 Additive", "SH 8400", BYK Chemie "BYK 323" and "BYK 330" from Dow Corning Toray.

The surfactant may contain surfactants other than the fluorine-based surfactant and the silicone-based surfactant, and examples of the other surfactant include nonionic, anionic, cationic, and amphoteric surfactants.

Examples of the nonionic surfactant include: polyoxyethylene alkyl ethers, polyoxyethylene polyoxypropylene alkyl ethers, polyoxyethylene alkylphenyl ethers, polyoxyethylene alkyl esters, polyoxyethylene fatty acid esters, glycerin fatty acid esters, polyoxyethylene glycerin fatty acid esters, pentaerythritol fatty acid esters, polyoxyethylene pentaerythritol fatty acid esters, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, sorbitol fatty acid esters, polyoxyethylene sorbitol fatty acid esters, and the like. Examples of commercially available products of these include: polyoxyethylene surfactants such as "EMULGEN 104P" and "EMULGEN A60" manufactured by Kao corporation, and the like.

Examples of the anionic surfactant include: alkylsulfonic acid salts, alkylbenzenesulfonic acid salts, alkylnaphthalenesulfonic acid salts, polyoxyethylene alkyl ether sulfonic acid salts, alkylsulfates, alkylsulfate salts, higher alcohol sulfate ester salts, fatty alcohol sulfate ester salts, polyoxyethylene alkyl ether sulfuric acid salts, polyoxyethylene alkylphenyl ether sulfuric acid salts, alkylphosphate esters, polyoxyethylene alkyl ether phosphoric acid salts, polyoxyethylene alkylphenyl ether phosphoric acid salts, and special polymer surfactants. Among these, a special polymer surfactant is preferable, and a special polycarboxylic acid type polymer surfactant is more preferable. As such an anionic surfactant, commercially available ones can be used, and examples thereof include alkyl sulfate salts such as "Emal 10" manufactured by Kao corporation, alkyl naphthalene sulfonates such as "Perex NB-L" manufactured by Kao corporation, and specific polymer surfactants such as "Homogenol L-18" and "Homogenol L-100" manufactured by Kao corporation.

Further, the cationic surfactant may be exemplified by quaternary ammonium salts, imidazoline derivatives, alkylamine salts, etc., and the amphoteric surfactant may be exemplified by betaine type compounds, imidazole compounds, etc

Salts, imidazolines, amino acids, and the like. Of these, quaternary ammonium salts are preferable, and stearyl trimethylammonium salts are more preferable. Examples of commercially available products include alkylamine salts such as "Acetamin 24" manufactured by Kao corporation, and quaternary ammonium salts such as "KOTAMIN 24P" and "KOTAMIN 86W" manufactured by Kao corporation.

In addition, two or more kinds of surfactants may be used in combination, and examples thereof include: silicone surfactant/fluorine surfactant, silicone surfactant/special polymer surfactant, fluorine surfactant/special polymer surfactant, and combinations thereof. Among these, a combination of a silicone surfactant and a fluorine surfactant is preferable. In the combination of the silicone surfactant and the fluorine surfactant, for example: "DFX-18" manufactured by Neos, "BYK-300" manufactured by BYK Chemie, "S-393" manufactured by BYK-330 "/AGC SEIMI CHEMICAL," F-478 "manufactured by" KP340 "/DIC," F-475 "manufactured by Shin-Etsu Silicone," SH7PA "/DS-401 manufactured by Dow Corning Toray," L-77 "manufactured by NUC,"/FC 4430 "manufactured by 3M Japan, and the like.

[1-1-6] polymerization inhibitor

The photosensitive resin composition for forming organic electroluminescent element partition walls of the present invention may contain a polymerization inhibitor. It is considered that the inclusion of the polymerization inhibitor inhibits radical polymerization, and therefore, the taper angle of the obtained partition wall can be increased.

Examples of the polymerization inhibitor include: hydroquinone, hydroquinone monomethyl ether, methylhydroquinone, methoxyphenol, 2, 6-di-tert-butyl-4-cresol (BHT), and the like. Among these polymerization inhibitors, hydroquinone or methoxyphenol is preferable, and methylhydroquinone is more preferable, from the viewpoint of polymerization inhibiting ability.

The polymerization inhibitor preferably contains one or more species. In general, when the alkali-soluble resin (C) is produced, a polymerization inhibitor may be contained in the resin, and the resin may be used as the polymerization inhibitor of the present invention, or a polymerization inhibitor which is the same as or different from the polymerization inhibitor in the resin may be added in the production of the photosensitive resin composition.

The content of the polymerization inhibitor in the photosensitive resin composition is usually 0.0005 mass% or more, preferably 0.001 mass% or more, more preferably 0.01 mass% or more, and usually 0.3 mass% or less, preferably 0.2 mass% or less, more preferably 0.1 mass% or less, based on the total solid content of the photosensitive resin composition. When the value is equal to or higher than the lower limit value, the taper angle tends to be increased, and when the value is equal to or lower than the upper limit value, the sensitivity tends to be kept high.

[1-1-7] ultraviolet absorber

The photosensitive resin composition for forming organic electroluminescent element partition walls of the present invention may contain an ultraviolet absorber. The ultraviolet absorber is added for the following purpose: the photocuring profile is controlled by absorbing a specific wavelength of a light source for exposure with an ultraviolet absorber. By adding the ultraviolet absorber, effects such as improvement of the taper shape after development and elimination of residue remaining in the unexposed portion after development can be obtained. As the ultraviolet absorber, for example, a compound having a maximum absorption at a wavelength of 250nm to 400nm can be used from the viewpoint of inhibiting the light absorption of the initiator.

Examples of the ultraviolet absorber include: benzotriazole compounds, triazine compounds, benzophenone compounds, benzoate compounds, cinnamic acid derivatives, naphthalene derivatives, anthracene and its derivatives, dinaphthalene compounds, phenanthroline compounds, dyes, and the like.

These ultraviolet absorbers may be used alone or in combination of two or more.

Among these, from the viewpoint of increasing the taper angle, a benzotriazole-based compound and/or a hydroxyphenyltriazine-based compound is preferable, and a benzotriazole-based compound is particularly preferable.

Among the benzotriazole-based compounds, preferred is a benzotriazole compound represented by the following general formula (Z1) from the viewpoint of tapered shape.

[ chemical formula 57]

In the above formula (Z1), R^1eAnd R^2eEach independently represents a hydrogen atom, an alkyl group optionally having a substituent, a group represented by the following general formula (Z2), or a group represented by the following general formula (Z3). R^3eRepresents a hydrogen atom or a halogen atom.

[ chemical formula 58]

In the above formula (Z2), R^4eRepresents an alkylene group optionally having a substituent, R^5eRepresents an alkyl group optionally having a substituent.

[ chemical formula 59]

In the above formula (Z3), R^6eRepresents an alkylene group optionally having a substituent, R^7eRepresents a hydrogen atom or a methyl group.

(R^1eAnd R^2e)

In the above formula (Z1), R^1eAnd R^2eEach independently represents a hydrogen atom, an alkyl group optionally having a substituent, a group represented by the general formula (Z2), or a group represented by the general formula (Z3).

Examples of the alkyl group include linear, branched or cyclic alkyl groups. The number of carbon atoms is preferably 1 or more, more preferably 2 or more, further preferably 4 or more, and further preferably 10 or less, more preferably 6 or less, further preferably 4 or less.

Specific examples of the alkyl group include: methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, and the like. Among these alkyl groups, a tert-butyl group is preferable.

Further, as the substituent optionally having an alkyl group, there may be mentioned: methoxy, ethoxy, chloro, bromo, fluoro, hydroxy, amino, epoxy, oligoethylene glycol, phenyl, carboxy, acryloyl, methacryloyl, and the like.

(R^3e)

In the above formula (Z1), R^3eRepresents a hydrogen atom or a halogen atom.

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like.

Of these, R is preferred from the viewpoint of synthesis^3eIs a hydrogen atom.

(R^4e)

In the above formula (Z2), R^4eRepresents an alkylene group optionally having a substituent.

Examples of the alkylene group include linear, branched or cyclic alkylene groups. The number of carbon atoms is usually 1 or more, preferably 2 or more, and preferably 6 or less, more preferably 4 or less, and further preferably 3 or less.

