JP2018018036A - Photosensitive resin composition for forming partition wall, partition wall, organic electroluminescent element, image display device and illumination - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photosensitive resin composition for forming a partition wall that reduces an amount of outgas when operating a light emitting element, has high reliability, causes few residues, and secures excellent application properties in inkjet system.SOLUTION: A photosensitive resin composition for forming a partition wall contains (A) an ethylenic unsaturated compound, (B) a photopolymerization initiator and (C) an alkali-soluble resin, the (C) alkali-soluble resin containing (C1) an epoxy (meth) acrylate resin, and (C2) an acryl copolymer resin having an ethylenically unsaturated group in a side chain.SELECTED DRAWING: None

Description

  The present invention relates to a partition-forming photosensitive resin composition used for forming a partition, and in particular, a partition composed of the partition-forming photosensitive resin composition, an organic electroluminescence device including the partition, and the organic electric field. The present invention relates to an image display device including a light emitting element and illumination.

  Conventionally, an organic electroluminescent device included in an organic electric field display or organic electric field illumination has a barrier rib (bank) formed on a substrate, and various functional layers are laminated in a region surrounded by the barrier rib. It is manufactured. As a method for forming such a partition easily, a method of forming by a photolithography method using a photosensitive resin composition is known (see Patent Document 1).

  In addition, as a method for laminating various functional layers in the region surrounded by the partition walls, first, an ink containing a material constituting the functional layer is prepared, and then the prepared ink is injected into the region surrounded by the partition walls. How to do is known. Among these methods, an ink jet method is often employed because a predetermined amount of ink is easily injected accurately into a predetermined location.

Furthermore, when the functional layer is formed using ink, the partition wall has ink repellency for the purpose of preventing the ink from adhering to the partition wall or preventing the ink injected between adjacent regions from being mixed together. It may be required to grant.
In recent years, various properties in addition to ink repellency are required for the partition walls, and various photosensitive resin compositions have been developed. For example, Patent Document 2 describes a method of reducing the residue in the opening by selecting a material related to specific light absorption. On the other hand, as in Patent Document 3, a method for selecting an initiator species is described in order to reduce outgas generated during the formation of the partition walls. Patent Document 4 describes a method of mixing different resin types in order to improve dispersibility and storage stability.

JP 2010-262940 A International Publication No. 2015/125787 Pamphlet JP 2011-146375 A International Publication No. 2013/069789 Pamphlet

In recent years, in order to improve the drive life of an element, there is a demand for reducing outgas generated from the partition during light emission after the partition and element formation.
As a result of investigations by the present inventors, the photosensitive resin composition for forming a partition described in Patent Documents 2 and 4 achieves both reduction of residue, ink repellency, and reduction of outgas during long-time operation of the light emitting device. Has been found to be difficult. Furthermore, it has been found that the partition wall-forming photosensitive resin composition described in Patent Document 3 has insufficient reduction of outgas during long-term operation of the light-emitting device.
Therefore, an object of the present invention is to provide a photosensitive resin composition for forming a partition wall, which has a small amount of outgas when operating a light emitting device, high reliability, little residue, and good coating properties in an ink jet method.
Another object of the present invention is to provide a partition formed using the photosensitive resin composition for forming a partition, an organic electroluminescent element including the partition, an image display apparatus including the organic electroluminescent element, and illumination. To

As a result of intensive studies by the present inventors, in the photosensitive resin composition for forming a partition wall containing an ethylenically unsaturated compound, a photopolymerization initiator, and an alkali-soluble resin, the above problem can be solved by using a specific alkali-soluble resin in combination. The inventors have found that this can be solved, and have completed the present invention.
That is, the gist of the present invention is as follows.

[1] A partition-forming photosensitive resin composition comprising (A) an ethylenically unsaturated compound, (B) a photopolymerization initiator, and (C) an alkali-soluble resin,
The (C) alkali-soluble resin contains (C1) an epoxy (meth) acrylate resin, and (C2) an acrylic copolymer resin having an ethylenically unsaturated group in the side chain. Resin composition.
[2] The partition wall-forming photosensitive resin composition according to [1], wherein the (C2) acrylic copolymer resin includes a partial structure represented by the following general formula (I).

(In formula (I), R ¹ represents a hydrogen atom or a methyl group. R ² represents an alkenyl group which may have a substituent or a group represented by the following general formula (II). R ³ represents Represents a hydrogen atom or a group represented by the following general formula (III).)

(In the formula (II), R ⁴ represents an alkenyl group which may have a substituent. Α represents an alkylene group which may have a substituent, an arylene group which may have a substituent, Or an alkenylene group which may have a substituent, * represents a bond to the carbonyl carbon.

(In the above formula (III), β is a residue of a dicarboxylic acid.)
[3] The [C1] epoxy (meth) acrylate resin contains at least one of the resins represented by the following general formulas (C1-1) to (C1-6): [1] or [2] The photosensitive resin composition for barrier rib formation as described in 2.

(In formula (C1-1), R ¹¹¹ represents a hydrogen atom, a halogen atom, an alkyl group, or an aryl group, and n ¹¹¹ represents an integer of 0 to 20.)

(In the formula (C1-2), R ¹²¹ represents a hydrogen atom, a halogen atom, an alkyl group or an aryl group, and n ¹²¹ represents an integer of 0 to 20.)

(In the formula (C1-3), R ¹³¹ represents a hydrogen atom, a halogen atom, an alkyl group or an aryl group. M ¹³¹ and n ¹³¹ each independently represents an integer of 0 to 20. γ is a single bond, —CO. —, —CH ₂ —, —C (CH ₃ ) ₂ —, a group represented by the following formula (IV), or a group represented by the following formula (V): δ represents a hydrogen atom or a polybasic acid residue. )

(In the formula (C1-4), R ¹⁴¹ represents an alkyl group or a halogen atom, and p represents an integer of 0 to 4.)

(In the formula (C1-6), R ¹⁶¹ represents a hydrogen atom, a halogen atom, an alkyl group or an aryl group, and n ¹⁶¹ represents an integer of 0 to 20.
In the formulas (C1-1) to (C1-6), A represents a group represented by the following general formula (VI). )

(In formula (VI), R ¹⁷¹ represents a hydrogen atom or a methyl group, R ¹⁷² represents an alkylene group, m ¹⁷¹ represents an integer of 0 to 10. δ represents a hydrogen atom or a polybasic acid residue. Represents.)
[4] The (C1) epoxy (meth) acrylate resin is a resin obtained by adding an ethylenically unsaturated monocarboxylic acid or an ester compound to an epoxy resin and further reacting with a polybasic acid or an anhydride thereof. ] The photosensitive resin composition for partition formation in any one of [3].
[5] The barrier rib-forming photosensitivity according to any one of [1] to [4], wherein the content ratio of the (C1) epoxy (meth) acrylate resin in the (C) alkali-soluble resin is 30 to 95% by mass. Resin composition.
[6] The partition wall forming photosensitive resin composition according to any one of [1] to [5], wherein the (C) alkali-soluble resin has an average acid value of 50 mg-KOH / g or less.
[7] The photosensitive resin composition for forming a partition wall according to any one of [1] to [6], further comprising (D) a liquid repellent.
[8] The photosensitive resin composition for forming a partition wall according to [7], wherein the liquid repellent (D) has a crosslinking group.
[9] The photosensitive resin composition for forming a partition wall according to any one of [1] to [8], further containing a chain transfer agent.

[10] The photosensitive resin composition for forming a partition wall according to any one of [1] to [9], further comprising an ultraviolet absorber.
[11] A partition composed of the photosensitive resin composition for forming a partition according to any one of [1] to [10].
[12] An organic electroluminescence device comprising the partition wall according to [11].
[13] An image display device comprising the organic electroluminescent element according to [12].
[14] An illumination including the organic electroluminescent element according to [12].

  According to the present invention, it is possible to provide a photosensitive resin composition for forming a partition wall, which has a small amount of outgas when operating a light emitting device, high reliability, little residue, and good coating properties in an inkjet method.

FIG. 1 is an explanatory diagram of a method for evaluating a taper angle of a partition wall.

Hereinafter, the present invention will be described in detail. In addition, the following description is an example of embodiment of this invention, and this invention is not specified to these, unless the summary is exceeded.
In the present invention, “(meth) acryl” means “acryl and / or methacryl”, and “total solids” means all components other than the solvent in the photosensitive resin composition. Shall mean. Furthermore, the numerical range represented using “to” in the present invention means 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” means that both a single polymer (homopolymer) and a copolymer (copolymer) are included, and “(acid) anhydride”, “ The term “(anhydrous)... Acid” means to include both an acid and its anhydride.
In the present invention, the partition material refers to bank material, wall material, and wall material, and similarly, the partition material refers to bank, wall, and wall.
In the present invention, the weight average molecular weight refers to a polystyrene equivalent weight average molecular weight (Mw) by GPC (gel permeation chromatography).

[1] Photosensitive resin composition for forming a partition The photosensitive resin composition for forming a partition of the present invention contains (A) an ethylenically unsaturated compound, (B) a photopolymerization initiator, and (C) an alkali-soluble resin. A photosensitive resin composition for forming a partition, wherein the (C) alkali-soluble resin comprises (C1) an epoxy (meth) acrylate resin, and (C2) an acrylic copolymer resin having an ethylenically unsaturated group in a side chain. It is characterized by containing. Furthermore, other components may be further included as necessary, and for example, (D) a liquid repellent, a chain transfer agent, and an ultraviolet absorber may be included.

  In the present invention, the partition wall is, for example, a material for partitioning a functional layer (organic layer) in the active drive organic electroluminescence device, and is a material for forming the functional layer in the partitioned region (pixel region). It is used to form pixels and the like composed of functional layers and partition walls by ejecting and drying a certain ink.

[1-1] Components and composition of the photosensitive resin composition for forming a partition The components and the composition of the photosensitive resin composition for forming a partition of the present invention will be described.
The photosensitive resin composition for forming a partition wall of the present invention (hereinafter sometimes simply referred to as “photosensitive resin composition”) includes (A) an ethylenically unsaturated compound, (B) a photopolymerization initiator, and (C) an alkali. It contains a soluble resin and usually further contains a solvent. Moreover, it is preferable to use the photosensitive resin composition for partition formation of this invention in order to form a liquid-repellent partition, It is preferable to contain (D) liquid repellent from the viewpoint which concerns, and the said ( You may use what shows the effect | action as a liquid repellent as A)-(C) component.

[1-1-1] (A) component; ethylenically unsaturated compound The photosensitive resin composition for partition formation of the present invention contains (A) an ethylenically unsaturated compound. (A) It is thought that it becomes high sensitivity by including an ethylenically unsaturated compound.
As used herein, an ethylenically unsaturated compound means a compound having at least one ethylenically unsaturated bond in the molecule, but it is polymerizable, crosslinkable, and a developer solution for exposed and non-exposed areas associated therewith. In view of the ability to expand the difference in solubility, the compound is preferably a compound having two or more ethylenically unsaturated bonds in the molecule, and the unsaturated bond is derived from a (meth) acryloyloxy group, That is, it is more preferable that it is a (meth) acrylate compound.

In the present invention, it is particularly desirable to use a polyfunctional ethylenic monomer having two or more ethylenically unsaturated bonds in one molecule. The number of ethylenically unsaturated groups contained in the polyfunctional ethylenic monomer is not particularly limited, but is preferably 2 or more, more preferably 3 or more, still more preferably 5 or more, and preferably 15 or less, more preferably Is 10 or less. By setting it as the said lower limit or more, there exists a tendency for polymerizability to improve and to become high sensitivity, and there exists a tendency for developability to become more favorable by setting it as the said upper limit or less.
Specific examples of the ethylenically unsaturated compound include an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid; an ester of an aromatic polyhydroxy compound and an unsaturated carboxylic acid; an aliphatic polyhydroxy compound and an aromatic polyhydroxy compound And esters obtained by an esterification reaction of a polyvalent hydroxy compound such as an unsaturated carboxylic acid and a polybasic carboxylic acid.

  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, Acrylic acid esters of aliphatic polyhydroxy compounds such as pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, glycerol acrylate, etc. In the same way, itaconic acid ester instead of itaconate, Maleic acid esters in which instead of the crotonic acid ester or maleate was changed to and the like.

Examples of the ester of an aromatic polyhydroxy compound and an unsaturated carboxylic acid include acrylic acid esters and methacrylic acid esters of aromatic polyhydroxy compounds such as hydroquinone diacrylate, hydroquinone dimethacrylate, resorcin diacrylate, resorcin dimethacrylate, pyrogallol triacrylate and the like. Etc.
Esters obtained by esterification reaction of polyvalent hydroxy compounds such as aliphatic polyhydroxy compounds and aromatic polyhydroxy compounds with unsaturated carboxylic acids and polybasic carboxylic acids are not necessarily a single substance, but are representative. Specific examples 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, acrylic acid, adipic acid, Examples include butanediol and glycerin condensates.

In addition, as an example of the polyfunctional ethylenic monomer used in the present invention, a polyisocyanate compound and a hydroxyl group-containing (meth) acrylate ester or a polyisocyanate compound and a polyol and a hydroxyl group-containing (meth) acrylate ester are reacted. Urethane (meth) acrylates as obtained; epoxy acrylates such as addition reaction product of polyvalent epoxy compound and hydroxy (meth) acrylate or (meth) acrylic acid; acrylamides such as ethylenebisacrylamide; diallyl phthalate Allyl esters such as: 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-5003, UX-5005 (manufactured by Nippon Kayaku Co., Ltd.), U-2PPA, U-6LPA, U -10PA, U-33H, UA-53H, UA-32P, UA-1100H (made by Shin-Nakamura Chemical Co., Ltd.), UA-306H, UA-510H, UF-8001G (made by Kyoeisha Chemical Co., Ltd.), UV-1700B , UV-7600B, UV-7605B, UV-7630B, UV7640B (manufactured by Nippon Synthetic Chemical).

Among these, it is preferable to use ester (meth) acrylates or urethane (meth) acrylates as the ethylenically unsaturated compound (A) from the viewpoint of an appropriate taper angle and sensitivity, and dipentaerythritol hexa (meth) acrylate. Dipentaerythritol penta (meth) acrylate, 2-tris (meth) acryloyloxymethylethylphthalic acid, pentaerythritol tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate More preferably, a basic acid anhydride adduct, a dibasic acid anhydride adduct of pentaerythritol tri (meth) acrylate, or the like is used.
These may be used alone or in combination of two or more.

In the present invention, the molecular weight of the (A) ethylenically unsaturated compound is not particularly limited, but is preferably 100 or more, more preferably 150 or more, and still more preferably 200 or more, from the viewpoint of sensitivity, liquid repellency, and taper angle. Even more preferably 300 or more, particularly preferably 400 or more, most preferably 500 or more, preferably 1000 or less, more preferably 700 or less. The number of carbon atoms of the (A) ethylenically unsaturated compound is not particularly limited, but is preferably 7 or more, more preferably 10 or more, still more preferably 15 or more, and still more from the viewpoint of sensitivity, liquid repellency, and taper angle. It is preferably 20 or more, particularly preferably 25 or more, preferably 50 or less, more preferably 40 or less, still more preferably 35 or less, and particularly preferably 30 or less.
Further, from the viewpoint of sensitivity, liquid repellency, and taper angle, ester (meth) acrylates, epoxy (meth) acrylates, and urethane (meth) acrylates are preferable. Among them, pentaerythritol tetra (meth) acrylate and pentaerythritol are preferable. Tri (meth) acrylate dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate and other trifunctional or more ester (meth) acrylates, 2,2,2-tris (meth) acryloyloxymethylethylphthal Acid, acid anhydride adducts to tri- or higher functional ester (meth) acrylates such as dibasic acid anhydride adducts of acid and dipentaerythritol penta (meth) acrylate are sensitive, liquid repellent and taper angle surfaces And more preferred.