Specific examples of the alkylene group include: methylene, ethylene, propylene, butylene, and the like. Of these, ethylene is preferable.

Further, as the substituent optionally having the alkylene group, there may be mentioned: methoxy, ethoxy, chloro, bromo, fluoro, hydroxy, amino, epoxy, oligoethylene glycol, phenyl, carboxy, acryloyl, methacryloyl, and the like.

Of these, R is preferred^4eIs an ethylene group.

(R^5e)

In the above formula (Z2), R^5eRepresents an alkyl group optionally having a substituent.

Examples of the alkyl group include linear, branched or cyclic alkyl groups. The number of carbon atoms is preferably 4 or more, more preferably 5 or more, and still more preferably 7 or more, and further preferably 15 or less, more preferably 10 or less, and still more preferably 9 or less.

Specific examples of the alkyl group include: methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, and the like.

Further, as the substituent optionally having an alkyl group, there may be mentioned: methoxy, ethoxy, chloro, bromo, fluoro, hydroxy, amino, epoxy, oligoethylene glycol, phenyl, carboxyl, acryloyl, methacryloyl, and the like.

Of these, R is preferable from the viewpoint of taper shape^5eHeptyl, octyl and nonyl.

(R^6e)

In the above formula (Z3), R^6eRepresents an alkylene group optionally having a substituent.

Of these, R is preferable from the viewpoint of taper shape^1eIs tert-butyl, R^2eIs a group represented by the above formula (Z2) (wherein, R^4eIs ethylene, R^5eAlkyl with 7-9 carbon atoms), R^3eA compound being a hydrogen atom, or R^1eIs a hydrogen atom, R^2eIs a group represented by the above formula (Z3) (wherein, R^6eIs ethylene, R^7eIs methyl), R^3eCompounds which are hydrogen atoms, more preferably R^1eIs tert-butyl, R^2eIs a group represented by the above formula (Z2) (wherein, R^4eIs ethylene, R^5eAlkyl with 7-9 carbon atoms), R^3eA compound which is a hydrogen atom.

Specific examples of the benzotriazole compound include: 2- (5-methyl-2-hydroxyphenyl) benzotriazole, 2- (2-hydroxy-5-t-butylphenyl) -2H-benzotriazole, a mixture of octyl-3- [ 3-t-butyl-4-hydroxy-5- (5-chloro-2H-benzotriazol-2-yl) phenyl ] propionate and 2-ethylhexyl-3- [ 3-t-butyl-4-hydroxy-5- (5-chloro-2H-benzotriazol-2-yl) phenyl ] propionate, 2- [ 2-hydroxy-3, 5-bis (. alpha.,. alpha. -dimethylbenzyl) phenyl ] -2H-benzotriazole, a salt thereof, a hydrate thereof, and a pharmaceutical composition comprising the same, 2- (3-tert-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole, 2- (3, 5-di-tert-amyl-2-hydroxyphenyl) benzotriazole, 2- (2 '-hydroxy-5' -tert-octylphenyl) benzotriazole, phenylpropanoic acid, 3- (2H-benzotriazol-2-yl) -5- (1, 1-dimethylethyl) -4-hydroxy, C7-9 side chain and linear alkyl ester compounds, 2- (2H-benzotriazol-2-yl) -4, 6-bis (1-methyl-1-phenylethyl) phenol, 2- (2H-benzotriazol-2-yl) -6- (1-methyl-1-phenylethyl) phenol ) -4- (1,1,3, 3-tetramethylbutyl) phenol. Among these, from the viewpoint of the cone angle and the exposure sensitivity, a compound of 3- (2H-benzotriazol-2-yl) -5- (1, 1-dimethylethyl) -4-hydroxy, C7-9 side chain and linear alkyl ester is preferable.

Examples of commercially available benzotriazole compounds include: SUMISORB 200, SUMISORB 250, SUMISORB 300, SUMISORB 340, SUMISORB 350 (manufactured by Sumitomo Chemical Co., Ltd.), JF77, JF78, JF79, JF80, JF83 (manufactured by North City Chemical industry), TINUVIN PS, TINUVIN99-2, TINUVIN109, TINUVIN384-2, TINUVIN326, TINUVIN900, TIVIN 928, TINUVIN1130 (manufactured by BASF), EVERSORB70, EVERSORB71, EVERSORB72, EVERSORB73, EVERSORB74, EVERSORB75, EVERSORB76, EVERSORB234, EVERSORB77, EVERSORB78, EVERSORB80, EVERSORB81 (manufactured by Taiwan industry Co., ToMISORB 100, ToMISORB 600, TOMISORB 703, ESORB, ESSEVA, ESSERB 702, ISSERB 702, ISSERB and so on Chemical industry co.

Examples of the triazine compound include: 2- [4, 6-bis (2, 4-dimethylphenyl) -1,3, 5-triazin-2-yl ] -5-octyloxyphenol, 2- [4, 6-bis (2, 4-dimethylphenyl) -1,3, 5-triazin-2-yl ] -5- [3- (dodecyloxy) -2-hydroxypropoxy ] phenol, the reaction product of 2- (2, 4-dihydroxyphenyl) -4, 6-bis (2, 4-dimethylphenyl) -1,3, 5-triazine with glycidic acid (2-ethylhexyl) ester, 2, 4-bis [ 2-hydroxy-4-butoxyphenyl ] -6- (2, 4-dibutoxyphenyl) -1,3, 5-triazine, and the like. Among these, from the viewpoint of the cone angle and the exposure sensitivity, a hydroxyphenyltriazine compound is preferable.

Examples of commercially available triazine compounds include: TINUVIN400, TINUVIN405, TINUVIN460, TINUVIN477, TINUVIN479 (manufactured by BASF) and the like.

Examples of other ultraviolet absorbers include: benzophenone compounds such as SUMISORB 130 (manufactured by Sumitomo chemical Co., Ltd.), EVERSORB10, EVERSORB11, EVERSORB12 (manufactured by Taiwan Yongsho chemical industry Co., Ltd.), Tomisorb 800 (manufactured by API Corporation), SEESORB100, SEESORB101S, SEESORB102, SEESORB103, SEESORB105, SEESORB106, SEESORB107, SEESORB151 (manufactured by SHIPRO SEI KAI); benzoic acid ester compounds such as SUMISORB 400 (manufactured by Sumitomo chemical Co., Ltd.) and phenyl salicylate; cinnamic acid derivatives such as 2-ethylhexyl cinnamate, 2-ethylhexyl p-methoxycinnamate, isopropyl methoxycinnamate, and isoamyl methoxycinnamate; naphthalene derivatives such as α -naphthol, β -naphthol, α -naphthol methyl ether, α -naphthol ethyl ether, 1, 2-dihydroxynaphthalene, 1, 3-dihydroxynaphthalene, 1, 4-dihydroxynaphthalene, 1, 5-dihydroxynaphthalene, 1, 6-dihydroxynaphthalene, 1, 7-dihydroxynaphthalene, 1, 8-dihydroxynaphthalene, 2, 3-dihydroxynaphthalene, 2, 6-dihydroxynaphthalene, 2, 7-dihydroxynaphthalene and the like; anthracene such as anthracene and 9, 10-dihydroxyanthracene, and derivatives thereof; azo dyes, benzophenone dyes, aminoketone dyes, quinoline dyes, anthraquinone dyes, diphenylcyanoacrylate dyes, triazine dyes, p-aminobenzoic acid dyes, and the like; and so on. Among these, cinnamic acid derivatives and naphthalene derivatives are preferably used from the viewpoint of exposure sensitivity, and cinnamic acid derivatives are particularly preferably used.

The content ratio of the ultraviolet absorber in the photosensitive resin composition of the present invention is: the content is usually 0.01% by mass or more, preferably 0.05% by mass or more, more preferably 0.1% by mass or more, further preferably 0.5% by mass or more, and particularly preferably 1% by mass or more, and is usually 15% by mass or less, preferably 10% by mass or less, more preferably 5% by mass or less, and further preferably 3% by mass or less, based on the total solid content. When the value is equal to or higher than the lower limit, the taper angle tends to be large, and when the value is equal to or lower than the upper limit, high sensitivity tends to be obtained.

The blending ratio of the photopolymerization initiator (B) to the ultraviolet absorber is usually 1 part by mass or more, preferably 10 parts by mass or more, more preferably 30 parts by mass or more, further preferably 50 parts by mass or more, and particularly preferably 80 parts by mass or more, and usually 500 parts by mass or less, preferably 300 parts by mass or less, more preferably 200 parts by mass or less, and further preferably 150 parts by mass or less, based on the blending amount of the ultraviolet absorber to 100 parts by mass of the photopolymerization initiator (B). When the lower limit value is not less than the above-mentioned lower limit value, the taper angle tends to be large, and when the upper limit value is not more than the above-mentioned upper limit value, high sensitivity tends to be obtained.

[1-1-8] thermal polymerization initiator

Further, the photosensitive resin composition for forming partition walls of an organic electroluminescent element of the present invention may contain a thermal polymerization initiator. By containing the thermal polymerization initiator, the degree of crosslinking of the film tends to be increased. Specific examples of such a thermal polymerization initiator include: azo compounds, organic peroxides, and hydrogen peroxide. These thermal polymerization initiators may be used alone or in combination of two or more.

When a thermal polymerization initiator is used in combination with a photopolymerization initiator in the light-sensitive resin composition in the expectation of improvement in sensitivity and increase in crosslinking density of the film, the total content ratio of these components is preferably set to the content ratio of the photopolymerization initiator in the light-sensitive resin composition, and the combined use ratio of the photopolymerization initiator and the thermal polymerization initiator is preferably 5 to 300 parts by mass of the thermal polymerization initiator per 100 parts by mass of the photopolymerization initiator in view of sensitivity.

[1-1-9] AMINO COMPOUNDS

The photosensitive resin composition for forming a spacer wall of an organic electroluminescent element of the present invention may contain an amino compound for promoting thermal curing. In this case, the content of the amino compound in the photosensitive resin composition is usually 40% by mass or less, preferably 30% by mass or less, based on the total solid content of the photosensitive resin composition. The content is usually 0.5% by mass or more, preferably 1% by mass or more. When the content is less than the upper limit, the storage stability tends to be maintained, and when the content is more than the lower limit, sufficient thermosetting property tends to be secured.

Examples of the amino compound include: an amino compound having at least 2 of methylol groups and alkoxymethyl groups obtained by condensation-modifying an alcohol having 1 to 8 carbon atoms as a functional group. Specific examples thereof include: a melamine resin obtained by polycondensation of melamine and formaldehyde; benzoguanamine resin obtained by condensation polymerization of benzoguanamine and formaldehyde; glycoluril resin obtained by polycondensation of glycoluril and formaldehyde; urea resins obtained by condensation polymerization of urea and formaldehyde; a resin obtained by copolycondensation of formaldehyde with at least two of melamine, benzoguanamine, glycoluril, urea, and the like; modified resins obtained by modifying methylol groups of the above resins by alcohol condensation. These amino compounds may be used alone or in combination of two or more. Among these, the amino compound is preferably a melamine resin and a modified resin thereof, more preferably a modified resin having a methylol group modification ratio of 70% or more, and particularly preferably a modified resin having a methylol group modification ratio of 80% or more.

Specific examples of the amino compound include melamine resins and modified resins thereof, for example: "Cymel" (registered trademark) 300, 301, 303, 350, 736, 738, 370, 771, 325, 327, 703, 701, 266, 267, 285, 232, 235, 238, 1141, 272, 254, 202, 1156, 1158, manufactured by SaiTech corporation, and "Nicarac" (registered trademark) MW-390, MW-100LM, MX-750LM, MW-30M, MX-45, MX-302, manufactured by Sanwa Chemical corporation, and the like. Examples of the benzoguanamine resin and modified resins thereof include: "Cymel" (registered trademark) 1123, 1125, 1128, and the like, manufactured by SaiTech corporation. Examples of the glycoluril resin and modified resin thereof include: "Cymel" (registered trademark) 1170, 1171, 1174, and 1172 manufactured by SaiTech corporation, and "Nicarac" (registered trademark) MX-270 manufactured by Sanwa Chemical corporation, and the like. In addition, examples of the urea resin and the modified resin thereof include: "UFR" (registered trademark) 65 and 300 manufactured by SaiTech corporation, and "Nicarac" (registered trademark) MX-290 manufactured by Sanwa Chemical corporation, and the like.

[1-1-10] coloring agent

In the photosensitive resin composition for forming a partition wall of an organic electroluminescent element of the present invention, a colorant may be contained for the purpose of coloring the partition wall. As the colorant, known colorants such as pigments and dyes can be used. In addition, when a pigment is used, for example, a known dispersing agent or dispersing aid may be used in combination so that the pigment can be stably present in the photosensitive resin composition without coagulation or the like. In particular, coloring the liquid-repellent partition walls black provides an effect of obtaining a clear pixel display. As the black colorant, in addition to a black dye or a black pigment, carbon black, titanium black, and the like, coloring to black by mixing an organic pigment is also effective in obtaining an effect of low conductivity. The content of the colorant is usually 60 mass% or less, preferably 40 mass% or less, based on the total solid content of the photosensitive resin composition, from the viewpoint of platemaking properties and color characteristics.

On the other hand, in the case of reducing the amount of outgas generated from the partition walls, the partition walls are preferably made transparent, and in this case, the content ratio of the colorant is preferably 10% by mass or less, more preferably 5% by mass or less, and particularly preferably 0% by mass, based on the total solid content of the photosensitive resin composition.

[1-1-11] coating Performance improver and development improver

The photosensitive resin composition for forming a spacer of an organic electroluminescent element of the present invention may contain a coating property improver and a development modifier for improving coating property and development solubility. As the coating property improving agent or the development improving agent, for example, a known cationic, anionic, nonionic, fluorine-based, or silicone-based surfactant can be used. As the development modifier, a known development modifier such as an organic carboxylic acid or an acid anhydride thereof may be used. From the viewpoint of sensitivity, the content thereof is usually 20 mass% or less, preferably 10 mass% or less, based on the total solid content of the photosensitive resin composition.

[1-1-12] silane coupling agent

In order to improve adhesion to the substrate, it is also preferable to add a silane coupling agent to the photosensitive resin composition for forming a spacer of an organic electroluminescent element of the present invention. Various silane coupling agents such as epoxy, methacrylic, amino, and imidazole can be used as the silane coupling agent, and epoxy and imidazole silane coupling agents are particularly preferable from the viewpoint of improving adhesion. From the viewpoint of adhesion, the content thereof is usually 20 mass% or less, preferably 15 mass% or less, with respect to the total solid content of the photosensitive resin composition.

[1-1-13] phosphoric acid adhesion improver

In order to improve the adhesion to the substrate, it is also preferable to add a phosphoric acid-based adhesion improver to the photosensitive resin composition for forming a spacer of an organic electroluminescent element of the present invention. The phosphate adhesion improver is preferably a phosphate containing a (meth) acryloyloxy group, and particularly preferably an adhesion improver represented by the following general formulae (Va), (Vb), and (Vc).

[ chemical formula 60]

In the above general formulae (Va), (Vb), (Vc), R⁸Represents a hydrogen atom or a methyl group, r and r' are each independently an integer of 1 to 10, and s is 1, 2 or 3.

[1-1-14] inorganic Filler

The photosensitive resin composition for forming a spacer wall of an organic electroluminescent element of the present invention may further contain an inorganic filler in order to improve the strength as a cured product and to improve the excellent flatness, taper angle, and the like of a coating film due to a moderate interaction (formation of a matrix structure) with an alkali-soluble resin. Examples of such inorganic fillers include: talc, silica, alumina, barium sulfate, magnesium oxide, and a surface-treated product thereof with various silane coupling agents.

The average particle diameter of these inorganic fillers is usually 0.005 to 20 μm, preferably 0.01 to 10 μm. The average particle diameter in the present embodiment is a value measured by a laser diffraction scattering particle size distribution measuring apparatus manufactured by Beckman Coulter corporation and the like. Among these inorganic fillers, silica sol and silica sol modified products are particularly preferable because they tend to have excellent dispersion stability and an excellent effect of improving the cone angle. When the photosensitive resin composition for forming a partition wall of an organic electroluminescent element of the present invention contains such an inorganic filler, the content thereof is usually 5% by mass or more, preferably 10% by mass or more, usually 80% by mass or less, preferably 70% by mass or less, relative to the total solid content, from the viewpoint of sensitivity.