  The content ratio of the (A) ethylenically unsaturated compound in the photosensitive resin composition of the present invention is usually 5% by mass or more, preferably 10% by mass or more, more preferably 20% by mass or more, based on the total solid content. More preferably 30% by mass or more, particularly preferably 40% by mass or more, usually 80% by mass or less, preferably 70% by mass or less, more preferably 60% by mass or less, still more preferably 55% by mass or less, particularly preferably 50% by mass. % Or less. When it is at least the lower limit, the sensitivity and taper angle during exposure tend to be good, and when it is at most the upper limit, developability tends to be good.

  Further, the content ratio of (A) the ethylenically unsaturated compound with respect to 100 parts by mass of (C) alkali-soluble resin is usually 15 parts by mass or more, preferably 30 parts by mass or more, more preferably 50 parts by mass or more, and further preferably 80 parts. It is preferably at least 90 parts by mass, particularly preferably at most 150 parts by mass, preferably at most 130 parts by mass, more preferably at most 120 parts by mass, even more preferably at most 110 parts by mass. When the amount is not more than the above upper limit value, the developability tends to be good, and when it is not less than the above lower limit value, the sensitivity is good at the time of exposure and the taper angle tends to be good.

[1-1-2] Component (B): Photopolymerization Initiator The photosensitive resin composition for forming a partition wall of the present invention contains (B) a photopolymerization initiator. The photopolymerization initiator is not particularly limited as long as it is a compound that polymerizes the ethylenically unsaturated bond of the (A) ethylenically unsaturated compound with actinic rays, and a known photopolymerization initiator is used. Can do.

  In the photosensitive resin composition of the present invention, a photopolymerization initiator that is usually used in this field can be used as the photopolymerization initiator (B). Examples of such photopolymerization initiators include hexaarylbiimidazole photopolymerization initiators, acylphosphine oxide photopolymerization initiators, oxime photopolymerization initiators, triazine photopolymerization initiators, and acetophenone photopolymerization initiators. Agent, benzophenone photopolymerization initiator, hydroxybenzene photopolymerization initiator, thioxanthone photopolymerization initiator, anthraquinone photopolymerization initiator, ketal photopolymerization initiator, titanocene photopolymerization initiator, halogenated hydrocarbon derivative Systemic photopolymerization initiator, organoborate photopolymerization initiator, onium salt photopolymerization initiator, sulfone compound photopolymerization initiator, carbamic acid derivative photopolymerization initiator, sulfonamide photopolymerization initiator, tria Examples include a reel methanol photopolymerization initiator.

  As the hexaarylbiimidazole compound, hexagonal compounds represented by the following general formula (1-1) and / or the following general formula (1-2) are used in terms of absorbance and sensitivity, and matching properties with the absorption wavelength of the ultraviolet absorber. Arylbiimidazole photoradical initiators are preferred.

In the above formulas, R ^{11 to} R ¹³ are each independently a hydrogen atom, an optionally substituted alkyl group having 1 to 4 carbon atoms, or an optionally substituted alkoxy group having 1 to 4 carbon atoms. Or a halogen atom, and m, n and l each independently represents an integer of 0 to 5.

Although it will not specifically limit if carbon number of the alkyl group of R < ¹¹ > -R < ¹³ > exists in the range of 1-4, Preferably it is 3 or less from a viewpoint of a sensitivity, More preferably, it is 2 or less. The alkyl group may be linear or cyclic. Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, and an isopropyl group. Among them, a methyl group and an ethyl group are preferable. As the substituent that the alkyl group having 1 to 4 carbon atoms of R ^{11 to} R ¹³ may have, a monovalent non-metallic atomic group other than hydrogen is used. As a preferable example, a halogen atom (— F, -Br, -Cl, -I), a hydroxyl group, and an alkoxy group.

The number of carbon atoms of the alkoxy group of R ^{11 to} R ¹³ is not particularly limited as long as it is within the range of 1 to 4, but is preferably 3 or less, more preferably 2 or less from the viewpoint of sensitivity. The alkyl group part of the alkoxy group may be a chain or a ring. Specific examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, an isopropyloxy group, and a butoxy group, and among them, a methoxy group and an ethoxy group are preferable. Examples of the substituent that the alkoxy group having 1 to 4 carbon atoms of R ^{11 to} R ¹³ may have include an alkyl group and an alkoxy group, and an alkyl group is preferable.

Examples of the halogen atom of R ^{11 to} R ¹³ include a chlorine atom, an iodine atom, a bromine atom, and a fluorine atom. Among these, from the viewpoint of ease of synthesis, a chlorine atom or a fluorine atom is preferable, and a chlorine atom is more preferable. preferable.
Among these, from the viewpoints of sensitivity and ease of synthesis, R ^{11 to} R ¹³ are preferably each independently a halogen atom, and more preferably a chlorine atom.

  m, n and l each independently represent an integer of 0 to 5, but from the viewpoint of ease of synthesis, at least one of m, n and l is preferably an integer of 1 or more, and m, n and l More preferably, one of them is 1 and the other two are 0.

  Examples of the hexaarylbiimidazole compound represented by the general formula (1-1) and / or the general formula (1-2) include 2,2′-bis (o-chlorophenyl) -4,5,4 ′, 5′-tetraphenylbiimidazole, 2,2′-bis (o-methylphenyl) -4,5,4 ′, 5′-tetraphenylbiimidazole, 2,2′-bis (o-chlorophenyl) -4, 4 ', 5,5'-tetra (o, p-dichlorophenyl) biimidazole, 2,2'-bis (o, p-dichlorophenyl) -4,4', 5,5'-tetra (o, p-dichlorophenyl) ) Biimidazole, 2,2′-bis (o-chlorophenyl) -4,4 ′, 5,5′-tetra (p-fluorophenyl) biimidazole, 2,2′-bis (o-chlorophenyl) -4, 4 ', 5,5'-te La (o, p-dibromophenyl) biimidazole, 2,2′-bis (o-bromophenyl) -4,4 ′, 5,5′-tetra (o, p-dichlorophenyl) biimidazole, 2,2 ′ -Bis (o-chlorophenyl) -4,4 ′, 5,5′-tetra (p-chloronaphthyl) biimidazole and the like. Among them, a hexaphenylbiimidazole compound is preferable, and a compound in which the o-position of the benzene ring bonded to the 2,2′-position on the imidazole ring is substituted with a methyl group, a methoxy group, or a halogen atom is more preferable. The benzene ring bonded to the 4,4 ′, 5,5′-position on the imidazole ring is preferably unsubstituted or substituted with a halogen atom or a methoxy group.

  (B) As a photopolymerization initiator, either a hexaarylbiimidazole compound represented by general formula (1-1) or a hexaarylbiimidazole compound represented by general formula (1-2) is used. It is also possible to use both in combination. When used in combination, the ratio is not particularly limited. In addition, B-1 used in the Example has a structure that satisfies the general formula (1-1).

  Examples of the acylphosphine oxide photopolymerization initiator include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide, and the like. .

  Examples of the oxime photopolymerization initiator include JP-T 2004-534797, JP-A 2000-80068, JP-A 2006-36750, JP-A 2008-179611, JP-A 2012-526185, Examples include oxime ester compounds described in Table 2012-519191. Among these, from the viewpoint of sensitivity, N-acetoxy-N- {4-acetoxyimino-4- [9-ethyl-6- (o-toluoyl) -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, 4-acetoxyimino-5 [9-Ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -5-oxopentanoic acid methyl has the product names OXE-01, OXE-02, OXE-03 (BASF Corporation). ), TR-PBG-304, TR-PBG-305 (manufactured by Changzhou Strong Company), NCI-831, NCI-930 (manufactured by ADEKA) and the like. be able to.

Examples of the acetophenone photopolymerization initiator include 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 1-hydroxycyclohexyl phenyl ketone, and 1-hydroxy-1- (p-dodecylphenyl) ketone. 1-hydroxy-1-methylethyl- (p-isopropylphenyl) ketone, 1-trichloromethyl- (p-butylphenyl) ketone, α-hydroxy-2-methylphenylpropanone, 2-methyl-1 [4- (Methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone-1-one, 2-benzyl-2-dimethylamino-1 -(4-morpholinophenyl) butan-1-one, 4-dimethylaminoethyl Benzoate, 4-dimethylaminoisoamylbenzoate, 4-diethylaminoacetophenone, 4-dimethylaminopropiophenone, 2-ethylhexyl-1,4-dimethylaminobenzoate, 2,5-bis (4-diethylaminobenzal) cyclohexanone, 7- Examples include diethylamino-3- (4-diethylaminobenzoyl) coumarin, 4- (diethylamino) chalcone and the like.
Examples of the benzophenone photopolymerization initiator include benzophenone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 2-carboxybenzophenone, 2-chlorobenzophenone, 4-bromobenzophenone, Michler's ketone, and the like.

Examples of the hydroxybenzene photopolymerization initiator include 2-hydroxy-4-n-octoxybenzophenone, 2-hydroxy-4-benzylbenzophenone, 2- (2-hydroxy-5-methylphenyl) benzotriazole, 4- Examples thereof include di-t-butylphenyl-3,5-di-t-butyl-4-hydroxybenzoate.
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. Can be mentioned.
Examples of the anthraquinone photopolymerization initiator include 2-methylanthraquinone, and examples of the ketal photopolymerization initiator include benzyldimethyl ketal.

  Examples of titanocene photopolymerization initiators include dicyclopentadienyl titanium dichloride, dicyclopentadienyl titanium bisphenyl, dicyclopentadienyl titanium bis (2,4-difluorophenyl), and dicyclopentadienyl titanium. Bis (2,6-difluorophenyl), dicyclopentadienyl titanium bis (2,4,6-trifluorophenyl), dicyclopentadienyl titanium bis (2,3,5,6-tetrafluorophenyl), Dicyclopentadienyl titanium bis (2,3,4,5,6-pentafluorophenyl), di (methylcyclopentadienyl) titanium bis (2,6-difluorophenyl), di (methylcyclopentadienyl) Titanium bis (2,3,4,5,6-pentafluoro Phenyl), dicyclopentadienyl titanium bis [2,6-difluoro-3- (1-pyrrolyl) phenyl], and the like. Of these, titanium compounds having a dicyclopentadienyl structure and a bisphenyl structure are preferable from the viewpoint of sensitivity, and those in which the o-position of the bisphenyl ring is substituted with a halogen atom are particularly preferable.

  Examples of the halogenated hydrocarbon derivative-based photopolymerization initiator include halomethylated s-triazine derivatives, such as 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- (α, α, β-trichloroethyl) -4,6-bis (trichloromethyl) -s-triazine, 2-phenyl-4,6-bis (trichloro Methyl) -s-triazine, 2- (p-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (3,4-epoxyphenyl) -4, -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 (trichloro) Methyl) -s-triazine, 2- (p-methoxy-m-hydroxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (pi-propyloxystyryl) -4,6- Bis (trichloromethyl) -s-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-methoxynaphthyl) -4 6-bis (trichloromethyl) -s-triazine, 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 Halomethylated s-triazine derivatives such as bis (trihalomethyl) -s-triazines are preferable from the viewpoint of sensitivity.

  Examples of the organic boronate photopolymerization initiator include organic boron ammonium complexes, organic boron phosphonium complexes, organic boron sulfonium complexes, organic boron oxosulfonium complexes, organic boron iodonium complexes, and organic boron transition metal coordination complexes. Examples of the organic boron anion include n-butyl-triphenyl boron anion, n-butyl-tris (2,4,6-trimethylphenyl) boron anion, and n-butyl-tris (p-methoxyphenyl). ) Boron anion, n-butyl-tris (p-fluorophenyl) boron anion, n-butyl-tris (m-fluorophenyl) boron anion, n-butyl-tris (3-fluoro-4-methylphenyl) boron anion, n-butyl-tris (2,6-difluorophenyl) boron anion, n Butyl-tris (2,4,6-trifluorophenyl) boron anion, n-butyl-tris (2,3,4,5,6-pentafluorophenyl) boron anion, n-butyl-tris (p-chlorophenyl) Alkyl-triphenyl boron anions such as boron anion and n-butyl-tris (2,6-difluoro-3-pyrrolylphenyl) boron anion are preferred from the viewpoint of sensitivity, and the counter cation includes ammonium cation and phosphonium cation. In addition, onium compounds such as sulfonium cation and iodonium cation are preferable from the viewpoint of sensitivity, and organic ammonium cations such as tetraalkylammonium are particularly preferable from the viewpoint of sensitivity.

  Examples of the onium salt photopolymerization initiator include ammonium salts such as tetramethylammonium bromide and tetraethylammonium bromide, diphenyliodonium hexafluoroarsenate, diphenyliodonium tetrafluoroborate, diphenyliodonium p-toluenesulfonate, and diphenyliodonium camphor. Iodonium salts such as sulfonate, dicyclohexyliodonium hexafluoroarsenate, dicyclohexyliodonium tetrafluoroborate, dicyclohexyliodonium p-toluenesulfonate, dicyclohexyliodonium camphorsulfonate, triphenylsulfonium hexafluoroarsenate, triphenylsulfonium tetrafluoroborate, triflate Sulfonyl sulfonium p- toluenesulfonate, triphenylsulfonium camphorsulfonate, tri-cyclohexyl hexafluoroarsenate, tri-cyclohexyl sulfonium tetrafluoroborate, tri-cyclohexyl sulfonium p- toluenesulfonate, sulfonium salts such as tri-cyclohexyl sulfonium camphorsulfonate, and the like.

  Examples of the sulfone compound photopolymerization initiator include bis (phenylsulfonyl) methane, bis (p-hydroxyphenylsulfonyl) methane, bis (p-methoxyphenylsulfonyl) methane, bis (α-naphthylsulfonyl) methane, Bis (sulfonyl) methane compounds such as bis (β-naphthylsulfonyl) methane, bis (cyclohexylsulfonyl) methane, bis (t-butylsulfonyl) methane, phenylsulfonyl (cyclohexylsulfonyl) methane, phenylcarbonyl (phenylsulfonyl) methane, naphthyl Carbonyl (phenylsulfonyl) methane, phenylcarbonyl (naphthylsulfonyl) methane, cyclohexylcarbonyl (phenylsulfonyl) methane, t-butylcarbonyl (phenylsulfonyl) methane, Carbonyl (sulfonyl) methane compounds such as phenylcarbonyl (cyclohexylsulfonyl) methane, phenylcarbonyl (t-butylcarbonyl) methane, bis (phenylsulfonyl) diazomethane, bis (p-hydroxyphenylsulfonyl) diazomethane, bis (p-methoxyphenylsulfonyl) ) Diazomethane, bis (α-naphthylsulfonyl) diazomethane, bis (β-naphthylsulfonyl) diazomethane, bis (cyclohexylsulfonyl) diazomethane, bis (t-butylsulfonyl) diazomethane, phenylsulfonyl (cyclohexylsulfonyl) diazomethane, bis (sulfonyl) diazomethane Compound, phenylcarbonyl (phenylsulfonyl) diazomethane, naphthylcarbonyl (phenylsulfonyl) diazometa Carbonyl (sulfonyl) such as phenyl, phenylcarbonyl (naphthylsulfonyl) diazomethane, cyclohexylcarbonyl (phenylsulfonyl) diazomethane, t-butylcarbonyl (phenylsulfonyl) diazomethane, phenylcarbonyl (cyclohexylsulfonyl) diazomethane, phenylcarbonyl (t-butylcarbonyl) diazomethane ) Diazomethane compounds and the like.