[1-1-15] solvent

The photosensitive resin composition for forming a spacer of an organic electroluminescent element of the present invention usually contains a solvent, and the above-mentioned components may be used in a state of being dissolved or dispersed in the solvent (hereinafter, the photosensitive resin composition containing a solvent is also referred to as "photosensitive resin composition solution"). The solvent is not particularly limited, and examples thereof include the following organic solvents.

That is, there can be mentioned: glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-butyl ether, propylene glycol-tert-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-butyl ether, methoxymethylpentanol, dipropylene glycol monoethyl ether, dipropylene glycol monomethyl ether, 3-methyl-3-methoxybutanol, 3-methoxy-1-butanol, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, tripropylene glycol methyl ether, etc.; glycol dialkyl ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, and dipropylene glycol dimethyl ether; glycol alkyl ether acetates such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol mono-n-butyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, methoxybutyl acetate, 3-methoxybutyl acetate, methoxypentyl acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol mono-n-butyl ether acetate, dipropylene glycol monomethyl ether acetate, triethylene glycol monoethyl ether acetate, 3-methyl-3-methoxybutyl acetate, and 3-methoxy-1-butyl acetate; glycol diacetate esters such as ethylene glycol diacetate, 1, 3-butanediol diacetate, and 1, 6-hexanol diacetate; alkyl acetates such as cyclohexanol acetate; ethers such as amyl ether, diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, diamyl ether, ethyl isobutyl ether, and dihexyl ether; ketones such as acetone, methyl ethyl ketone, methyl amyl ketone, methyl isopropyl ketone, methyl isoamyl ketone, diisopropyl ketone, diisobutyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl amyl ketone, methyl butyl ketone, methyl hexyl ketone, methyl nonyl ketone, and methoxymethyl pentanone; monohydric or polyhydric alcohols such as methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, butylene glycol, diethylene glycol, dipropylene glycol, triethylene glycol, methoxymethylpentanol, glycerol, and benzyl alcohol; aliphatic hydrocarbons such as n-pentane, n-octane, diisobutylene, n-hexane, hexene, isoprene, dipentene, and dodecane; alicyclic hydrocarbons such as cyclohexane, methylcyclohexane, methylcyclohexene, and bicyclohexane; aromatic hydrocarbons such as benzene, toluene, xylene, and cumene; chain or cyclic esters such as amyl formate, ethyl acetate, butyl acetate, propyl acetate, amyl acetate, methyl isobutyrate, ethylene glycol acetate, ethyl propionate, propyl propionate, butyl butyrate, isobutyl butyrate, methyl isobutyrate, ethyl octanoate, butyl stearate, ethyl benzoate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, butyl 3-methoxypropionate, and γ -butyrolactone; alkoxycarboxylic acids such as 3-methoxypropionic acid and 3-ethoxypropionic acid; halogenated hydrocarbons such as butyl chloride and pentyl chloride; ether ketones such as methoxymethylpentanone; nitriles such as acetonitrile and benzonitrile; tetrahydrofuran such as tetrahydrofuran, dimethyltetrahydrofuran, dimethoxytetrahydrofuran, etc.

Commercially available solvents corresponding to the above include: mineral Spirit, Valsol #2, Apco #18Solvent, Apco thinker, Socal Solvent No.1 and No.2, Solvesso #150, Shell TS Solvent 28, carbitol, ethyl carbitol, butyl carbitol, methyl cellosolve, ethyl cellosolve acetate, methyl cellosolve acetate, Diglyme (all trade names), and the like.

The solvent is a solvent capable of dissolving or dispersing each component in the photosensitive resin composition, and can be selected according to the method of using the photosensitive resin composition of the present invention, but from the viewpoint of coatability, it is preferable to select a solvent having a boiling point in the range of 60 to 280 ℃ under atmospheric pressure (1013.25 hPa). More preferably a solvent having a boiling point of 70 ℃ or more and 260 ℃ or less, and is preferably, for example: propylene glycol monomethyl ether, 3-methoxy-1-butanol, propylene glycol monomethyl ether acetate, 3-methoxy-1-butyl acetate.

These solvents may be used singly or in combination of two or more. The solvent is preferably used so that the proportion of the total solid content in the photosensitive resin composition solution is usually 10% by mass or more, preferably 15% by mass or more, more preferably 20% by mass or more, and usually 90% by mass or less, preferably 50% by mass or less, more preferably 40% by mass or less, and still more preferably 30% by mass or less. When the lower limit value is not less than the above-mentioned lower limit value, a coating film tends to be obtained even with a high film thickness, and when the upper limit value is not more than the above-mentioned upper limit value, appropriate coating uniformity tends to be obtained.

[1-2] Properties of photosensitive resin composition for Forming spacer of organic electroluminescent element

The physical properties of the photosensitive resin composition for forming partition walls of an organic electroluminescent element of the present invention include, for example, acid value. The acid value of the entire solid content of the photosensitive resin composition for forming a spacer of an organic electroluminescent element is not particularly limited, but is preferably 20mgKOH/g or more, more preferably 22mgKOH/g or more, still more preferably 24mgKOH/g or more, still more preferably 26mgKOH/g or more, and particularly preferably 28mgKOH/g or more, and is usually 60mgKOH/g or less, preferably 55mgKOH/g or less, more preferably 50mgKOH/g or less, still more preferably 40mgKOH/g or less, and particularly preferably 35mgKOH/g or less. When the amount is not less than the lower limit, the solubility in the developer is high, and the unexposed portion can be sufficiently dissolved and removed, so that the taper angle tends to be large, and when the amount is not more than the upper limit, the development adhesion tends to be good.

[1-3] Process for producing photosensitive resin composition for Forming spacer of organic electroluminescent element

The photosensitive resin composition for forming partition walls of an organic electroluminescent element of the present invention can be prepared by mixing the above components with a stirrer. The photosensitive resin composition may be filtered by using a membrane filter or the like to make the photosensitive resin composition uniform.

[2] Spacer and method for forming spacer

The photosensitive resin composition of the present invention can be used for forming partition walls, particularly partition walls for partitioning organic layers (light emitting portions) of organic electroluminescent devices.

The method for forming the partition walls (dam) using the photosensitive resin composition for forming the partition walls of the organic electroluminescent element described above is not particularly limited, and a conventionally known method can be used. Examples of the method for forming the partition include a method including a coating step of coating a photosensitive resin composition for forming a partition wall of an organic electroluminescent element on a substrate to form a photosensitive resin composition layer, and an exposure step of exposing the photosensitive resin composition layer to light. A specific example of the method for forming such a partition wall is photolithography.

In the photolithography method, a photosensitive resin composition for forming a spacer wall of an organic electroluminescent element is applied to the entire surface of a region of a substrate where the spacer wall is to be formed to form a photosensitive resin composition layer. After the formed photosensitive resin composition layer is exposed to light according to a predetermined pattern of the partition walls, the exposed photosensitive resin composition layer is developed to form the partition walls on the substrate.

In a coating step of applying a photosensitive resin composition onto a substrate in a photolithography method, a photosensitive resin composition is applied onto a substrate on which partition walls are to be formed, using a contact transfer type coating apparatus such as a roll coater, a reverse coater, or a bar coater, or a non-contact type coating apparatus such as a spin coater (a spin coater) or a curtain flow coater, and a solvent is removed by drying as necessary, thereby forming a photosensitive resin composition layer.

Next, in an exposure step, the photosensitive resin composition is irradiated with active energy rays such as ultraviolet rays or excimer laser light using a negative mask, and the photosensitive resin composition layer is partially exposed in accordance with the pattern of the partition walls. The exposure may be performed using a light source emitting ultraviolet light, such as a high-pressure mercury lamp, an ultra-high pressure mercury lamp, a xenon lamp, or a carbon arc lamp. The exposure amount varies depending on the composition of the photosensitive resin composition, but is preferably 10 to 400mJ/cm²Left and right.

Next, in the developing step, the photosensitive resin composition layer exposed to light according to the pattern of the partition walls is developed in a developer to form the partition walls. The developing method is not particularly limited, and a dipping method, a spraying method, and the like can be used. Specific examples of the developer include: organic developers such as dimethylbenzylamine, monoethanolamine, diethanolamine, and triethanolamine, or aqueous solutions of sodium hydroxide, potassium hydroxide, sodium carbonate, ammonia, and quaternary ammonium salts. In addition, an antifoaming agent and a surfactant may be added to the developer.

Thereafter, the developed partition walls are post-baked and heat-cured. The post-baking is preferably carried out at 150 to 250 ℃ for 15 to 60 minutes.

The substrate for forming the partition walls is not particularly limited, and may be appropriately selected according to the kind of the organic electroluminescent element manufactured using the substrate on which the partition walls are formed. Preferred substrate materials include glass and various resin materials. Specific examples of the resin material include: polyesters such as polyethylene terephthalate; polyolefins such as polyethylene and polypropylene; a polycarbonate; poly (meth) acrylic resins; polysulfones; and (3) a polyimide. Among these substrate materials, glass and polyimide are preferable because of their excellent heat resistance. In addition, a transparent electrode layer of ITO, ZnO, or the like may be provided in advance on the surface of the substrate on which the spacer is to be formed, depending on the type of organic electroluminescent element to be manufactured.

[3] Organic electroluminescent element

The organic electroluminescent element of the present invention comprises the partition wall formed of the photosensitive resin composition for the partition wall of the organic electroluminescent element as described above.

Various optical elements can be manufactured using the substrate having the partition wall pattern manufactured by the above-described method. The method of forming the organic electroluminescent element is not particularly limited, but it is preferable to form an organic layer such as a pixel by injecting ink into a region surrounded by the partition walls on the substrate after forming the pattern of the partition walls on the substrate by the above-mentioned method.

Examples of the type of the organic electroluminescent element include a bottom emission type and a top emission type.

In the bottom emission type, for example, a partition wall is formed on a glass substrate on which a transparent electrode is laminated, and a hole transport layer, a light emitting layer, an electron transport layer, and a metal electrode layer are laminated in an opening surrounded by the partition wall. On the other hand, in the top emission type, for example, a partition wall is formed on a glass substrate on which a metal electrode layer is laminated, and an electron transport layer, a light emitting layer, a hole transport layer, and a transparent electrode layer are laminated in an opening surrounded by the partition wall.

The light-emitting layer may be an organic electroluminescent layer as described in japanese patent application laid-open nos. 2009-146691 and 5734681. Further, quantum dots as described in japanese patent No. 5653387 and japanese patent No. 5653101 may be used.

When the taper angle of the partition walls is small and the lower portions of the partition walls have a skirt shape as shown in fig. 1, light does not emit even if the vapor deposition layer is formed on the upper portions of the portions, which leads to a reduction in the light emission area. In addition, in the case of manufacturing the light-emitting layer by the ink jet method, since the ink for forming an organic layer is repelled at the skirt portion of the partition wall, the region surrounded by the partition wall may not be uniformly covered with the ink for forming an organic layer. On the other hand, by forming the ink jet recording head into a favorable shape having a large taper angle and no sag, the region surrounded by the partition walls can be made to emit light, and the ink jet recording head can be uniformly coated with the ink for forming an organic layer. This can eliminate, for example, the problem of halo in the organic EL display element.

As the solvent used in forming the ink for forming an organic layer, water, an organic solvent, and a mixed solvent thereof can be used. The organic solvent is not particularly limited as long as it can be removed from the formed film after the ink is injected. Specific examples of the organic solvent include: toluene, xylene, anisole, mesitylene, tetralin, cyclohexylbenzene, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methanol, ethanol, isopropanol, ethyl acetate, butyl acetate, 3-phenoxytoluene, and the like. In addition, a surfactant, an antioxidant, a viscosity modifier, an ultraviolet absorber, and the like may be added to the ink.

As a method of injecting ink into the region surrounded by the partition walls, an ink jet method is preferable because a small amount of ink can be easily injected into a predetermined portion. The ink used for forming the organic layer may be appropriately selected depending on the kind of the organic electroluminescent element to be manufactured. When the ink is injected by the ink jet method, the viscosity of the ink is not particularly limited as long as the ink can be ejected well from the ink jet head, but is preferably 4 to 20mPa · s, more preferably 5 to 10mPa · s. The viscosity of the ink can be adjusted by adjusting the solid content in the ink, changing the solvent, adding a viscosity modifier, and the like.

[4] Image display device

An image display device of the present invention includes the organic electroluminescent element described above. The type and structure of the image display device are not particularly limited as long as the organic electroluminescent element is contained, and for example, an active-drive type organic electroluminescent element can be used and assembled by a conventional method. For example, the image display device of the present invention can be formed by a method described in "organic EL display" (OHM corporation, 16 years, 8 months, 20 days, heaven, saint, thousand years, and cuntian yo). For example, an image display may be performed by combining an organic electroluminescent element that emits white light with a color filter, or an image display may be performed by combining organic electroluminescent elements having different luminescent colors such as RGB.

[5] Illumination device

The illumination of the present invention includes the organic electroluminescent element described above. The type and structure thereof are not particularly limited, and the organic electroluminescent element of the present invention can be assembled by a conventional method. The organic electroluminescent element may be of a simple matrix driving type or an active matrix driving type.

In order to make the illumination of the present invention emit white light, an organic electroluminescent element that emits white light may be used. Further, the organic electroluminescence elements having different emission colors may be combined to mix the colors into white, or the color mixing ratio may be adjusted to provide a color mixing function.

Examples

The photosensitive resin composition for forming a spacer for an organic electroluminescent element of embodiment 1 of the present invention will be described below with reference to specific examples, but the present invention is not limited to the following examples within the scope not exceeding the gist thereof.

[1] Preparation and evaluation of photosensitive resin composition for Forming spacer of organic electroluminescent element

Photosensitive resin compositions for forming partition walls of organic electroluminescent elements of examples and comparative examples were prepared by using the respective components at the mixing ratios (parts by mass) shown in table 1 and stirring the respective components uniformly using propylene glycol monomethyl ether acetate so that the content of the total solid content became 25% by mass. The numerical values in table 1 represent the values of the solid content.

The symbols in the table indicate the following meanings.

a-1: dipentaerythritol hexaacrylate (DPHA) (manufactured by Nippon Kabushiki Kaisha)

b-1: 2,2 '-bis (2-chlorophenyl) -4, 4', 5,5 '-tetraphenyl-1, 2' -biimidazole (manufactured by Baotu chemical Co., Ltd.)

b-2: irgacure 369 (Compound having the following chemical Structure, manufactured by BASF Corp.)

[ chemical formula 61]

d-1: megafac RS-72-K (fluorine type oligomer having olefinic double bond, manufactured by DIC Co., Ltd.)

e-1: 2-mercaptobenzimidazole (manufactured by Tokyo Kaisha)

e-2: pentaerythritol tetrakis (3-mercaptopropionate) (product of Kasei chemical Co., Ltd.)

f-1: TINUVIN 384-2 (ultraviolet absorber manufactured by BASF corporation)

g-1: KAYAMER PM-21 (made by Nippon Kagaku Co., Ltd.)

c-1: the following alkali-soluble resin having an ethylenically unsaturated group (corresponding to epoxy (meth) acrylate resin (c1-1))

100 parts by mass of a bisphenol A type epoxy compound (a mixture of compounds having an epoxy equivalent of 186g/eq and n in the formula of 1 to 20), 40 parts by mass of acrylic acid, 0.06 part by mass of p-methoxyphenol, 2.4 parts by mass of triphenylphosphine, and 126 parts by mass of propylene glycol monomethyl ether acetate were charged into a reaction vessel, and stirred at 95 ℃ until the acid value reached 5mgKOH/g or less. Then, to 80 parts by mass of the reaction solution obtained by the above reaction, 12 parts by mass of propylene glycol monomethyl ether acetate was added, 4.5 parts by mass of succinic anhydride was added, and the reaction mixture was reacted at 95 ℃ for 3 hours to obtain an alkali-soluble resin (c-1) solution having a solid acid value of 60mgKOH/g and a weight-average molecular weight (Mw) in terms of polystyrene as measured by GPC of 8,000.