Examples of the carbamic acid derivative-based photopolymerization initiator include benzoyl cyclohexyl carbamate, 2-nitrobenzyl cyclohexyl carbamate, 3,5-dimethoxybenzyl cyclohexyl carbamate, and 3-nitrophenyl cyclohexyl carbamate.
Examples of the sulfonamide photopolymerization initiator include N-cyclohexyl-4-methylphenylsulfonamide, N-cyclohexyl-2-naphthylsulfonamide and the like, and examples of the triarylmethanol photopolymerization initiator include Examples thereof include triphenylmethanol and tri (4-chlorophenyl) methanol.

  One of these photopolymerization initiators may be included alone in the photosensitive resin composition, or two or more thereof may be included. Among these photopolymerization initiators, the hexaarylbiimidazole compound is particularly preferable in terms of high surface curability due to its high absorbance and high liquid repellency and high taper angle.

  As a content rate of (B) photoinitiator in the photosensitive resin composition of this invention, it is 0.01 mass% or more normally with respect to the total solid of the photosensitive resin composition, Preferably it is 0.1 mass. % Or more, more preferably 0.5% by weight or more, further preferably 1% by weight or more, particularly preferably 1.5% by weight or more, and usually 25% by weight or less, preferably 10% by weight or less, more preferably 8% by weight. It is at most 5% by mass, more preferably at most 5% by mass, particularly preferably at most 3% by mass. When the amount is not less than the lower limit, there is a tendency that a coating film is formed without developing film loss during development, and sufficient liquid repellency tends to occur, and when the amount is not more than the upper limit, a desired pattern shape is formed. It tends to be easier.

  The blending ratio of (B) photopolymerization initiator to (A) ethylenically unsaturated compound in the photosensitive resin composition is 1 part by mass or more with respect to 100 parts by mass of (A) ethylenically unsaturated compound. Is preferably 2 parts by mass or more, more preferably 3 parts by mass or more, more preferably 200 parts by mass or less, more preferably 100 parts by mass or less, further preferably 50 parts by mass or less, and more preferably 20 parts by mass or less. More preferred is 10 parts by mass or less, and most preferred is 6 parts by mass or less. There exists a tendency for it to become suitable sensitivity by setting it as the said lower limit or more, and there exists a tendency for a desired pattern shape to become easy to form by setting it as the said upper limit or less.

  Moreover, it is preferable to use a chain transfer agent in combination with the photopolymerization initiator. Examples of the chain transfer agent include mercapto group-containing compounds, carbon tetrachloride, and the like, and since a chain transfer effect tends to be high, it is more preferable to use a compound having a mercapto group. This is probably because bond cleavage is likely to occur due to the small S—H bond energy, and hydrogen pulling reaction and chain transfer reaction are likely to occur. Effective for improving sensitivity and surface curability.

  Examples of the mercapto group-containing compound include 2-mercaptobenzothiazole, 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 3-mercapto-1,2,4-triazole, 2-mercapto-4 (3H) -quinazoline, β- Mercapto group-containing compounds having an aromatic ring such as mercaptonaphthalene and 1,4-dimethylmercaptobenzene; hexanedithiol, decanedithiol, butanediol bis (3-mercaptopropionate), butanediol bisthioglycolate, ethylene glycol Bis (3-mercaptopropionate), ethylene glycol bisthioglycolate, trimethylolpropane tris (3-mercaptopropionate), trimethylolpropane tristhioglycolate, trishydroxyl Lutristhiopropionate, pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tris (3-mercaptopropionate), butanediol bis (3-mercaptobutyrate), ethylene glycol bis (3-mercaptobutyrate) Rate), trimethylolpropane tris (3-mercaptobutyrate), pentaerythritol tetrakis (3-mercaptobutyrate), pentaerythritol tris (3-mercaptobutyrate), 1,3,5-tris (3-mercaptobutyloxy) Examples thereof include aliphatic mercapto group-containing compounds such as ethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, particularly compounds having a plurality of mercapto groups.

  Of these, 2-mercaptobenzothiazole and 2-mercaptobenzimidazole are preferable among the mercapto group-containing compounds having an aromatic ring, and trimethylolpropane tris (3- Mercaptopropionate), pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tris (3-mercaptopropionate), trimethylolpropane tris (3-mercaptobutyrate), pentaerythritol tetrakis (3-mercaptobutyrate) Rate), pentaerythritol tris (3-mercaptobutyrate), 1,3,5-tris (3-mercaptobutyloxyethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -Trion is Masui.

In terms of sensitivity, an aliphatic mercapto group-containing compound is preferable, and specifically, 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-mercaptobutyloxyethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione is preferred, pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tetrakis (3 Mercaptobutylate) is more preferable.
Various types of these can be used alone or in combination of two or more.

Among these, from the viewpoint of increasing the taper angle, one or more selected from the group consisting of 2-mercaptobenzothiazole, 2-mercaptobenzimidazole, and 2-mercaptobenzoxazole, and a photopolymerization initiator are combined. It is preferred to use as a photopolymerization initiator system. For example, 2-mercaptobenzothiazole may be used, 2-mercaptobenzoimidazole may be used, and 2-mercaptobenzothiazole and 2-mercaptobenzimidazole may be used in combination.
From the viewpoint of sensitivity, it is preferable to use one or more selected from the group consisting of pentaerythritol tetrakis (3-mercaptopropionate) and pentaerythritol tetrakis (3-mercaptobutyrate). Furthermore, from the viewpoint of sensitivity, 1 or 2 or more selected from the group consisting of 2-mercaptobenzothiazole, 2-mercaptobenzoimidazole, and 2-mercaptobenzoxazole, pentaerythritol tetrakis (3-mercaptopropionate), It is preferable to use one or two or more selected from the group consisting of pentaerythritol tetrakis (3-mercaptobutyrate) and a photopolymerization initiator in combination.

  The content of the chain transfer agent in the photosensitive resin composition of the present invention is usually 0.01% by mass or more, preferably 0.025% by mass or more, based on the total solid content of the photosensitive resin composition. 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. It is. The sensitivity tends to be increased by setting it to the lower limit value or more, and the desired pattern tends to be easily formed by setting the upper limit value or less.

  Moreover, as a compounding ratio of the chain transfer agent to the (B) photopolymerization initiator in the photosensitive resin composition, 10 parts by mass or more is preferable with respect to 100 parts by mass of the (B) photopolymerization initiator, and 25 masses. Is more preferably 50 parts by mass or more, more preferably 80 parts by mass or more, particularly preferably 500 parts by mass or less, more preferably 400 parts by mass or less, further preferably 300 parts by mass or less, and 200 parts by mass. The following are particularly preferred: When the value is not less than the lower limit value, the sensitivity tends to be high. When the value is not more than the upper limit value, a desired pattern tends to be easily formed.

[1-1-3] Component (C); alkali-soluble resin The photosensitive resin composition for forming a partition wall of the present invention contains (C) an alkali-soluble resin. In the present invention, the alkali-soluble resin is not particularly limited as long as it can be developed with a developer, but an alkali developer is preferable as the developer, and therefore an alkali-soluble resin is used in the present invention. Examples of the alkali-soluble resin include various resins containing a carboxyl group or a hydroxyl group. Among them, those having a carboxyl group that is more excellent in developability are preferable. Further, because of the reason that a partition wall having an appropriate taper angle can be obtained and that the partition wall can be prevented from flowing out due to heat melting and liquid repellency can be maintained, it is more ethylenic. It is more preferable that it has an unsaturated group.

In the present invention, the (C1) epoxy (meth) acrylate resin among the alkali-soluble resins contains less outgas, has less influence on the light emitting layer, has high light emission efficiency, and has an excellent device driving life. One reason is that it has a rigid main skeleton and is difficult to decompose against heat. Moreover, (C2) By containing the acrylic copolymer resin which has an ethylenically unsaturated group in a side chain, developability is favorable, there are few residues etc. and luminous efficiency becomes high. One reason is that the main skeleton does not contain an aromatic ring or the like, so that the developer easily penetrates into the film.
The (C1) epoxy (meth) acrylate resin is described in detail below.

[(C1) Epoxy (meth) acrylate resin]
(C1) The epoxy (meth) acrylate resin is a resin obtained by adding an ethylenically unsaturated monocarboxylic acid or an ester compound to an epoxy resin and further reacting with a polybasic acid or an anhydride thereof. For example, by ring-opening addition of a carboxyl group of an unsaturated monocarboxylic acid to an epoxy group of an epoxy resin, an ethylenically unsaturated bond is added to the epoxy compound via an ester bond (—COO—). The thing which one carboxy group of the polybasic acid anhydride was added to the hydroxyl group produced in that case is mentioned. Moreover, when adding a polybasic acid anhydride, what was added by adding a polyhydric alcohol simultaneously is also mentioned.

Here, the epoxy resin includes the raw material compound before the resin is formed by thermosetting, and the epoxy resin can be appropriately selected from known epoxy resins. Moreover, the epoxy resin can use the compound obtained by making a phenolic compound and epihalohydrin react. The phenolic compound is preferably a compound having a divalent or divalent or higher phenolic hydroxyl group, and may be a monomer or a polymer.
Specifically, for example, bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, phenol novolac epoxy resin, cresol novolac epoxy resin, biphenyl novolac epoxy resin, trisphenol epoxy resin, polymerization of phenol and dicyclopentane Epoxy resin, dihydroxyoxyfluorene type epoxy resin, dihydroxyalkyleneoxyl fluorene type epoxy resin, diglycidyl etherified product of 9,9-bis (4′-hydroxyphenyl) fluorene, 1,1-bis (4′-hydroxy) Phenyl) adamantane diglycidyl ether, and the like, and those having an aromatic ring in the main chain can be suitably used.

  Among them, from the viewpoint of high cured film strength, bisphenol A epoxy resin, phenol novolac epoxy resin, cresol novolac epoxy resin, polymerized epoxy resin of phenol and dicyclopentadiene, 9,9-bis (4′-hydroxyphenyl) fluorene Diglycidyl etherified compounds are preferable, and bisphenol A epoxy resin is more preferable.

  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 adduct, penta Erythritol tri (meth) acrylate tetrahydrophthalic anhydride adduct, dipentaerythritol penta (meth) acrylate succinic anhydride adduct, dipentaerythritol penta (meth) acrylate phthalic anhydride adduct, dipentaerythritol penta (meth) acrylate tetrahydro Examples include phthalic anhydride adducts, reaction products of (meth) acrylic acid and ε-caprolactone. Among these, (meth) acrylic acid is preferable from the viewpoint of sensitivity.

  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, and anhydrides thereof. Among these, from the outgas viewpoint, succinic anhydride, maleic anhydride, tetrahydrophthalic anhydride, or hexahydrophthalic anhydride is preferable, succinic anhydride or tetrahydrophthalic anhydride is more preferable, and succinic anhydride is preferable. The product is more preferable.

By using a polyhydric alcohol, the molecular weight of the (C1) epoxy (meth) acrylate resin can be increased, branching can be introduced into the molecule, and the molecular weight and viscosity tend to be balanced. In addition, the rate of introduction of acid groups into the molecule can be increased, and there is a tendency that balance of sensitivity, adhesion, etc. is easily obtained.
Examples of the polyhydric alcohol include one or more polyhydric alcohols selected from trimethylolpropane, ditrimethylolpropane, pentaerythritol, dipentaerythritol, trimethylolethane, and 1,2,3-propanetriol. Preferably there is.

  The acid value of the (C1) epoxy (meth) acrylate resin is not particularly limited, but is preferably 10 mg-KOH / g or more, more preferably 20 mg-KOH / g or more, still more preferably 30 mg-KOH / g or more, 40 mg-KOH / G or more is more preferable, 50 mg-KOH / g or more is particularly preferable, 200 mg-KOH / g or less is preferable, 180 mg-KOH / g or less is more preferable, 150 mg-KOH / g or less is more preferable, 100 mg -KOH / g or less is still more preferable, and 80 mg-KOH / g or less is especially preferable. When the amount is not less than the lower limit value, the developability of the unexposed portion tends to be improved, and when the value is not more than the upper limit value, there is a tendency that a film that does not cause film reduction or the like can be generated.

  The weight average molecular weight (Mw) of the (C1) epoxy (meth) acrylate resin is not particularly limited, but is usually 1000 or more, preferably 2000 or more, more preferably 3000 or more, still more preferably 4000 or more, still more preferably 5000 or more, Particularly preferably, it is 6000 or more, most preferably 7000 or more, and usually 30000 or less, preferably 20000 or less, more preferably 15000 or less, and further preferably 10,000 or less. By setting it to the lower limit value or more, there is a tendency that a film that does not cause film reduction or the like can be generated, and by setting the upper limit value or less, the developability of the unexposed area tends to be improved.

  (C) The content ratio 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 40% by mass or more, and further preferably 50% by mass or more, 60 mass% or more is especially preferable, 95 mass% or less is preferable, 90 mass% or less is more preferable, and 85 mass% or less is further more preferable. When the amount is not less than the lower limit, the amount of outgassing tends to be reduced, and when the amount is not more than the upper limit, developability of unexposed areas is improved, residue is reduced, and ink jet suitability is good. Tend to be.

  (C1) The epoxy (meth) acrylate resin can be synthesized by a conventionally known method. Specifically, the epoxy resin is dissolved in an organic solvent, and in the presence of a catalyst and a thermal polymerization inhibitor, the acid or ester compound having an ethylenically unsaturated bond is added to cause addition reaction, and further a polybasic acid or its A method of continuing the reaction by adding an anhydride can be used.

  Here, 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. Examples of the catalyst include tertiary amines such as triethylamine, benzyldimethylamine, and tribenzylamine, and tertiary amines such as tetramethylammonium chloride, methyltriethylammonium chloride, tetraethylammonium chloride, tetrabutylammonium chloride, and trimethylbenzylammonium chloride. 1 type or 2 types or more, such as quaternary ammonium salts, phosphorus compounds, such as a triphenylphosphine, and stibines, such as a triphenylstibine, are mentioned. Furthermore, examples of the thermal polymerization inhibitor include one or more of hydroquinone, hydroquinone monomethyl ether, methyl hydroquinone and the like.

  The acid or ester compound having an ethylenically unsaturated bond is usually 0.7 to 1.3 chemical equivalents, preferably 0.9 to 1.1 chemical equivalents, relative to one chemical equivalent of the epoxy group of the epoxy resin. The amount can be. Moreover, as temperature at the time of addition reaction, it is 60-150 degreeC normally, Preferably it can be set as the temperature of 80-120 degreeC. Further, the polybasic acid (anhydride) is used in an amount of usually 0.1 to 1.2 chemical equivalents, preferably 0.2 to 1.1 based on 1 chemical equivalent of the hydroxyl group generated in the addition reaction. The amount can be a chemical equivalent.

  The chemical structure of the (C1) epoxy (meth) acrylate resin is not particularly limited, but contains at least one of the resins represented by the following general formulas (C1-1) to (C1-6) from the viewpoint of outgassing. It is preferable. (C1) The epoxy (meth) acrylate resin may contain one kind of resin, or may contain two or more kinds of resins.

In formula (C1-1), R ¹¹¹ represents a hydrogen atom, a halogen atom, an alkyl group or an aryl group, and n ¹¹¹ represents an integer of 0 to 20.