[ chemical formula 62]

(G represents a glycidyl group)

c-2: the following acrylic copolymer resin (corresponding to (c2) acrylic copolymer resin)

An alkali-soluble acrylic copolymer resin (c-2) solution obtained by adding acrylic acid to a copolymer resin comprising tricyclodecane methacrylate/styrene/glycidyl methacrylate (molar ratio: 0.032/0.069/0.899) as a constituent monomer so as to cause an equivalent addition reaction with glycidyl methacrylate, and further adding succinic anhydride so as to achieve a molar ratio of 0.24 relative to 1 mole of the copolymer resin. The solvent is propylene glycol monomethyl ether acetate. The weight average molecular weight (Mw) in terms of polystyrene measured by GPC was 4,800, and the solid acid value was 62.1 mgKOH/g.

c-3: the following acrylic copolymer resins

An alkali-soluble acrylic copolymer resin (c-3) solution obtained by adding acrylic acid to a copolymer resin containing tricyclodecane methacrylate/styrene/glycidyl methacrylate (molar ratio: 0.3/0.1/0.6) as a constituent monomer so as to cause an equivalent addition reaction with glycidyl methacrylate, and further adding tetrahydrophthalic anhydride so as to achieve a 0.39 molar ratio with respect to 1 mole of the copolymer resin. The solvent is propylene glycol monomethyl ether acetate. The polystyrene-equivalent weight average molecular weight (Mw) measured by GPC was 8,400, and the solid acid value was 81.4 mgKOH/g.

Evaluation of physical properties of the photosensitive resin composition for forming a spacer of an organic electroluminescent element was carried out by the following method.

(measurement of acid value)

The acid value can be measured by the method described in JIS K0070-. The acid value of the photosensitive resin composition can be calculated from the acid value and the content of the acid group-containing component such as the resin, in addition to direct measurement of the photosensitive resin composition.

(measurement of gas quantity)

The photosensitive resin composition for spacer formation was applied onto a glass substrate using a spin coater so as to be 1.7 μm thick after heat curing. Thereafter, the resultant coating film was dried by heating at 95 ℃ for 2 minutes on a hot plate without using a mask at an exposure of 100mJ/cm²The entire surface was exposed. The intensity at a wavelength of 365nm was 7.5mW/cm². Subsequently, spray development was performed for 60 seconds using a 2.38 mass% TMAH (tetramethylammonium hydroxide) aqueous solution at 24 ℃, and then washing was performed for 10 seconds using pure water. The substrate was heat-cured at 230 ℃ for 30 minutes in an oven, to obtain a substrate for measuring a gas amount with a cured product.

The degasification of the prepared gas amount measuring substrate (40 mm. times.8 mm, 4 pieces) heated at 230 ℃ for 20 minutes in a heating furnace was analyzed by GC/MS (product name: 5973N, Agilent Technologies Co.) and the total area of all the components of the detected peak was calculated. Herein, the peak corresponding to tetramethylammonium derived from TMAH (tetramethylammonium hydroxide) aqueous solution was calculated by excluding it. Then, the total of the detected peak areas was converted into toluene amount using a calibration curve, and the toluene amount was divided by the measured substrate area to calculate the amount of degassing (ng/cm) in terms of toluene per unit area ²). The results are shown in Table 1. The calibration curve was prepared by performing GC/MS measurement using toluene of a known concentration and plotting the amount of toluene and the peak area value of the detected gas.

(measurement of contact Angle)

The photosensitive resin composition for spacer formation was applied onto a glass substrate by a spin coater so as to have a thickness of 1.7 μm after heat curing. Thereafter, the resultant coating film was dried by heating at 95 ℃ for 2 minutes on a hot plate without using a mask at an exposure of 100mJ/cm²The entire surface was exposed. The intensity at a wavelength of 365nm was 7.5mW/cm². Subsequently, spray development was performed for 60 seconds using a 2.38 mass% TMAH (tetramethylammonium hydroxide) aqueous solution at 24 ℃, and then washing was performed for 10 seconds using pure water. The substrate was cured by heating at 230 ℃ for 30 minutes in an oven, to obtain a substrate for measuring a contact angle with a cured product.

The contact angle was measured using a Drop Master 500 contact angle measuring apparatus manufactured by Kyowa interface science corporation under conditions of 23 ℃ and 50% humidity. To the contact angle measurement substrate cured product was added dropwise 0.7. mu.L of propylene glycol methyl ether acetate, and the contact angle after 1 second was measured. The measurement results are shown in Table 1. The case where the contact angle is large indicates high liquid repellency.

[2] Formation and evaluation of partition wall

The formation of the partition walls and the performance evaluation were performed by the following methods.

(formation of partition wall)

The photosensitive resin composition for forming the partition walls was applied onto the ITO film of the glass substrate having the surface ITO film formed on the surface thereof by using a spin coater so as to have a thickness of 1.7 μm after heat curing. Thereafter, the coating film was dried by heating at 95 ℃ for 2 minutes on a hot plate, and the obtained coating film was subjected to exposure with an exposure gap of 16 μm and an intensity at a wavelength of 365nm of 7.5mW/cm using a photomask (a mask having a plurality of coating portions of 80 μm × 280 μm at intervals of 10 μm)²So that the exposure amount reaches 100mJ/cm²The exposure was performed in the manner of (1). The ultraviolet irradiation at this time was performed in the air. Subsequently, the resultant was spray-developed with a 2.38 mass% TMAH (tetramethylammonium hydroxide) aqueous solution at 24 ℃ for 60 seconds, and then washed with pure water for 1 minute. So that unnecessary parts are removed and formed by these operationsThe patterned substrate was cured by heating at 230 ℃ for 30 minutes in an oven to form lattice-shaped partition walls.

(evaluation of taper angle and line width of spacer wall)

The lattice-like partition walls were cut to prepare samples for cross-sectional observation, and the cross-sectional shapes of the partition walls were observed by a scanning electron microscope (SEM, Keyence corporation) to measure the taper angles thereof. The measurement results are shown in Table 1. The sectional shape of the partition wall was observed to be a substantially trapezoidal shape.

In the cross-sectional view, as shown in fig. 1, the interface between the barrier ribs 1 and the ITO film 2 is represented by S, and the height of the barrier ribs is represented by H. In the oblique side of the partition wall, a tangent to the oblique side in contact with the interface S is designated as T, and an angle formed by the tangent T and the interface S is measured as a taper angle. The larger the taper angle, the more favorable the developability and the less likely residue to be generated, and the more likely wetting-out will occur in the inkjet coating.

(evaluation of suitability for inkjet coating of partition wall)

On the substrate having the lattice-shaped partition walls, the pixel portion surrounded by the lattice-shaped partition walls was subjected to ink-jet coating using DMP-2831 manufactured by Fuji Film co. As the ink, coating of 80pL per 1 pixel was performed using a solvent (isoamyl benzoate) alone, and whether or not there was a collapse (a phenomenon in which the ink was mixed into an adjacent pixel portion across the partition walls) was evaluated. The evaluation results are shown in table 1. The more the liquid repellency was higher, the more the liquid repellency was not deteriorated.

[ evaluation of outbreak ]

O: the ink can be applied to the inside of the pixel without overflowing the partition wall.

And (delta): a part of the ink flows up to the upper surfaces of the partition walls, but hardly flows out to the partition walls.

X: the ink overflows from the pixel to the entire upper surface of the partition wall, and is mixed into the adjacent pixel portion. (burst)

(evaluation of taper Angle and line Width of Barrier rib-2)

The photosensitive resin compositions for spacer formation of examples 1 and 2 were applied to the ITO film of the glass substrate having the ITO film formed on the surface thereof by a spin coater so as to have a thickness of 1.7 μm after heat curing. Thereafter, a coating film obtained by heat drying on a hot plate under the same conditions as described above was subjected to the same exposure, development, and heat curing to form lattice-shaped partition walls, except that a photomask (a mask having a plurality of coating portions of 80 μm × 280 μm at 40 μm intervals) was used.