In formula (C1-2), R ¹²¹ represents a hydrogen atom, a halogen atom, an alkyl group or an aryl group, and n ¹²¹ represents an integer of 0 to 20.

In formula (C1-3), R ¹³¹ represents a hydrogen atom, a halogen atom, an alkyl group or an aryl group, and m ¹³¹ and n ¹³¹ each independently represents an integer of 0 to 20. In addition, ^m131 and ⁿ¹³¹ mean the number of repeating units, and do not indicate that it is a block copolymer. γ represents a single bond, —CO—, —CH ₂ —, —C (CH ₃ ) ₂ —, a group represented by the following formula (IV), or a group represented by the following formula (V). δ represents a hydrogen atom or a polybasic acid residue.

In formula (C1-4), R ¹⁴¹ represents an alkyl group or a halogen atom, and p represents an integer of 0 to 4.

In formula (C1-6), R ¹⁶¹ represents a hydrogen atom, a halogen atom, an alkyl group or an aryl group, and n ¹⁶¹ represents an integer of 0 to 20.

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

In formula (VI), R ¹⁷¹ represents a hydrogen atom or a methyl group, R ¹⁷² represents an alkylene group, and m ¹⁷¹ represents an integer of 0 to 10. Δ represents a hydrogen atom or a polybasic acid residue.

(R ¹¹¹ )
In the above formula (C1-1), R ¹¹¹ represents a hydrogen atom, a halogen atom, an alkyl group or an aryl group.
Examples of the halogen atom for R ¹¹¹ include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
In addition, examples of the alkyl group for R ¹¹¹ include linear, branched, or cyclic alkyl groups. The carbon number is usually 1 or more, preferably 10 or less, more preferably 5 or less, and still more preferably 2 or less. When the amount is not less than the lower limit, there is a tendency that the film is not reduced during development, and when the amount is not more than the upper limit, the developability of the unexposed portion tends to be improved.

  Specific examples of the alkyl group include methyl group, ethyl group, n-propyl group, 2-propyl group, n-butyl group, isobutyl group, tert-butyl group, cyclohexyl group, cyclohexylmethyl group, cyclohexylethyl group, 3- A methylbutyl group etc. are mentioned. Among these, a methyl group or an ethyl group is preferable from the viewpoint of developability.

Examples of the aryl group for R ¹¹¹ include an aromatic hydrocarbon ring group and an aromatic heterocyclic group. The number of carbon atoms is usually 4 or more, preferably 15 or less, more preferably 10 or less, and even more preferably 6 or less. When the amount is not less than the lower limit, there is a tendency that the film is not reduced during development, and when the amount is not more than the upper limit, the developability of the unexposed portion tends to be improved.

  The aromatic hydrocarbon ring in the aromatic hydrocarbon ring group may be a single ring or a condensed ring, for example, a benzene ring, naphthalene ring, anthracene ring, phenanthrene having one free valence. And groups such as a ring, a perylene ring, a tetracene ring, a pyrene ring, a benzpyrene ring, a chrysene ring, a triphenylene ring, an acenaphthene ring, a fluoranthene ring, and a fluorene ring. The aromatic heterocyclic ring in the aromatic heterocyclic group may be a monocyclic ring or a condensed ring. For example, a furan ring, a benzofuran ring, a thiophene ring, a benzoic ring having one free valence. Thiophene ring, pyrrole ring, pyrazole ring, imidazole ring, oxadiazole ring, indole ring, carbazole ring, pyrroloimidazole ring, pyrrolopyrazole ring, pyrrolopyrrole ring, thienopyrrole ring, thienothiophene ring, furopyrrole ring, furofuran ring, thienofuran ring , Benzisoxazole ring, benzoisothiazole ring, benzimidazole ring, pyridine ring, pyrazine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, isoquinoline ring, cinoline ring, quinoxaline ring, phenanthridine ring, benzimidazole ring , Perimidine ring, Nazorin ring, quinazolinone ring, groups such as azulene ring. Among these, a benzene ring is more preferable from the viewpoint of developability.

Among these, from the viewpoint of developability, R ¹¹¹ is preferably a hydrogen atom or a methyl group, and more preferably a hydrogen atom. More preferably, the two R ¹¹¹ bonded to one benzene ring are both hydrogen atoms.

(N ¹¹¹ )
In the formula (C1-1), although n ¹¹¹ represents an integer of 0 to 20, preferably 0 or more, more preferably 1 or more, more preferably 2 or more, preferably 15 or less, more preferably 10 or less 5 or less is more preferable. When the amount is not less than the lower limit, there is a tendency that the film is not reduced during development, and when the amount is not more than the upper limit, the developability of the unexposed portion tends to be improved.

( ^R121 )
In the above formula (C1-2), R ¹²¹ represents a hydrogen atom, a halogen atom, an alkyl group or an aryl group.
Examples of the halogen atom for R ¹²¹ include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
In addition, examples of the alkyl group for R ¹²¹ include a linear, branched, or cyclic alkyl group. The carbon number is usually 1 or more, preferably 10 or less, more preferably 5 or less, and still more preferably 2 or less. When the amount is not less than the lower limit, there is a tendency that the film is not reduced during development, and when the amount is not more than the upper limit, the developability of the unexposed portion tends to be improved.

  Specific examples of the alkyl group include methyl group, ethyl group, n-propyl group, 2-propyl group, n-butyl group, isobutyl group, tert-butyl group, cyclohexyl group, cyclohexylmethyl group, cyclohexylethyl group, 3- A methylbutyl group etc. are mentioned. Among these, a methyl group and an ethyl group are preferable from the viewpoint of developability.

Examples of the aryl group for R ¹²¹ include an aromatic hydrocarbon ring group and an aromatic heterocyclic group. The number of carbon atoms is usually 4 or more, preferably 6 or more, preferably 15 or less, more preferably 10 or less, and still more preferably 6 or less. When the amount is not less than the lower limit, there is a tendency that the film is not reduced during development, and when the amount is not more than the upper limit, the developability of the unexposed portion tends to be improved.

  The aromatic hydrocarbon ring in the aromatic hydrocarbon ring group may be a single ring or a condensed ring, for example, a benzene ring, naphthalene ring, anthracene ring, phenanthrene having one free valence. And groups such as a ring, a perylene ring, a tetracene ring, a pyrene ring, a benzpyrene ring, a chrysene ring, a triphenylene ring, an acenaphthene ring, a fluoranthene ring, and a fluorene ring. The aromatic heterocyclic ring in the aromatic heterocyclic group may be a monocyclic ring or a condensed ring. For example, a furan ring, a benzofuran ring, a thiophene ring, a benzoic ring having one free valence. Thiophene ring, pyrrole ring, pyrazole ring, imidazole ring, oxadiazole ring, indole ring, carbazole ring, pyrroloimidazole ring, pyrrolopyrazole ring, pyrrolopyrrole ring, thienopyrrole ring, thienothiophene ring, furopyrrole ring, furofuran ring, thienofuran ring , Benzisoxazole ring, benzoisothiazole ring, benzimidazole ring, pyridine ring, pyrazine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, isoquinoline ring, cinoline ring, quinoxaline ring, phenanthridine ring, benzimidazole ring , Perimidine ring, Nazorin ring, quinazolinone ring, groups such as azulene ring. Among these, a benzene ring is preferable from the viewpoint of developability.

Among these, from the viewpoint of developability, R ¹²¹ is preferably a hydrogen atom or a methyl group, and more preferably a hydrogen atom. More preferably, the two R ¹²¹ bonded to one benzene ring are both hydrogen atoms.

(N ¹²¹ )
In the formula (C1-2), n ¹²¹ represents an integer of 0 to 20, preferably 2 or more, more preferably 3 or more, further preferably 5 or more, and preferably 16 or less, more preferably 14 or less. 12 or less is more preferable. When the amount is not less than the lower limit value, there is a tendency that the film is not reduced during development. When the value is not more than the upper limit value, the developability of the unexposed portion tends to be improved.

(R ¹³¹ )
In the above formula (C1-3), R ¹³¹ represents a hydrogen atom, a halogen atom, an alkyl group or an aryl group.
Examples of the halogen atom for R ¹³¹ include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
In addition, examples of the alkyl group for R ¹³¹ include a linear, branched, or cyclic alkyl group. The number of carbon atoms is usually 1 or more, preferably 15 or less, more preferably 10 or less, and still more preferably 6 or less. When the amount is not less than the lower limit value, there is a tendency that the film is not reduced during development. When the value is not more than the upper limit value, the developability of the unexposed portion tends to be improved.

  Specific examples of the alkyl group include methyl group, ethyl group, n-propyl group, 2-propyl group, n-butyl group, isobutyl group, tert-butyl group, cyclohexyl group, cyclohexylmethyl group, cyclohexylethyl group, 3- A methylbutyl group etc. are mentioned. Among these, a methyl group and an ethyl group are preferable from the viewpoint of developability.

Examples of the aryl group for R ¹³¹ include an aromatic hydrocarbon ring group and an aromatic heterocyclic group. The number of carbon atoms is usually 4 or more, preferably 6 or more, preferably 15 or less, more preferably 10 or less, and even more preferably 6 or less. When the amount is not less than the lower limit, there is a tendency that the film is not reduced during development, and when the amount is not more than the upper limit, the developability of the unexposed portion tends to be improved.

  The aromatic hydrocarbon ring in the aromatic hydrocarbon ring group may be a single ring or a condensed ring, for example, a benzene ring, naphthalene ring, anthracene ring, phenanthrene having one free valence. And groups such as a ring, a perylene ring, a tetracene ring, a pyrene ring, a benzpyrene ring, a chrysene ring, a triphenylene ring, an acenaphthene ring, a fluoranthene ring, and a fluorene ring. The aromatic heterocyclic ring in the aromatic heterocyclic group may be a monocyclic ring or a condensed ring. For example, a furan ring, a benzofuran ring, a thiophene ring, a benzoic ring having one free valence. Thiophene ring, pyrrole ring, pyrazole ring, imidazole ring, oxadiazole ring, indole ring, carbazole ring, pyrroloimidazole ring, pyrrolopyrazole ring, pyrrolopyrrole ring, thienopyrrole ring, thienothiophene ring, furopyrrole ring, furofuran ring, thienofuran ring , Benzisoxazole ring, benzoisothiazole ring, benzimidazole ring, pyridine ring, pyrazine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, isoquinoline ring, cinoline ring, quinoxaline ring, phenanthridine ring, benzimidazole ring , Perimidine ring, Nazorin ring, quinazolinone ring, groups such as azulene ring. Among these, a benzene ring is more preferable from the viewpoint of developability.

Among these, from the viewpoint of developability, R ¹³¹ is preferably a hydrogen atom or a methyl group, and more preferably a hydrogen atom. Further, it is more preferable that two R ¹³¹ bonded to one benzene ring are both hydrogen atoms.

(M ¹³¹ )
In the formula (C1-3), m ¹³¹ represents an integer of 0 to 20, preferably 2 or more, more preferably 5 or more, still more preferably 10 or more, and preferably 18 or less, more preferably 16 or less. 14 or less is more preferable. When the amount is not less than the lower limit, there is a tendency that the film is not reduced during development, and when the amount is not more than the upper limit, the developability of the unexposed portion tends to be improved.

(N ¹³¹ )
In the formula (C1-3), n ¹³¹ represents an integer of 0 to 20, preferably 1 or more, more preferably 2 or more, further preferably 3 or more, and preferably 18 or less, more preferably 16 or less. 14 or less is more preferable. When the amount is not less than the lower limit, the developability of the unexposed area tends to be improved, and when the amount is not more than the upper limit, there is a tendency that no film reduction occurs during development.

(Γ)
In the formula (C1-3), γ is a single bond, —CO—, —CH ₂ —, —C (CH ₃ ) ₂ —, a group represented by the formula (IV), or a group represented by the formula (V). Represents. Among these, —C (CH ₃ ) ₂ — is preferable from the viewpoint of developability and outgas.

(R ¹⁴¹ )
In the formula (C1-4), R ¹⁴¹ represents an alkyl group or a halogen atom.
^Examples of the alkyl group for R ¹⁴¹ include a linear, branched or cyclic alkyl group. The carbon number is usually 1 or more, preferably 10 or less, more preferably 5 or less, and still more preferably 2 or less. When the amount is not less than the lower limit, there is a tendency that the film is not reduced during development, and when the amount is not more than the upper limit, the developability of the unexposed portion tends to be improved.

  Specific examples of the alkyl group include methyl group, ethyl group, n-propyl group, 2-propyl group, n-butyl group, isobutyl group, tert-butyl group, cyclohexyl group, cyclohexylmethyl group, cyclohexylethyl group, 3- A methylbutyl group etc. are mentioned. Among these, a methyl group and an ethyl group are preferable from the viewpoint of developability.

Examples of the halogen atom for R ¹⁴¹ include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

Among these, from the viewpoint of developability, R ¹⁴¹ is preferably a hydrogen atom or a methyl group, and more preferably a methyl group.

(P)
In said formula (C1-4), p represents the integer of 0-4 each independently. From the viewpoint of developability, 0 or more is preferable, and 2 or less is preferable. When the amount is not less than the lower limit, there is a tendency that the film is not reduced during development, and when the amount is not more than the upper limit, the developability of the unexposed portion tends to be improved.

(R ¹⁶¹ )
In the above formula (C1-6), R ¹⁶¹ represents a hydrogen atom, a halogen atom, an alkyl group or an aryl group.
Examples of the halogen atom for R ¹⁶¹ include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
In addition, examples of the alkyl group for R ¹⁶¹ include a linear, branched, or cyclic alkyl group. The carbon number is usually 1 or more, preferably 10 or less, more preferably 5 or less, and still more preferably 2 or less. When the amount is not less than the lower limit, there is a tendency that the film is not reduced during development, and when the amount is not more than the upper limit, the developability of the unexposed portion tends to be improved.

  Specific examples of the alkyl group include methyl group, ethyl group, n-propyl group, 2-propyl group, n-butyl group, isobutyl group, tert-butyl group, cyclohexyl group, cyclohexylmethyl group, cyclohexylethyl group, 3- A methylbutyl group etc. are mentioned. Among these, a methyl group is preferable from the viewpoint of developability.

Examples of the aryl group for R ¹⁶¹ include an aromatic hydrocarbon ring group and an aromatic heterocyclic group. The number of carbon atoms is usually 4 or more, preferably 6 or more, preferably 15 or less, more preferably 10 or less, and even more preferably 6 or less. When the amount is not less than the lower limit, there is a tendency that the film is not reduced during development, and when the amount is not more than the upper limit, the developability of the unexposed portion tends to be improved.

  The aromatic hydrocarbon ring in the aromatic hydrocarbon ring group may be a single ring or a condensed ring, for example, a benzene ring, naphthalene ring, anthracene ring, phenanthrene having one free valence. And groups such as a ring, a perylene ring, a tetracene ring, a pyrene ring, a benzpyrene ring, a chrysene ring, a triphenylene ring, an acenaphthene ring, a fluoranthene ring, and a fluorene ring. The aromatic heterocyclic ring in the aromatic heterocyclic group may be a monocyclic ring or a condensed ring. For example, a furan ring, a benzofuran ring, a thiophene ring, a benzoic ring having one free valence. Thiophene ring, pyrrole ring, pyrazole ring, imidazole ring, oxadiazole ring, indole ring, carbazole ring, pyrroloimidazole ring, pyrrolopyrazole ring, pyrrolopyrrole ring, thienopyrrole ring, thienothiophene ring, furopyrrole ring, furofuran ring, thienofuran ring , Benzisoxazole ring, benzoisothiazole ring, benzimidazole ring, pyridine ring, pyrazine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, isoquinoline ring, cinoline ring, quinoxaline ring, phenanthridine ring, benzimidazole ring , Perimidine ring, Nazorin ring, quinazolinone ring, groups such as azulene ring. Among these, a benzene ring is preferable from the viewpoint of developability.

Among these, from the viewpoint of developability, R ¹⁶¹ is preferably a hydrogen atom or a methyl group, and more preferably a methyl group.

(N ¹⁶¹ )
In the formula (C1-6), n ¹⁶¹ represents an integer of 0 to 20, preferably 1 or more, more preferably 2 or more, and preferably 15 or less, more preferably 10 or less. When the amount is not less than the lower limit, there is a tendency that the film is not reduced during development, and when the amount is not more than the upper limit, the developability of the unexposed portion tends to be improved.

( ^R172 )
In the formula (V), R ¹⁷² represents an alkylene group.
^Examples of the alkylene group for R ¹⁷² include a linear, branched or cyclic alkylene group. The number of carbon atoms is usually 1 or more, preferably 2 or more, preferably 4 or less, more preferably 3 or less, and still more preferably 2 or less. When the amount is not less than the lower limit, there is a tendency that the film is not reduced during development, and when the amount is not more than the upper limit, the developability of the unexposed portion tends to be improved.

  Specific examples of the alkylene group include methylene group, ethylene group, propylene group, isopropylene group, butylene group and the like. Among these, an ethylene group and a propylene group are preferable from the viewpoint of developability.

(M ¹⁷¹ )
In the formula (V), m ¹⁷¹ represents an integer of 0 to 10, preferably 1 or more, and more preferably 5 or less. When the amount is not less than the lower limit, the developability of the unexposed area tends to be improved, and when the amount is not more than the upper limit, there is a tendency that no film reduction occurs during development.

(Δ)
In the formulas (C1-3) and (V), δ represents a hydrogen atom or a polybasic acid residue.
The polybasic acid residue represents a monovalent group obtained by removing one OH group from a polybasic acid.
Examples of the polybasic acid in the polybasic acid residue 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 the like, from the viewpoint of developability, reliability, outgas, succinic anhydride, maleic anhydride, tetrahydrophthalic anhydride, or hexahydrophthalic anhydride Preferably, succinic anhydride or tetrahydrophthal More preferably anhydride, succinic anhydride is more preferable.

  Among the resins represented by the general formulas (C1-1) to (C1-6), the epoxy represented by the general formula (C1-2) or (C1-3) from the viewpoint of outgas amount and inkjet coating property. A (meth) acrylate resin is preferable, and an epoxy (meth) acrylate resin represented by the general formula (C1-3) is more preferable.

[(C2) Acrylic copolymer resin having an ethylenically unsaturated group in the side chain]
Next, the (C2) acrylic copolymer resin having an ethylenically unsaturated group in the side chain will be described in detail.
(C2) The acrylic copolymer resin has an ethylenically unsaturated group in the side chain. By having an ethylenically unsaturated group, photocuring occurs due to exposure, resulting in a stronger film, less film loss during development, and the effect of reducing the amount of outgas that is not easily thermally decomposed during post-baking. It is thought that it is obtained.

(Partial structure represented by general formula (I))
(C2) The partial structure containing a side chain having an ethylenically unsaturated group, contained in the acrylic copolymer resin, is not particularly limited. It is preferable to include.

In the formula (I), R ¹ represents a hydrogen atom or a methyl group. R ² represents an alkenyl group which may have a substituent or a group represented by the following general formula (II). R ³ represents a hydrogen atom or a group represented by the following general formula (III).

In formula (II), R ⁴ represents an alkenyl group which may have a substituent. α represents an alkylene group which may have a substituent, an arylene group which may have a substituent, or an alkenylene group which may have a substituent. * Represents a bond to the carbonyl carbon.

式（ＩＩＩ）中、βはジカルボン酸の残基である。

In formula (III), β is a residue of a dicarboxylic acid.

(R ² )
In the formula (I), R ² represents an alkenyl group which may have a substituent or a group represented by the general formula (II).

Examples of the alkenyl group for R ² include linear, branched or cyclic alkenyl groups. The carbon number is preferably 2 or more, preferably 20 or less, more preferably 16 or less, further preferably 12 or less, and still more preferably 8 or less, It is particularly preferably 6 or less, and most preferably 4 or less. When the amount is not less than the lower limit, there is a tendency that the film is not reduced during development. When the amount is not more than the upper limit, the developability of the unexposed portion tends to be improved.

  Specific examples of the alkenyl group include ethenyl group, propenyl group, butyryl group, cyclohexenyl group and the like. Among these, from the viewpoint of developability and curability, an ethenyl group or a propenyl group is preferable, and an ethenyl group is more preferable.

  Examples of the substituent that the alkenyl group may have include an alkyl group, an alkenyl group, an alkynyl group, a hydroxyl group, a carboxyl group, a chloro group, a bromo group, a fluoro group, an alkoxy group, a hydroxyalkyl group, a thiol group, Examples thereof include a sulfide group. Among these, from the viewpoint of developability, an alkyl group or an alkenyl group is preferable, and an alkyl group is more preferable. When it has two or more substituents, the substituents may be linked to form a ring.

Among these, R ² is preferably an ethenyl group or a propenyl group, and more preferably an ethenyl group, from the viewpoints of developability and curability.

(R ⁴ )
In the formula (II), R ⁴ represents an alkenyl group which may have a substituent.

Examples of the alkenyl group for R ⁴ include linear, branched or cyclic alkenyl groups. The carbon number is preferably 2 or more, preferably 20 or less, more preferably 16 or less, further preferably 12 or less, and still more preferably 8 or less, It is particularly preferably 6 or less, and most preferably 4 or less. When the amount is not less than the lower limit, there is a tendency that the film is not reduced during development. When the amount is not more than the upper limit, if the developability of the unexposed portion is improved, the curability tends to be improved.

  Specific examples of the alkenyl group include ethenyl group, propenyl group, butyryl group, cyclohexenyl group and the like. Among these, from the viewpoint of developability and curability, an ethenyl group or a propenyl group is preferable, and an ethenyl group is more preferable.

  Examples of the substituent that the alkenyl group may have include an alkyl group, an alkenyl group, an alkynyl group, a hydroxyl group, a carboxyl group, a chloro group, a bromo group, a fluoro group, an alkoxy group, a hydroxyalkyl group, a thiol group, Examples thereof include a sulfide group. Among these, from the viewpoint of developability, an alkyl group or an alkenyl group is preferable, and an alkyl group is more preferable. When it has two or more substituents, the substituents may be linked to form a ring.

As described above, R ⁴ represents an alkenyl group which may have a substituent. Among these, from the viewpoint of developability, R ⁴ is preferably an ethenyl group or a propenyl group, and more preferably an ethenyl group. .

(Α)
In the formula (II), α represents an alkylene group which may have a substituent, an arylene group which may have a substituent, or an alkenylene group which may have a substituent.
Examples of the alkylene group for 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 preferably 22 or less, more preferably 20 or less, and even more preferably 18 or less, It is more 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, there is a tendency that the film is not reduced during development, and when the amount is not more than the upper limit, the developability of the unexposed portion tends to be improved.

  Specific examples of the alkylene group include a methylene group, an ethylene group, a propylene group, a cyclohexylene group, a methylcyclohexylene group, a bicyclo [2.2.1] heptane group, and a methylbicyclo [2.2.1] heptane group. Can be mentioned. Among these, from the viewpoint of developability, an ethylene group, a cyclohexylene group or a methylcyclohexylene group is preferable, and an ethylene group is more preferable.

  Examples of the substituent that the alkylene group may have include an alkenyl group, an alkynyl group, a hydroxyl group, a carboxyl group, a chloro group, a bromo group, a fluoro group, an alkoxy group, a hydroxyalkyl group, a thiol group, and a sulfide group. Is mentioned. Among these, alkenyl is preferable from the viewpoint of the remaining film ratio. Moreover, when it has two or more substituents, substituents may connect and may form the ring.

Examples of the arylene group for α include a divalent aromatic hydrocarbon ring group and a divalent aromatic heterocyclic group. The number of carbon atoms is preferably 6 or more, preferably 24 or less, more preferably 22 or less, further preferably 20 or less, and still more preferably 18 or less, It is particularly preferably 16 or less, and most preferably 14 or less. When the amount is not less than the lower limit, there is a tendency that the film is not reduced during development, and when the amount is not more than the upper limit, the developability of the unexposed portion tends to be improved.
The aromatic hydrocarbon ring in the aromatic hydrocarbon ring group may be a single ring or a condensed ring, such as a benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, tetracene ring, pyrene. And groups such as a ring, a benzpyrene ring, a chrysene ring, a triphenylene ring, an acenaphthene ring, a fluoranthene ring, and a fluorene ring.
In addition, the aromatic heterocyclic group in the aromatic heterocyclic group may be a single ring or a condensed ring, such as a furan ring, a benzofuran ring, a thiophene ring, a benzothiophene ring, a pyrrole ring, or a pyrazole ring. , Imidazole ring, oxadiazole ring, indole ring, carbazole ring, pyrroloimidazole ring, pyrrolopyrazole ring, pyrrolopyrrole ring, thienopyrrole ring, thienothiophene ring, furopyrrole ring, furofuran ring, thienofuran ring, benzoisoxazole ring, benzoiso Thiazole ring, benzimidazole ring, pyridine ring, pyrazine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, isoquinoline ring, sinoline ring, quinoxaline ring, phenanthridine ring, benzimidazole ring, perimidine ring, quinazoline ring, quinazolino Rings include groups such as azulene ring. Among these, from the viewpoint of developability, a benzene ring group or a naphthalene ring group is preferable, and a benzene ring group is more preferable.

  Examples of the substituent that the arylene group may have include an alkyl group, an alkenyl group, an alkynyl group, a hydroxyl group, a carboxyl group, a chloro group, a bromo group, a fluoro group, an alkoxy group, a hydroxyalkyl group, a thiol group, Examples thereof include a sulfide group. Among these, from the viewpoint of developability, a hydroxyl group or a carboxyl group is preferable, and a carboxyl group is more preferable. Moreover, when it has two or more substituents, substituents may connect and may form the ring.

  Specific examples of the arylene group having a substituent include a carboxylbenzene ring group.

  Moreover, as an alkenylene group in (alpha), a linear, branched or cyclic alkenylene group is mentioned. The number of carbon atoms is preferably 2 or more, preferably 22 or less, more preferably 20 or less, further preferably 18 or less, and still more preferably 16 or less, It is particularly preferably 14 or less, and most preferably 12 or less. When the amount is not less than the lower limit, there is a tendency that the film is not reduced during development, and when the amount is not more than the upper limit, the developability of the unexposed portion tends to be improved.

  Specific examples of the alkenylene group include an ethenylene group, a propenylene group, a cyclohexenylene group, and a methylethenylene group. Among these, from the viewpoint of developability, an ethenylene group and a cyclohexenylene group are preferable, and an ethenylene group is more preferable.

  Examples of the substituent that the alkenylene group may have include an alkyl group, an alkenyl group, an alkynyl group, a hydroxyl group, a carboxyl group, a chloro group, a bromo group, a fluoro group, an alkoxy group, a hydroxyalkyl group, a thiol group, Examples thereof include a sulfide group. Among these, from the viewpoint of the remaining film ratio, an alkyl group or an alkenyl group is preferable, and an alkyl group is more preferable. Moreover, when it has two or more substituents, substituents may connect and may form the ring.

  As described above, α represents an alkylene group which may have a substituent, an arylene group which may have a substituent, or an alkenylene group which may have a substituent. From the viewpoint of properties, an alkylene group or an alkenylene group is preferable, and an alkylene group is more preferable.

(R ³ )
The formula (I) represents a hydrogen atom or a group represented by the following general formula (III).

In the formula (III), β is a dicarboxylic acid residue.
R ³ is preferably a group represented by the general formula (III) from the viewpoint of alkali developability.

(Β)
In the formula (III), β is a dicarboxylic acid residue. The dicarboxylic acid residue means a divalent group obtained by removing two COOH groups from a divalent carboxylic acid.
Examples of the residue of the dicarboxylic acid include an alkylene group which may have a substituent, an arylene group which may have a substituent, or an alkenylene group which may have a substituent.
Examples of the alkylene group for β include a linear, branched or cyclic alkylene group. The number of carbon atoms is preferably 1 or more, more preferably 2 or more, preferably 20 or less, more preferably 18 or less, and further preferably 16 or less, It is more preferably 14 or less, particularly preferably 12 or less, and most preferably 10 or less. When the amount is not less than the lower limit, there is a tendency that the film is not reduced during development, and when the amount is not more than the upper limit, the developability of the unexposed portion tends to be improved.

  Specific examples of the alkylene group include a methylene group, an ethylene group, a propylene group, a cyclohexylene group, a methylcyclohexylene group, a bicyclo [2.2.1] heptylene group, and a methylbicyclo [2.2.1] heptylene group. Can be mentioned. Among these, from the viewpoint of developability, reliability, and outgas, an ethylene group, a cyclohexylene group, or a methylcyclohexylene group is preferable, and an ethylene group is more preferable.

  Examples of the substituent that the alkylene group may have include an alkenyl group, an alkynyl group, a hydroxyl group, a carboxyl group, a chloro group, a bromo group, a fluoro group, an alkoxy group, a hydroxyalkyl group, a thiol group, and a sulfide group. Is mentioned. Among these, an alkenyl group is preferable from the viewpoint of the remaining film ratio. Moreover, when it has two or more substituents, substituents may connect and may form the ring.

  Specific examples of the alkylene group having a substituent include a methylene ethylene group, an octenyl ethylene group, and a dodecenyl ethylene group.

Examples of the arylene group in β include a divalent aromatic hydrocarbon ring group and a divalent aromatic heterocyclic group. The number of carbon atoms is preferably 6 or more, preferably 24 or less, more preferably 20 or less, further preferably 18 or less, and still more preferably 16 or less, It is particularly preferably 14 or less, and most preferably 12 or less. When the amount is not less than the lower limit, there is a tendency that the film is not reduced during development, and when the amount is not more than the upper limit, the developability of the unexposed portion tends to be improved.
The aromatic hydrocarbon ring in the aromatic hydrocarbon ring group may be a single ring or a condensed ring, such as a benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, tetracene ring, pyrene. And groups such as a ring, a benzpyrene ring, a chrysene ring, a triphenylene ring, an acenaphthene ring, a fluoranthene ring, and a fluorene ring.
In addition, the aromatic heterocyclic group in the aromatic heterocyclic group may be a single ring or a condensed ring, such as a furan ring, a benzofuran ring, a thiophene ring, a benzothiophene ring, a pyrrole ring, or a pyrazole ring. , Imidazole ring, oxadiazole ring, indole ring, carbazole ring, pyrroloimidazole ring, pyrrolopyrazole ring, pyrrolopyrrole ring, thienopyrrole ring, thienothiophene ring, furopyrrole ring, furofuran ring, thienofuran ring, benzoisoxazole ring, benzoiso Thiazole ring, benzimidazole ring, pyridine ring, pyrazine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, isoquinoline ring, sinoline ring, quinoxaline ring, phenanthridine ring, benzimidazole ring, perimidine ring, quinazoline ring, quinazolino Rings include groups such as azulene ring. Among these, from the viewpoint of developability, a benzene ring group or a naphthalene ring group is preferable, and a benzene ring group is more preferable.