As a result of observing the sectional shape of the partition walls using a scanning electron microscope (SEM, Keyence corporation) in the same manner as described above and measuring the taper angle and the line width thereof, the taper angles of examples 1 and 2 were 29 ° and 20 °, respectively, and the line widths of examples 1 and 2 were 40 μm, respectively. The opening widths (lateral width and vertical width) of the lower portions of the partition walls were measured, and the opening area was calculated by multiplying these widths, and as a result, both of examples 1 and 2 were 100%. The opening area is a relative value to the corresponding mask shielding portion area. The smaller the taper angle, the larger the line width of the partition wall and the smaller the opening area.

[ Table 1] (parts by mass)

The mixing ratio indicates the mixing ratio of the solid components to the total solid components

As is clear from Table 1, the amount of outgassing of the substrate obtained by using the photosensitive resin composition for spacer formation comprising the alkali-soluble resin (c-1) and (c-2) to which succinic acid was added as in examples 1 to 5 was significantly reduced as compared with the substrate obtained by using the photosensitive resin composition for spacer formation comprising the alkali-soluble resin (c-3) to which tetrahydrophthalic acid was added as in comparative example 1.

From this, it was confirmed that the photosensitive resin composition for forming partition walls, which contains an alkali-soluble resin to which an acid having a short carbon chain such as succinic acid is added, had a smaller amount of outgas under the gas measurement conditions of being cured by heating at 230 ℃ for 30 minutes of post-baking and then being heated at 230 ℃ as compared with the photosensitive resin composition for forming partition walls, which contains an alkali-soluble resin to which an acid having a long carbon chain such as tetrahydrophthalic acid is added. It is considered that this is because acids with short carbon chains such as succinic acid are substantially decomposed and removed at the time of post baking, and gas derived from the acids is not generated even when the post baking is further heated at 230 ℃.

Further, as is clear from table 1, the photosensitive resin composition containing the chain transfer agent as in example 5 has a sufficiently larger taper angle than the photosensitive resin composition containing no chain transfer agent as in comparative example 2. It is considered that the inclusion of the chain transfer agent improves the deactivation of radicals near the surface due to oxygen inhibition or the like, thereby improving the surface curability and increasing the taper angle.

It was also found that the contact angle was sufficiently large, and that the coating could be performed without any collapse even in the inkjet coating. This is presumably because the inclusion of a chain transfer agent can improve the surface curability, suppress the outflow of the liquid repellent, and fix the liquid repellent in the vicinity of the surface.

Further, as is clear from comparative examples 2 to 4, even if the contact angle is the same, the force (surface energy) causing the ink to expand outward of the partition walls at the side surfaces of the partition walls becomes small in the case of a larger taper angle, and the surface curability at the upper portions of the partition walls becomes higher even in the case of the partition walls having undergone thinning, and the liquid repellent can be further fixed in the vicinity of the surface, and as a result, the ink jet application suitability becomes better.

It is considered that, by comparing examples 1 and 2, the (c1) epoxy (meth) acrylate resin is less likely to be permeated with the alkali developing solution than the (c2) acrylic copolymer resin, and therefore, the taper angle of example 2 becomes larger than that of example 1.

The photosensitive resin composition for forming a spacer of an organic electroluminescent element of embodiment 2 of the present invention will be described below with reference to specific experimental examples, but the present invention is not limited to the following experimental examples within the scope not exceeding the gist thereof.

[I] Preparation of photosensitive resin composition for spacer wall formation

The photosensitive resin compositions for forming partition walls in experimental examples and comparative experimental examples were prepared by using the respective components at the mixing ratios (parts by mass) described in table 2 and stirring the respective components uniformly using propylene glycol monomethyl ether acetate so that the content of the total solid content became 25% by mass.

The symbols in the table indicate the following meanings.

a-11: a mixture of the following ethylenically unsaturated compounds [ (A1) a mixture of an ethylenically unsaturated compound having an acid group and (A2) an ethylenically unsaturated compound having no acid group ]

A mixture (hydroxyl value: 113mgKOH/g)490 parts by mass of pentaerythritol triacrylate and pentaerythritol tetraacrylate was reacted at 100 ℃ for 5 hours in the presence of 148 parts by mass of phthalic anhydride, 2.5 parts by mass of triethylamine and 0.25 part by mass of hydroquinone to obtain a mixture a-11 containing a phthalic anhydride-modified product of pentaerythritol triacrylate and pentaerythritol tetraacrylate as shown below at a mass ratio of 70: 30.

[ chemical formula 63]

a-12: the following mixture of ethylenically unsaturated compounds [ (A1) mixture of ethylenically unsaturated compounds having an acid group and (A2) ethylenically unsaturated compounds having no acid group ]

A mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate (hydroxyl value 100mgKOH/g)561 parts by mass was reacted at 100 ℃ for 5 hours in the presence of 100 parts by mass of succinic anhydride, 2.5 parts by mass of triethylamine and 0.25 part by mass of hydroquinone to give a mixture a-12 containing a succinic anhydride-modified pentaerythritol triacrylate and pentaerythritol tetraacrylate as shown below in a ratio of 60:40 (mass ratio).

[ chemical formula 64]

a-13: a mixture of the following ethylenically unsaturated compounds [ (A1) a mixture of an ethylenically unsaturated compound having an acid group and (A2) an ethylenically unsaturated compound having no acid group ]

A mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (hydroxyl value: 51mgKOH/g) was reacted at 1,000 parts by mass in the presence of 49 parts by mass of succinic anhydride, 2.5 parts by mass of triethylamine and 0.25 part by mass of hydroquinone at 100 ℃ for 5 hours to obtain a mixture a-13 containing a succinic anhydride-modified dipentaerythritol pentaacrylate, dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate shown below in a mass ratio of 25:25: 50.

[ chemical formula 65]

a-14: pentaerythritol tetraacrylate (PE-4A) (product of Kyoeisha chemical Co., Ltd.)

b-1: 2,2 '-bis (2-chlorophenyl) -4, 4', 5,5 '-tetraphenyl-1, 2' -biimidazole (manufactured by Baotuzu chemical industry Co., Ltd.)

c-4: the following ethylenically unsaturated group-containing resin (epoxy acrylate resin)

100 parts by mass of a bisphenol A type epoxy compound (a mixture of compounds having an epoxy equivalent of 186g/eq and n in the formula of 1 to 20), 40 parts by mass of acrylic acid, 0.06 part by mass of p-methoxyphenol, 2.4 parts by mass of triphenylphosphine, and 126 parts by mass of propylene glycol monomethyl ether acetate were charged into a reaction vessel, and stirred at 95 ℃ until the acid value reached 5mgKOH/g or less. Then, to 80 parts by mass of the reaction solution obtained by the above reaction, 3 parts by mass of propylene glycol monomethyl ether acetate and 3 parts by mass of succinic anhydride were added, and the reaction was carried out at 95 ℃ for 3 hours to obtain an alkali-soluble resin (c-4) solution having a solid acid value of 40mgKOH/g and a weight average molecular weight (Mw) of 8,000 in terms of polystyrene as measured by GPC.

[ chemical formula 66]

(G represents a glycidyl group)

e-1: 2-mercaptobenzimidazole (manufactured by Tokyo Kasei K.K.)

e-2: pentaerythritol tetrakis (3-mercaptopropionate) (product of lake chemical Co., Ltd.)

f-1: TINUVIN 384-2 (ultraviolet absorber manufactured by BASF corporation)

g-1: KAYAMER PM-21 (manufactured by Nippon Kabushiki Kaisha)

[ Table 2] (parts by mass)

[ II ] formation of cured product and partition wall, and evaluation thereof

Hereinafter, a method of evaluating the performance of each photosensitive resin composition will be described.

(production of substrate for measuring contact Angle)

The photosensitive resin composition for forming the partition walls was applied on the ITO film of the glass substrate having the ITO film formed on the surface thereof by a spin coater so as to be 1.5 μm thick after heat curing, and 10 substrates were prepared for each of the photosensitive resin compositions for forming the partition walls. Then, the film is dried by heating on a hot plate at 100 ℃ for 2 minutes, and the obtained coating film is exposed to 50 to 500mJ/cm of light for each substrate without using a mask²In the range of 50mJ/cm²The interval of (a) is changed to perform exposure. The intensity at a wavelength of 365nm in this case was 40mW/cm². Next, the mixture was introduced into a reactor using a 2.38 mass% TMAH (tetramethylammonium hydroxide) aqueous solution at 24 DEG C After 60 seconds of spray development, the substrate was washed with pure water for 10 seconds. The substrate was heated and cured at 230 ℃ for 30 minutes in an oven, and a substrate for measuring a contact angle with a cured product formed was obtained.