  Examples of the substituent that the arylene group may have include an alkyl group, an alkenyl group, an alkynyl group, a hydroxyl group, a carboxyl group, a chloro group, a bromo group, a fluoro group, an alkoxy group, a hydroxyalkyl group, a thiol group, Examples thereof include a sulfide group. Among these, from the viewpoint of developability, a hydroxyl group or a carboxyl group is preferable, and a carboxyl group is more preferable. Moreover, when it has two or more substituents, substituents may connect and may form the ring.

  Specific examples of the arylene group having a substituent include a carboxylbenzene ring group.

  Examples of the alkenylene group in β include a linear, branched or cyclic alkenylene group. The number of carbon atoms is preferably 2 or more, preferably 20 or less, more preferably 16 or less, further preferably 10 or less, and still more 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, there is a tendency that the film is not reduced during development, and when the amount is not more than the upper limit, the developability of the unexposed portion tends to be improved.

  Specific examples of the alkenylene group include an ethenylene group, a propenylene group, a cyclohexenylene group, and a methylethenylene group. Among these, from the viewpoint of developability, an ethenylene group or a cyclohexenylene group is preferable, and a cyclohexenylene group is more preferable.

  Examples of the substituent that the alkenylene group may have include an alkyl group, an alkenyl group, an alkynyl group, a hydroxyl group, a carboxyl group, a chloro group, a bromo group, a fluoro group, an alkoxy group, a hydroxyalkyl group, a thiol group, Examples thereof include a sulfide group. Among these, from the viewpoint of the remaining film ratio, an alkyl group or an alkenyl group is preferable, and an alkyl group is more preferable. Moreover, when it has two or more substituents, substituents may connect and may form the ring.

  Thus, β includes an alkylene group which may have a substituent, an arylene group which may have a substituent, or an alkenylene group which may have a substituent. Among these, from the viewpoint of developability, an alkylene group or an alkenylene group is preferable, and an alkylene group is more preferable.

  (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 20 mol% or more, and more preferably 30 mol% or more. More preferably, 50 mol% or more is particularly preferable, 99 mol% or less is preferable, 97 mol% or less is more preferable, and 95 mol% or less is more preferable. When the amount is not less than the lower limit value, the sensitivity tends to be high, and when the amount is not more than the upper limit value, there is a tendency that moderate dissolution developability is obtained.

(Partial structure represented by the general formula (I ′))
(C2) When the acrylic copolymer resin includes a partial structure represented by the general formula (I), the other partial structures included are not particularly limited. From the viewpoint of heat resistance and film strength, for example, the following general formula ( The partial structure represented by I ′) is preferably included.

In the above formula (I ′), R ⁵ represents a hydrogen atom or a methyl group, and R ⁶ represents an alkyl group which may have a substituent, an aryl group which may have a substituent, or a substituent. An alkenyl group that may be present.

(R ⁶ )
In the formula (I ′), R ⁶ represents an alkyl group which may have a substituent, an aryl group which may have a substituent, or an alkenyl group which may have a substituent.
Examples of the alkyl group for R ⁶ include linear, branched or cyclic alkyl groups. The number of carbon atoms is preferably 1 or more, more preferably 3 or more, still more preferably 5 or more, and is preferably 20 or less, more preferably 18 or less, It is more preferably 16 or less, still more preferably 14 or less, and particularly preferably 12 or less. When the amount is not less than the lower limit, there is a tendency that the film is not reduced during development, and when the amount is not more than the upper limit, the developability of the unexposed portion tends to be improved.

Specific examples of the alkyl group include a methyl group, an ethyl group, a cyclohexyl group, a dicyclopentanyl group, and a dodecanyl group. Among these, from the viewpoint of developability, a dicyclopentanyl group or a dodecanyl group is preferable, and a dicyclopentanyl group is more preferable.
The substituents that the alkyl group may have include methoxy group, ethoxy group, chloro group, bromo group, fluoro group, hydroxy group, amino group, epoxy group, oligoethylene glycol group, phenyl group, carboxyl group , An acryloyl group, a methacryloyl group, and the like. From the viewpoint of developability, a hydroxy group and an oligoethylene glycol group are preferable.

Examples of the aryl group for R ⁶ include a monovalent aromatic hydrocarbon ring group and a monovalent aromatic heterocyclic group. The number of carbon atoms is preferably 6 or more, preferably 24 or less, more preferably 22 or less, still more preferably 20 or less, and particularly preferably 18 or less. When the amount is not less than the lower limit, there is a tendency that the film is not reduced during development, and when the amount is not more than the upper limit, the developability of the unexposed portion tends to be improved.
The aromatic hydrocarbon ring in the aromatic hydrocarbon ring group may be a single ring or a condensed ring, such as a benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, tetracene ring, pyrene. And groups such as a ring, a benzpyrene ring, a chrysene ring, a triphenylene ring, an acenaphthene ring, a fluoranthene ring, and a fluorene ring.
In addition, the aromatic heterocyclic group in the aromatic heterocyclic group may be a single ring or a condensed ring, such as a furan ring, a benzofuran ring, a thiophene ring, a benzothiophene ring, a pyrrole ring, or a pyrazole ring. , Imidazole ring, oxadiazole ring, indole ring, carbazole ring, pyrroloimidazole ring, pyrrolopyrazole ring, pyrrolopyrrole ring, thienopyrrole ring, thienothiophene ring, furopyrrole ring, furofuran ring, thienofuran ring, benzoisoxazole ring, benzoiso Thiazole ring, benzimidazole ring, pyridine ring, pyrazine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, isoquinoline ring, sinoline ring, quinoxaline ring, phenanthridine ring, benzimidazole ring, perimidine ring, quinazoline ring, quinazolino Rings include groups such as azulene ring. Among these, from the viewpoint of developability, a benzene ring group or a naphthalene ring group is preferable, and a benzene ring group is more preferable.
The substituents that the aryl group may have include methyl group, ethyl group, propyl group, methoxy group, ethoxy group, chloro group, bromo group, fluoro group, hydroxy group, amino group, epoxy group, oligo group, Examples thereof include an ethylene glycol group, a phenyl group, and a carboxyl group, and a hydroxy group and an oligoethylene glycol group are preferable from the viewpoint of developability.

Examples of the alkenyl group for R ⁶ include linear, branched or cyclic alkenyl groups. The number of carbon atoms is preferably 2 or more, preferably 22 or less, more preferably 20 or less, further preferably 18 or less, and still more preferably 16 or less. 14 or less is particularly preferable. When the amount is not less than the lower limit, there is a tendency that the film is not reduced during development, and when the amount is not more than the upper limit, the developability of the unexposed portion tends to be improved.

  Examples of the substituent that the alkenyl group may have include methyl group, ethyl group, propyl group, methoxy group, ethoxy group, chloro group, bromo group, fluoro group, hydroxy group, amino group, epoxy group, oligo group Examples thereof include an ethylene glycol group, a phenyl group, and a carboxyl group, and a hydroxy group and an oligoethylene glycol group are preferable from the viewpoint of developability.

Thus, R ⁶ represents an alkyl group which may have a substituent, an aryl group which may have a substituent, or an alkenyl group which may have a substituent. From the viewpoint of developability, an alkyl group or alkenyl is preferable, and an alkyl group is more preferable.

  (C2) The content of the partial structure represented by the general formula (I ′) contained in the acrylic copolymer resin is not particularly limited, but is preferably 1 mol% or more, more preferably 2 mol% or more, and 3 mol% or more. Is more preferably 95 mol% or less, more preferably 80 mol% or less, still more preferably 70% mol or less, and particularly preferably 50 mol% or less. When it is at least the lower limit, heat resistance and film strength tend to be good, and when it is at most the upper limit, there is a tendency for moderate developability.

(Partial structure represented by general formula (I ''))
(C2) In the case where the acrylic copolymer resin includes a partial structure represented by the general formula (I), the partial structure included therein is represented by the following general formula (I ″) from the viewpoint of heat resistance and film strength A partial structure is preferably included.

In the above formula (I ″), R ⁷ represents a hydrogen atom or a methyl group, R ⁸ represents an alkyl group which may have a substituent, an alkenyl group which may have a substituent, or a substituent. The alkynyl group which may have, the hydroxyl group, the carboxyl group, the halogen atom, the alkoxy group which may have a substituent, the thiol group, or the alkyl sulfide group which may have a substituent is represented. t represents an integer of 0 to 5.

(R ⁸⁾
In the formula (I ″), R ⁸ represents an alkyl group which may have a substituent, an alkenyl group which may have a substituent, an alkynyl group which may have a substituent, a hydroxyl group, A carboxyl group, a halogen atom, an optionally substituted alkoxy group, a thiol group, or an optionally substituted alkyl sulfide group is represented.
Examples of the alkyl group for R ⁸ include a linear, branched, or cyclic alkyl group. The number of carbon atoms is preferably 1 or more, more preferably 3 or more, still more preferably 5 or more, and is preferably 20 or less, more preferably 18 or less, It is more preferably 16 or less, still more preferably 14 or less, and particularly preferably 12 or less. When the amount is not less than the lower limit, there is a tendency that the film is not reduced during development, and when the amount is not more than the upper limit, the developability of the unexposed portion tends to be improved.

Specific examples of the alkyl group include a methyl group, an ethyl group, a cyclohexyl group, a dicyclopentanyl group, and a dodecanyl group. Among these, from the viewpoint of developability, a dicyclopentanyl group or a dodecanyl group is preferable, and a dicyclopentanyl group is more preferable.
The substituents that the alkyl group may have include methoxy group, ethoxy group, chloro group, bromo group, fluoro group, hydroxy group, amino group, epoxy group, oligoethylene glycol group, phenyl group, carboxyl group , An acryloyl group, a methacryloyl group, and the like. From the viewpoint of developability, a hydroxy group and an oligoethylene glycol group are preferable.

Examples of the alkenyl group for R ⁸ include linear, branched or cyclic alkenyl groups. The number of carbon atoms is preferably 2 or more, preferably 22 or less, more preferably 20 or less, further preferably 18 or less, and still more preferably 16 or less. 14 or less is particularly preferable. When the amount is not less than the lower limit, there is a tendency that the film is not reduced during development, and when the amount is not more than the upper limit, the developability of the unexposed portion tends to be improved.

  Examples of the substituent that the alkenyl group may have include methyl group, ethyl group, propyl group, methoxy group, ethoxy group, chloro group, bromo group, fluoro group, hydroxy group, amino group, epoxy group, oligo group Examples thereof include an ethylene glycol group, a phenyl group, and a carboxyl group, and a hydroxy group and an oligoethylene glycol group are preferable from the viewpoint of developability.

Examples of the alkynyl group for R ⁸ include linear, branched or cyclic alkynyl groups. The number of carbon atoms is preferably 2 or more, preferably 22 or less, more preferably 20 or less, further preferably 18 or less, and still more preferably 16 or less. 14 or less is particularly preferable. When the amount is not less than the lower limit, there is a tendency that the film is not reduced during development, and when the amount is not more than the upper limit, the developability of the unexposed portion tends to be improved.

  Examples of the substituent that the alkynyl group may have include methyl group, ethyl group, propyl group, methoxy group, ethoxy group, chloro group, bromo group, fluoro group, hydroxy group, amino group, epoxy group, oligo group, Examples thereof include an ethylene glycol group, a phenyl group, and a carboxyl group, and a hydroxy group and an oligoethylene glycol group are preferable from the viewpoint of developability.

Examples of the halogen atom in R ⁸ include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Among these, a fluorine atom is preferable from the viewpoint of dielectric constant.

Examples of the alkoxy group for R ⁸ include linear, branched or cyclic alkoxy groups. The number of carbon atoms is preferably 1 or more, preferably 20 or less, more preferably 18 or less, further preferably 16 or less, and still more preferably 14 or less. , 12 or less is particularly preferable. When the amount is not less than the lower limit, there is a tendency that the film is not reduced during development, and when the amount is not more than the upper limit, the developability of the unexposed portion tends to be improved.

  In addition, as the substituent that the alkoxy group may have, methoxy group, ethoxy group, chloro group, bromo group, fluoro group, hydroxy group, amino group, epoxy group, oligoethylene glycol group, phenyl group, carboxyl group , An acryloyl group, a methacryloyl group, and the like. From the viewpoint of developability, a hydroxy group and an oligoethylene glycol group are preferable.

Examples of the alkyl sulfide group for R ⁸ include linear, branched or cyclic alkyl sulfide groups. The number of carbon atoms is preferably 1 or more, preferably 20 or less, more preferably 18 or less, further preferably 16 or less, and still more preferably 14 or less. , 12 or less is particularly preferable. When the amount is not less than the lower limit, there is a tendency that the film is not reduced during development, and when the amount is not more than the upper limit, the developability of the unexposed portion tends to be improved.

  In addition, as the substituent that the alkyl group in the alkyl sulfide group may have, 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 preferred.

Thus, R ⁸ is an alkyl group which may have a substituent, an alkenyl group which may have a substituent, an alkynyl group which may have a substituent, a hydroxyl group, a carboxyl group, a halogen, An atom, an alkoxy group, a hydroxyalkyl group, a thiol group, or an alkyl sulfide group that may have a substituent is represented, but among these, from the viewpoint of developability, a hydroxyl group or a carboxyl group is preferred, and a carboxyl group is more preferred. preferable.

  (C2) The content of the partial structure represented by the general formula (I '') contained in the acrylic copolymer resin is not particularly limited, but is preferably 1 mol% or more, more preferably 2 mol% or more, and 3 mol%. The above is more preferable, 5 mol% or more is particularly preferable, 90 mol% or less is preferable, 70 mol% or less is more preferable, 50 mol% or less is more preferable, 30 mol% or less is further more preferable, 20 mol%. The following is particularly preferable, and 10 mol% or less is most preferable. When it is at least the lower limit, the heat resistance tends to be good, and when it is at most the upper limit, there is a tendency for moderate developability.

(Partial structure represented by general formula (I ′ ″))
(C2) When the acrylic copolymer resin includes the partial structure represented by the general formula (I), the partial structure represented by the following general formula (I ′ ″) from the viewpoint of heat resistance Is preferably included.

In the above formula (I ′ ″), R ⁹ represents 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, and 30 mol. % Or more is more preferable, 90 mol% or less is preferable, 80 mol% or less is more preferable, 70 mol% or less is more preferable, and 50 mol% or less is especially preferable. When it is at least the lower limit, the heat resistance tends to be good, and when it is at most the upper limit, there is a tendency for moderate developability. On the other hand, from the viewpoint of outgassing, it is preferable that 0%, that is, the partial structure represented by the general formula (I ′ ″) is not included.

  The acid value of the (C2) acrylic copolymer resin is not particularly limited, but is preferably 5 mg-KOH / g or more, more preferably 10 mg-KOH / g or more, further preferably 15 mg-KOH / g or more, and 20 mg-KOH / g. The above is more preferable, 100 mg-KOH / g or less is preferable, 90 mg-KOH / g or less is more preferable, 70 mg-KOH / g or less is more preferable, and 50 mg-KOH / g or less is more preferable. When the amount is not less than the lower limit, the developability of the unexposed area tends to be improved, and when the amount is not more than the upper limit, there is a tendency that the film is not reduced during development.

  (C2) The weight average molecular weight (Mw) of the acrylic copolymer resin is not particularly limited, but is usually 1000 or more, preferably 1000 or more, more preferably 2000 or more, further preferably 3000 or more, still more preferably 4000 or more, particularly preferably. Is 5000 or more, and usually 30000 or less, preferably 20000 or less, more preferably 15000 or less, and still more preferably 10,000 or less. When the amount is not less than the lower limit, there is a tendency that the film is not reduced during development, and when the amount is not more than the upper limit, the developability of the unexposed portion tends to be improved.

  (C) The content ratio of the (C2) acrylic copolymer resin 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 70% by mass. % Or more is especially preferable, 60 mass% or less is preferable, 50 mass% or less is more preferable, and 40 mass% or less is further more preferable. When the amount is not less than the above lower limit value, the developability of the unexposed portion is improved, the residue is reduced, and the ink jet suitability tends to be good. There is a tendency to make it.

  Further, the (C2) acrylic copolymer resin is preferably 5% by mass or more, more preferably 10% by mass with respect to the total mass of the (C1) epoxy (meth) acrylate resin and the (C2) acrylic copolymer resin. 15 mass% is more preferable, 70 mass% or less is preferable, 50 mass% or less is more preferable, and 30 mass% or less is further more preferable. When the amount is not less than the above lower limit value, the developability of the unexposed portion is improved, the residue is reduced, and the ink jet suitability tends to be good. There is a tendency to make it.

  Specific examples of the (C2) acrylic copolymer resin will be described in detail below. Examples of the (C2) acrylic copolymer resin include a carboxyl group copolymer having an ethylenically unsaturated group in the (C2-a) side chain.

[C2-a] Copolymer of carboxyl group-containing copolymer having ethylenically unsaturated group in side chain [C2-a-1] unsaturated carboxylic acid and compound containing two or more ethylenically unsaturated groups As a carboxyl group-containing copolymer having an ethylenically unsaturated group in the side chain, for example, allyl (meth) acrylate, 3-allyloxy-2-hydroxypropyl (meth) acrylate, cinnamyl (meth) acrylate, crotonyl (meth) A compound containing two or more ethylenically unsaturated groups such as acrylate, methallyl (meth) acrylate, N, N-diallyl (meth) acrylamide, or vinyl (meth) acrylate, 1-chlorovinyl (meth) acrylate, 2-phenylvinyl (meth) acrylate, 1-propenyl (meth) acrylate, vinyl chloride A compound containing two or more ethylenically unsaturated groups such as rotonate and vinyl (meth) acrylamide, an unsaturated carboxylic acid such as (meth) acrylic acid, or an unsaturated carboxylic acid ester, and the like. Examples thereof include a copolymer obtained by copolymerization so that the proportion of the compound containing at least one ethylenically unsaturated group is 10 to 90 mol%, preferably about 30 to 80 mol%. .

  The acid value of this copolymer is preferably 30 to 250 mg-KOH / g from the viewpoint of development solubility, and the weight average molecular weight (Mw) is preferably 1000 to 300,000 from the viewpoint of development solubility. It is.

[C2-a-2] Epoxy group-containing unsaturated compound-modified carboxyl group-containing copolymer As a carboxyl group-containing copolymer having an ethylenically unsaturated group in the side chain, for example, a carboxyl group-containing copolymer, A modified carboxyl group-containing copolymer modified by reacting an epoxy group-containing unsaturated compound and adding an epoxy group of the epoxy group-containing unsaturated compound to a part of the carboxyl group of the carboxyl group-containing copolymer may be mentioned.
As the carboxyl group-containing copolymer, from the viewpoint of sensitivity, the carboxyl group-containing copolymer (meth) acrylate- (meth) acrylic acid copolymer and styrene- (meth) acrylate- (meth) described above. Acrylic acid copolymers are preferred.
The epoxy group-containing unsaturated compounds include allyl glycidyl ether, glycidyl (meth) acrylate, α-ethyl glycidyl (meth) acrylate, glycidyl crotonate, glycidyl isocrotonate, crotonyl glycidyl ether, monoalkyl itaconate Aliphatic epoxy group-containing unsaturated compounds such as glycidyl esters, monoalkyl monoglycidyl esters of fumaric acid, and maleic acid alkyl monoglycidyl esters, and 3,4-epoxycyclohexylmethyl (meth) acrylate, 2,3-epoxycyclopentylmethyl And alicyclic epoxy group-containing unsaturated compounds such as (meth) acrylate and 7,8-epoxy [tricyclo [5.2.1.0] dec-2-yl] oxyethyl (meth) acrylate. That.
Then, these epoxy group-containing unsaturated compounds are obtained by reacting 5 to 90 mol%, preferably about 30 to 70 mol%, of the carboxyl groups of the carboxyl group-containing copolymer. In addition, reaction can be implemented by a well-known method.

  The acid value of the epoxy group-containing unsaturated compound-modified carboxyl group-containing copolymer is preferably 30 to 250 mg-KOH / g from the viewpoint of developability, and from the viewpoint of developability, the weight average molecular weight (Mw ) Is preferably 1000 to 300,000.

[C2-a-3] Unsaturated carboxylic acid-modified epoxy group and carboxyl group-containing (co) polymer Further, as a carboxyl group-containing copolymer having an ethylenically unsaturated group in the side chain, for example, (meth) acrylic acid An unsaturated carboxylic acid such as the above-mentioned aliphatic epoxy group-containing unsaturated compound or alicyclic epoxy group-containing unsaturated compound, or further an unsaturated carboxylic acid ester or styrene, the former carboxyl group-containing unsaturated compound Is reacted with an unsaturated carboxylic acid such as (meth) acrylic acid to the copolymer obtained by copolymerization so that the proportion of the total amount of the polymer becomes 10 to 90 mol%, preferably about 30 to 80 mol%. A modified epoxy group and a carboxyl group-containing copolymer modified by adding a carboxyl group of an unsaturated carboxylic acid to the epoxy group of the copolymer, Can be mentioned.

  The acid value of the unsaturated carboxylic acid-modified epoxy group and carboxyl group-containing copolymer is preferably 30 to 250 mg-KOH / g from the viewpoint of developability, and from the viewpoint of developability, the weight average molecular weight ( Mw) is preferably 1000 to 300,000.

[C2-a-4] Acid-modified epoxy group-containing copolymer As a carboxyl group-containing (co) polymer having an ethylenically unsaturated group in the side chain, an epoxy group-containing (meth) acrylate and an ethylenically unsaturated compound In addition, an ethylenically unsaturated monocarboxylic acid is added to at least a part of the epoxy group of the copolymer, and a polybasic acid (anhydride) is added to at least a part of the hydroxyl group generated by the addition. An acid-modified epoxy group-containing (co) polymer obtained by adding.
Specifically, a copolymer of 5 to 99 mol% of an epoxy group-containing (meth) acrylate such as glycidyl (meth) acrylate and usually 2 to 95 mol% of an ethylenically unsaturated compound such as (meth) acrylic acid ester. Is added to an ethylenically unsaturated monocarboxylic acid to usually 10 to 100 mol% of the epoxy group contained in the copolymer, and a polybasic acid is added to usually 10 to 100 mol% of the hydroxyl group produced when the addition is added. An acid-modified epoxy group-containing (co) polymer obtained by adding (anhydride) is exemplified.

Here, the copolymerization ratio of the epoxy group-containing (meth) acrylate in the copolymer is not particularly limited, but is usually 5 mol% or more, preferably 20 mol% or more, more preferably 40 mol% or more, and still more preferably 60 mol%. It is at least mol%, more preferably at least 80 mol%, particularly preferably at least 90 mol%, and usually at most 99 mol%, preferably at most 98 mol%, more preferably at most 95 mol%. When the amount is not less than the lower limit value, the sensitivity tends to be high, and when the value is not more than the upper limit value, there is a tendency that appropriate development solubility is obtained.
On the other hand, the copolymerization ratio of the ethylenically unsaturated compound in the copolymer is not particularly limited, but is usually 1 mol% or more, preferably 3 mol% or more, more preferably 5 mol% or more, and usually 90 mol% or less. , Preferably 70 mol% or less, more preferably 50 mol% or less, still more preferably 30 mol% or less, and particularly preferably 10 mol% or less. When the amount is not less than the lower limit value, the sensitivity tends to be high, and when the value is not more than the upper limit value, there is a tendency that appropriate development solubility is obtained.

  Examples of the epoxy group-containing (meth) acrylate include aliphatic epoxy group-containing (meth) acrylates such as glycidyl (meth) acrylate and α-ethylglycidyl (meth) acrylate; 3,4-epoxycyclohexylmethyl (meth) acrylate, 2, Alicyclic epoxy group-containing (meth) acrylates such as 3-epoxycyclopentylmethyl (meth) acrylate and 7,8-epoxy [tricyclo [5.2.1.0] dec-2-yl] oxyethyl (meth) acrylate Can be mentioned.

  Here, as an ethylenically unsaturated compound such as (meth) acrylic acid ester, for example, one or more mono (meth) acrylates having a partial structure represented by the following formula (VI) may be used. preferable.

In formula (VI), R ^{1d to} R ^4d each independently represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and R ^5d and R ^6d each independently represent a hydrogen atom or carbon number. 1-10 alkyl groups are represented. R ^5d and R ^6d may be linked to form a ring. The ring formed by linking R ^5d and R ^6d is preferably an aliphatic ring, which may be saturated or unsaturated, and preferably has 5 to 6 carbon atoms.

The carbon number of the alkyl group in R ^{1d to} R ^4d is usually 1 or more, usually 10 or less, preferably 8 or less, and more preferably 5 or less. There exists a tendency for it to become suitable image development solubility by setting it as the said upper limit or less.
Among these, from the viewpoint of solubility, R ^{1d to} R ^4d are preferably hydrogen atoms.

The carbon number of the alkyl group in R ^5d and R ^6d is usually 1 or more, and is usually 10 or less, preferably 8 or less, more preferably 5 or less. There exists a tendency which shows appropriate solubility by setting it as the said lower limit or more, and there exists a tendency for hydrophilicity to be hold | maintained by setting it as the said upper limit or less.
Among these, from the viewpoint of development solubility, it is preferable that R ^5d and R ^6d are hydrogen atoms or R ^5d and R ^6d are connected to form an aliphatic ring having 5 to 6 carbon atoms.

  Among the above formulas (VI), mono (meth) acrylates having a structure represented by the following formula (VIa), (VIb), or (VIc) are preferable. By introducing these partial structures, it tends to be possible to increase the heat resistance and strength of mono (meth) acrylate. In addition, 1 type may be used for these mono (meth) acrylates and it may use 2 or more types together by arbitrary combinations and a ratio.

  As the mono (meth) acrylate having a partial structure represented by the above formula (VI), various known ones can be used, but those represented by the following formula (VII) in particular from the viewpoint of curability. Is preferred.

In formula (VII), R ^9d represents a hydrogen atom or a methyl group, and R ^10d represents the formula (VI).

  On the other hand, as the ethylenically unsaturated compound, for example, α-, o-, m-, p-alkyl of styrene other than the mono (meth) acrylate having the partial structure represented by the formula (VI) described above, Styrenes such as nitro, cyano, amide and ester derivatives, dienes such as butadiene, 2,3-dimethylbutadiene, isoprene and chloroprene, methyl (meth) acrylate, ethyl (meth) acrylate, (meth) acrylic acid n-propyl, (meth) acrylic acid-iso-propyl, (meth) acrylic acid-n-butyl, (meth) acrylic acid-sec-butyl, (meth) acrylic acid-tert-butyl, (meth) acrylic acid pentyl , Neopentyl (meth) acrylate, Isoamyl (meth) acrylate, Hexyl (meth) acrylate, (Meth) acrylic 2-ethylhexyl, lauryl (meth) acrylate, dodecyl (meth) acrylate, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, dicyclohexyl (meth) acrylate, ( (Meth) acrylate isobornyl, (meth) acrylate adamantyl, (meth) acrylate allyl, (meth) acrylate propargyl, (meth) acrylate phenyl, (meth) acrylate naphthyl, (meth) acrylate anthracenyl, (meth) ) Anthraninonyl acrylate, piperonyl (meth) acrylate, salicyl (meth) acrylate, furyl (meth) acrylate, furfuryl (meth) acrylate, tetrahydrofuryl (meth) acrylate, pyranyl (meth) acrylate, (Meta) Acry Benzyl lurate, phenethyl (meth) acrylate, cresyl (meth) acrylate, (meth) acrylic acid-1,1,1-trifluoroethyl, perfluoroethyl (meth) acrylate, (meth) acrylic acid per Fluoro-n-propyl, perfluoro-iso-propyl (meth) acrylate, triphenylmethyl (meth) acrylate, cumyl (meth) acrylate, 3- (N, N-dimethylamino) propyl (meth) acrylate , (Meth) acrylic acid esters such as (meth) acrylic acid-2-hydroxyethyl, (meth) acrylic acid-2-hydroxypropyl, (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 (Meth) acrylic acid amides such as N, N-di-iso-propylamide, (meth) acrylic acid anthracenylamide, (meth) acrylic acid anilide, (meth) acryloylnitrile, acrolein, vinyl chloride, Vinyl compounds such as vinylidene chloride, vinyl fluoride, vinylidene fluoride, N-vinyl pyrrolidone, vinyl pyridine, vinyl acetate, and unsaturated dicarboxylic acid diesters such as diethyl citraconic acid, diethyl maleate, diethyl fumarate, diethyl itaconate , N-phenylmaleimide, N-cyclohexylmaleimide, N-laurylmaleimide, monomaleimides such as N- (4-hydroxyphenyl) maleimide, and radically polymerizable compounds such as N- (meth) acryloylphthalimide.

  Among these, in order to impart superior heat resistance and strength, it is effective to use at least one selected from styrene, benzyl (meth) acrylate and monomaleimide as the ethylenically unsaturated compound. is there. In this case, from the viewpoint of heat resistance, the copolymerization ratio of at least one selected from styrene, benzyl (meth) acrylate and monomaleimide is usually 1 mol% or more, preferably 3 mol% or more, and usually 70 It is not more than mol%, preferably not more than 50 mol%, more preferably not more than 30 mol%, still more preferably not more than 10 mol%.

  As an ethylenically unsaturated monocarboxylic acid to be added to an epoxy group contained in a copolymer of an epoxy group-containing (meth) acrylate and an ethylenically unsaturated compound, a known one can be used, and a curable viewpoint Therefore, (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% of the epoxy group contained in the copolymer. It is at least mol%, more preferably at least 70 mol%, and usually at most 100 mol%. There exists a tendency which can improve sclerosis | hardenability by making the addition ratio of ethylenically unsaturated monocarboxylic acid more than the said lower limit. In addition, a well-known method can be employ | adopted as a method of adding ethylenically unsaturated monocarboxylic acid to the said copolymer.

  The polybasic acid (anhydride) to be added to the hydroxyl group generated when ethylenically unsaturated monocarboxylic acid is added to the copolymer is not particularly limited, and one known one may be used alone. Two or more kinds may be used in any combination and ratio. By adding such a component, alkali solubility can be imparted to the copolymer.

  The amount of polybasic acid (anhydride) added is usually 1 mol% or more, preferably 5 mol% or more of the hydroxyl group produced when ethylenically unsaturated monocarboxylic acid is added to the copolymer. Preferably it is 10 mol% or more, More preferably, it is 20 mol% or more, Most preferably, it is 30 mol% or more. Moreover, it is 100 mol% or less normally, Preferably, it is 90 mol% or less, More preferably, it is 80 mol% or less, More preferably, it is 50 mol% or less. There exists a tendency which can provide sufficient developability by setting it as the said lower limit or more, and there exists a tendency which can suppress that development advances too much and film | membrane dissolution by setting it as the said upper limit or less. In addition, a well-known method can be arbitrarily employ | adopted as a method of adding a polybasic acid (anhydride) to the hydroxyl group produced | generated when an ethylenically unsaturated monocarboxylic acid is added to the said copolymer.