(evaluation of contact Angle)

Since the curability of the composition varies depending on the sensitivity, the exposure amount for causing liquid repellency varies depending on the composition. The exposure amount which causes liquid repellency herein means an exposure amount at which the contact angle of the resulting cured product becomes 10 degrees or more. The contact angle with propylene glycol monomethyl ether acetate was measured using the substrate for measuring contact angle described above, and a substrate having a contact angle of 10 degrees or more was identified. The minimum exposure amount among the exposure amounts of these substrates at the time of production was set as the minimum exposure amount, and is shown in table 2. The contact angle was measured at 23 ℃ and 50% humidity using a Drop Master 500 contact angle measuring apparatus manufactured by Kyowa interface science corporation.

(preparation of partition wall)

The photosensitive resin composition for forming the partition walls was applied on the ITO film of the glass substrate having the surface ITO film formed on the surface thereof by a spin coater so as to be 1.5 μm thick after heat curing. Thereafter, the mixture was dried by heating on a hot plate at 100 ℃ for 2 minutes. The resulting coating film was exposed to light using a photomask. The exposure amount was set to the minimum exposure amount for liquid repellency, and the exposure gap was set to 16 μm. The photomask used was a mask having lattice-shaped openings (a mask having a plurality of coating portions of 80 μm × 280 μm at 40 μm intervals). Subsequently, similarly to the production of the substrate for contact angle measurement, the substrate was developed in a TMAH aqueous solution and then heat-cured to reach lattice-shaped partition walls.

(evaluation of ink-jet coating suitability)

On the substrate having the above-described lattice-shaped partition walls, the light-emitting sections (pixel sections) surrounded by the lattice-shaped partition walls were subjected to inkjet coating using DMP-2831 manufactured by Fuji Film co. As an ink, coating was performed using a solvent (isoamyl benzoate) alone at 40pL per 1 pixel portion, and wettability was evaluated. The more the entire area in the pixel portion is wetted, the less the residue and the like at the time of manufacturing the partition walls, and the better the developing property.

O: the ink spreads over the entire area within the pixel portion.

X: a portion to which the ink is not spread is generated in the pixel portion.

(production of substrate for measuring gas amount)

The photosensitive resin composition for forming partition walls was applied to the ITO film of the glass substrate having the surface ITO film formed on the surface thereof by a spin coater so as to be heated and cured to have a thickness of 1.5 μm. Thereafter, the coating film was dried by heating at 100 ℃ for 2 minutes on a hot plate and exposed to the above-mentioned minimum exposure amount for liquid repellency without using a mask. The intensity at a wavelength of 365nm in this case was 40mW/cm². Subsequently, the substrate was developed with a TMAH aqueous solution in the same manner as the substrate for measuring the contact angle, and then heated and cured at 230 ℃ for 30 minutes in an oven, whereby a substrate for measuring the amount of gas on which a cured product was formed was obtained.

(measurement of gas quantity)

The amount of outgas when the prepared gas amount measuring substrate (40 mm. times.8 mm, 4 pieces) was heated at 230 ℃ for 20 minutes in a heating furnace was analyzed by GC/MS (product name: 5973N, Agilent Technologies Co.) and the total area of all the components of the detected peak was calculated. Then, the total of the detected peak areas was converted into toluene amount using a calibration curve, and the toluene amount was divided by the measured substrate area to calculate the degassing amount (ng/cm) in terms of toluene per unit area²). The calibration curve was prepared by performing GC/MS measurement using toluene of a known concentration and plotting the amount of toluene and the peak area value of the detected gas.

As is clear from table 2, the partition walls obtained from the photosensitive resin compositions of the respective experimental examples containing the ethylenically unsaturated compound having an acid group at a specific ratio were excellent in ink jet coating suitability and low in degassing amount. This is because the use of an ethylenically unsaturated compound having an acid group with excellent solubility can suppress the generation of residue in the pixel portion to improve the ink jet characteristics, and the use of an amount of the ethylenically unsaturated compound having an acid group or less to suppress the generation of outgas originating from the acid group.

On the other hand, the partition wall obtained from the photosensitive resin composition of comparative example 1 containing a large amount of the ethylenically unsaturated compound having an acid group was excellent in ink jet coating suitability, but the amount of degassing was large, and it is considered that this is because the amount of degassing derived from an acid group was large. Further, it is considered that the partition walls obtained from the photosensitive resin composition of comparative example 2 containing no ethylenically unsaturated compound having an acid group are insufficient in ink jet coating suitability, and this is because residues are generated in the pixel portion.

In addition, regarding the ink jet application suitability, whether or not the ink spreads over the entire area within the pixel portion depends on whether or not the liquid repellency derived from the residue is generated within the pixel portion. Therefore, it is considered that the same results as those in the above experimental examples and comparative experimental examples can be obtained even when a solvent other than isoamyl benzoate is used.

While the present invention has been described in detail with reference to the specific embodiments, it will be understood by those skilled in the art that various changes and modifications may be made without departing from the spirit and scope of the invention. It should be noted that the present application was completed based on japanese patent application laid out on 2016 (japanese patent application 2016-.

Claims

1. A photosensitive resin composition for forming an organic electroluminescent element partition wall, comprising:

(A) an ethylenically unsaturated compound,

(B) Photopolymerization initiator, and

(C) an alkali-soluble resin which is capable of dissolving,

wherein the alkali-soluble resin (C) contains an alkali-soluble resin (C) having a partial structure represented by the following general formula (1),

the alkali-soluble resin (c) contains (c1) an epoxy (meth) acrylate resin, and the (c1) epoxy (meth) acrylate resin is at least one selected from the group consisting of: an epoxy (meth) acrylate resin having a repeating unit structure represented by the following formula (i), an epoxy (meth) acrylate resin having a partial structure represented by the following formula (ii), and an epoxy (meth) acrylate resin having a partial structure represented by the following formula (iii),

in the formula (i), R^aRepresents a hydrogen atom or a methyl group, R^bRepresents a 2-valent hydrocarbon group optionally having a substituent, the benzene ring in the formula (i) is optionally further substituted with an optional substituent, and represents a bonding position;

in the formula (ii), R^cEach independently represents a hydrogen atom or a methyl group, R^dRepresents a 2-valent hydrocarbon group having a cyclic hydrocarbon group as a side chain, and represents a bonding position;

in the formula (iii), R^eRepresents a hydrogen atom or a methyl group, γ represents a single bond, -CO-, an alkylene group optionally having a substituent, or a 2-valent cyclic hydrocarbon group optionally having a substituent, the benzene ring in the formula (iii) is optionally further substituted with an optional substituent, and represents a bonding position,

The photosensitive resin composition further contains (E) a chain transfer agent,

in the formula (1), R¹Represents a C1-4-valent hydrocarbon group optionally having a substituent, represents a bonding position,

the photosensitive resin composition further contains (D) a liquid repellent containing a liquid repellent having a crosslinking group.

2. The photosensitive resin composition for forming a spacer of an organic electroluminescent element according to claim 1, wherein the alkali-soluble resin (c) is a resin having an ethylenically unsaturated group.

3. The photosensitive resin composition for forming a spacer for an organic electroluminescent element according to claim 1, wherein the epoxy (meth) acrylate resin (c1) is obtained by adding an acid or ester compound having an ethylenically unsaturated bond to an epoxy resin and further adding a polybasic acid or an acid anhydride thereof.

4. The photosensitive resin composition for forming a spacer of an organic electroluminescent element according to claim 1, which further comprises an ultraviolet absorber.

5. The photosensitive resin composition for forming an organic electroluminescent element spacer according to claim 1, wherein the acid value of the photosensitive resin composition for forming an organic electroluminescent element spacer is 20mgKOH/g or more based on the total solid content.

6. A partition wall comprising the photosensitive resin composition for forming a partition wall of an organic electroluminescent element as claimed in any one of claims 1 to 5.

7. An organic electroluminescent element comprising the partition wall according to claim 6.

8. An image display device comprising the organic electroluminescent element according to claim 7.

9. An illumination comprising the organic electroluminescent element according to claim 7.