  The above epoxy group-containing copolymer modified with ethylenically unsaturated monocarboxylic acid and polybasic acid (anhydride) contains glycidyl (a part of carboxy group formed after addition of polybasic acid (anhydride)). Photosensitivity can be further improved by adding a glycidyl ether compound having a (meth) acrylate or an ethylenically unsaturated group. Moreover, developability can also be improved by adding the glycidyl ether compound which does not have an ethylenically unsaturated group to a part of carboxy group produced | generated after polybasic acid (anhydride) addition. Further, both of these may be added after the addition of the polybasic acid (anhydride).

Examples of the acid-modified epoxy group-containing copolymer described above include resins described in JP-A-8-297366 and JP-A-2001-89533. The weight average molecular weight (Mw) of the modified product is not particularly limited, but is usually 3,000 or more, preferably 5,000 or more, and usually 100,000 or less, preferably 50,000 or less, more preferably 30,000 or less, more preferably 20,000 or less, and particularly preferably 15,000 or less. There exists a tendency which can improve compatibility by setting it as the said lower limit or more, and there exists a tendency which can ensure solubility by setting it as the said upper limit or less. The molecular weight distribution [weight average molecular weight (Mw) / number average molecular weight (Mn)] is preferably 2.0 to 5.0 from the viewpoint of curability.
The acid value of the acid-modified epoxy group-containing copolymer is not particularly limited, but is preferably 5 mg-KOH / g or more, more preferably 10 mg-KOH / g or more, further preferably 20 mg-KOH / g or more, 150 mg-KOH / g or less is preferable, 120 mg-KOH / g or less is more preferable, 100 mg-KOH / g or less is more preferable, 80 mg-KOH / g or less is more preferable, and 50 mg-KOH / g or less is particularly preferable. There exists a tendency which can ensure solubility by setting it as the said lower limit or more, and there exists a tendency which can improve a film reduction by setting it as the said upper limit or less.

  As described above, the (C) alkali-soluble resin in the present invention contains (C1) an epoxy (meth) acrylate resin and (C2) an acrylic copolymer resin. May be included.

  Further, the average acid value of the alkali-soluble resin (C) is not particularly limited, but is preferably 10 mg-KOH / g or more, more preferably 20 mg-KOH / g or more, and preferably 30 mg-KOH / g or more, and 200 mg. -KOH / g or less is preferable, 150 mg-KOH / g or less is more preferable, 100 mg-KOH / g or less is more preferable, 70 mg-KOH / g or less is further more preferable, and 50 mg-KOH / g or less is particularly preferable. When the amount is not less than the lower limit value, moderate development solubility tends to be obtained, and when the value is not more than the upper limit value, development tends to proceed excessively and film dissolution tends to be suppressed. The average acid value of the alkali-soluble resin (C) can be measured by neutralization titration.

  The content ratio of the (C) alkali-soluble resin in the photosensitive resin composition of the present invention is usually 5% by mass or more, preferably 10% by mass or more, more preferably 20% by mass or more, based on the total solid content. The amount is preferably 30% by weight or more, particularly preferably 40% by weight or more, usually 90% by weight or less, preferably 70% by weight or less, more preferably 60% by weight or less. There exists a tendency which can be made into moderate development solubility and sensitivity by setting it as the said lower limit or more, and there exists a tendency which forms a desired pattern easily by setting it as the said upper limit or less.

  Further, the total content of (A) the ethylenically unsaturated compound and (C) the alkali-soluble resin in the total solid content is preferably 10% by mass or more, more preferably 30% by mass or more, and further preferably 60% by mass or more. Preferably, 90% by mass or more is particularly preferable, 100% by mass or less is preferable, 99% by mass or less is more preferable, and 97% by mass or less is more preferable. There exists a tendency which can be made into moderate development solubility and sensitivity by setting it as the said lower limit or more, and there exists a tendency which forms a desired pattern easily by setting it as the said upper limit or less.

[1-1-4] Component (D); Liquid Repellent Agent The photosensitive resin composition for forming a partition wall of the present invention may contain (D) a liquid repellent agent. In particular, when an organic electroluminescent device is produced by an ink jet method, it is preferable to contain (D) a liquid repellent, and since (D) it contains liquid repellent, it can impart liquid repellency to the surface of the partition wall. It is considered that the obtained partition wall can prevent color mixing for each pixel of the organic layer.
Examples of the liquid repellent include a silicone-containing compound and a fluorine-based compound, and preferably include a liquid repellent having a crosslinking group (hereinafter sometimes referred to as “crosslinking group-containing liquid repellent”). Examples of the crosslinking group include an epoxy group or an ethylenically unsaturated group, and an ethylenically unsaturated group is preferable from the viewpoint of suppressing the outflow of the liquid repellent component of the developer.
When the crosslinkable group-containing liquid repellent is used, when the formed coating film is exposed, the cross-linking reaction on the surface can be accelerated, and the liquid repellent is less likely to flow out during the development process. Can be considered to exhibit high liquid repellency.

  When a fluorine-based compound is used as the liquid repellent, the fluorine compound tends to be oriented on the surface of the partition wall and function to prevent ink bleeding and color mixing. More specifically, the group having a fluorine atom tends to function to repel ink and prevent ink bleeding and color mixing due to the ink entering the adjacent region beyond the partition wall.

  Specific examples of the crosslinkable group-containing liquid repellent, particularly the ethylenically unsaturated group-containing fluorine-based compound include, for example, perfluoroalkylsulfonic acid, perfluoroalkylcarboxylic acid, perfluoroalkylalkylene oxide adduct, perfluoroalkyltrialkylammonium salt. Oligomers containing perfluoroalkyl groups and hydrophilic groups, oligomers containing perfluoroalkyl groups and lipophilic groups, oligomers containing perfluoroalkyl groups, hydrophilic groups and new oil groups, urethanes containing perfluoroalkyl groups and hydrophilic groups, Mention may be made of fluorine-containing organic compounds such as fluoroalkyl esters and perfluoroalkyl phosphate esters. Commercially available products of these fluorine-containing compounds include “Megafac F116”, “Same F120”, “Same F142D”, “Same F144D”, “Same F150”, “Same F160”, “Same F171” manufactured by DIC, “Same F172”, “Same F173”, “Same F177”, “Same F178A”, “Same F178K”, “Same F179”, “Same F183”, “Same F184”, “Same F191”, “Same F812”, "Same F815", "Same F824", "Same F833", "DEFENSAMCF300", "Same MCF310", "Same MCF312", "Same MCF323", "Same RS72K", "Same RS304", "Same RS202", " “Same RS 201”, “Same RS 102”, “Same RS 101”, “Same RS 105”, “Same RS 401”, “Same RS 402”, “Same RS 501”, “Same "S502", "RS301", "RS303", "Mitsubishi FC431", "FC-4430", "Same FC4432" manufactured by 3M Japan, "Asahi Guard AG710", "Surflon S-382", "Asahi Glass" “SC-101”, “SC-102”, “SC-103”, “SC-104”, “SC-105”, “SC-106”, “OPTOOL DAC-HP” manufactured by Daikin Industries, Ltd. ”,“ HP-650 ”, and other commercially available fluorine-containing organic compounds can be used.

  As described above, when a fluorine-based compound is used as the liquid repellent, the F atom content in the liquid repellent is not particularly limited, but the fluorine atom content is preferably 1% by mass or more, and more preferably 5% by mass or more. Moreover, 50 mass% or less is preferable, and 25 mass% or less is more preferable. By setting it to the lower limit value or more, there is a tendency that the outflow to the pixel portion can be suppressed, and by setting the upper limit value or less, there is a tendency to show a high contact angle.

  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 liquid repellent of high molecular weight is preferable because the flow of the liquid repellent by firing can be suppressed, and the outflow of the liquid repellent from the bank can be suppressed. From this viewpoint, the number average molecular weight of the liquid repellent is 100 or more. Preferably, 500 or more is more preferable, 100,000 or less is preferable, and 10,000 or less is more preferable.

  The content ratio of the liquid repellent (D) in the photosensitive resin composition of the present invention is usually 0.01% by mass or more, preferably 0.05% by mass or more, more preferably 0.1% by mass with respect to the total solid content. % Or more, usually 1% by mass or less, preferably 0.5% by mass or less, more preferably 0.3% by mass or less. There exists a tendency which shows high liquid repellency by setting it as the said lower limit or more, and there exists a tendency which can suppress the outflow to a pixel part by setting it as the said upper limit or less.

On the other hand, in the photosensitive resin composition for forming a partition wall of the present invention, a surfactant may be used together with (D) the liquid repellent, and a surfactant may be used instead of (D) the liquid repellent. The surfactant can be used for the purpose of improving the coating property of the photosensitive resin composition for forming a partition wall as a coating solution and the developing property of the coating film, among which a fluorine-based or silicone-based surfactant is preferable. .
In particular, at the time of development, a silicone-based surfactant is preferable because it has an action of removing the residue of the photosensitive resin composition from the unexposed area and also has a function of expressing wettability. A surfactant is more preferred.

  As the fluorosurfactant, a compound having a fluoroalkyl or fluoroalkylene group in at least one of the terminal, main chain and side chain is suitable. Specifically, 1,1,2,2-tetrafluorooctyl (1,1,2,2-tetrafluoropropyl) ether, 1,1,2,2-tetrafluorooctyl hexyl ether, octaethylene glycol di ( 1,1,2,2-tetrafluorobutyl) ether, hexaethylene glycol di (1,1,2,2,3,3-hexafluoropentyl) ether, octapropylene glycol di (1,1,2,2- Tetrafluorobutyl) ether, hexapropylene glycol di (1,1,2,2,3,3-hexafluoropentyl) ether, sodium perfluorododecylsulfonate, 1,1,2,2,8,8,9, Examples include 9,10,10-decafluorododecane and 1,1,2,2,3,3-hexafluorodecane. Examples of these commercially available products include “BM-1000” and “BM-1100” manufactured by BM Chemie, “Megafuck F142D”, “Megafuck F172”, “Megafuck F173”, and “Megafuck F183” manufactured by DIC. ”,“ Megafuck F470 ”,“ Megafuck F475 ”,“ Megafuck F554 ”,“ Megafuck F559 ”,“ FC430 ”manufactured by 3M Japan,“ DFX-18 ”manufactured by Neos, and the like.

Examples of the silicone surfactant include “DC3PA”, “SH7PA”, “DC11PA”, “SH21PA”, “SH28PA”, “SH29PA”, “8032Additive”, “SH8400” manufactured by Toray Dow Corning, Commercial products such as “BYK323” and “BYK330” manufactured by Big Chemie may be mentioned.
Surfactants may include those other than fluorosurfactants and silicone surfactants, and other surfactants include nonionic, anionic, cationic, and amphoteric surfactants. It is done.

  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, sorbit fatty acid esters, polyoxy And ethylene sorbite fatty acid esters. Examples of these commercially available products include polyoxyethylene surfactants such as “Emulgen 104P” and “Emulgen A60” manufactured by Kao Corporation.

  Examples of the anionic surfactant include alkyl sulfonates, alkyl benzene sulfonates, alkyl naphthalene sulfonates, polyoxyethylene alkyl ether sulfonates, alkyl sulfates, alkyl sulfate esters, and higher alcohol sulfates. Ester salts, aliphatic alcohol sulfates, polyoxyethylene alkyl ether sulfates, polyoxyethylene alkyl phenyl ether sulfates, alkyl phosphate esters, polyoxyethylene alkyl ether phosphates, polyoxyethylene alkyl phenyl ether phosphates, special Examples thereof include polymer surfactants. Among these, special polymer surfactants are preferable, and special polycarboxylic acid type polymer surfactants are more preferable. Commercially available products can be used as such anionic surfactants, such as “Emar 10” manufactured by Kao Corporation for alkyl sulfate esters, and “Perex NB-L” manufactured by Kao Corporation for alkylnaphthalene sulfonates. Examples of special polymer surfactants include “Homogenol L-18” and “Homogenol L-100” manufactured by Kao Corporation.

Further, the cationic surfactants include quaternary ammonium salts, imidazoline derivatives, alkylamine salts and the like, and the amphoteric surfactants include betaine type compounds, imidazolium salts, imidazolines, amino acids. Etc. Of these, quaternary ammonium salts are preferred, and stearyltrimethylammonium salts are more preferred. Examples of commercially available products include “Acetamine 24” manufactured by Kao Corporation for alkylamine salts, and “Cotamine 24P” and “Cotamine 86W” manufactured by Kao Corporation for quaternary ammonium salts.
Further, the surfactant may be used in combination of two or more kinds, for example, silicone surfactant / fluorine surfactant, silicone surfactant / special polymer surfactant, fluorine surfactant. / Special polymer surfactant combinations and the like. Of these, a combination of silicone surfactant / fluorine surfactant is preferable. In this silicone surfactant / fluorine surfactant combination, for example, “DFX-18” manufactured by Neos, “BYK-300” or “BYK-330” manufactured by Big Chemie, and “S” manufactured by AGC Seimi Chemical Co., Ltd. -393 ", Shin-Etsu Silicone" KP340 "/ DIC" F-478 "or" F-475 ", Toray Dow Corning" SH7PA "/ Daikin" DS-401 ", NUC" L-77 "/" FC4430 "manufactured by 3M Japan.

[1-1-5] Ultraviolet Absorber The photosensitive resin composition for forming a partition wall of the present invention may contain an ultraviolet absorber. The ultraviolet absorber is added for the purpose of controlling the photocuring distribution by absorbing a specific wavelength of a light source used for exposure by the ultraviolet absorber. By adding the ultraviolet absorber, it is possible to improve the taper angle and shape after development, and to eliminate residues remaining in the non-exposed area after development. As the ultraviolet absorber, from the viewpoint of inhibiting the light absorption of the initiator, for example, a compound having an absorption maximum between wavelengths of 250 nm to 400 nm can be used.
As the ultraviolet absorber, a benzotriazole compound and / or a triazine compound is desirable. By including a benzotriazole-based compound and / or a triazine-based compound, it is considered that the light absorption rate at the bottom of the film of the initiator is reduced, and the effect of increasing the taper angle is obtained by reducing the bottom size.

  Among the benzotriazole compounds, a benzotriazole compound described by the following general formula (Z1) is preferable from the point of taper shape.

In the formula (Z1), R ^1e and R ^2e are each independently represented by a hydrogen atom, an alkyl group which may have a substituent, the following general formula (Z2), or the following general formula (Z3). Represents a group. R ^3e represents a hydrogen atom or a halogen atom.

In the above formula (Z2), R ^4e represents an alkylene group which may have a substituent, and R ^5e represents an alkyl group which may have a substituent.

In the above formula (Z3), R ^6e represents an alkylene group which may have a substituent, and R ^7e represents a hydrogen atom or a methyl group.
(R ^1e and R ^2e )
In the formula (Z1), R ^1e and R ^2e each independently represent a hydrogen atom, an alkyl group which may have a substituent, a group represented by the general formula (Z2) or 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, preferably 10 or less, more preferably 6 or less, More preferably, it is 4 or less.

Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, and a tert-butyl group. Among these, a tert-butyl group is preferable.
The substituents that the alkyl group may have include 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.

(R ^3e )
In the formula (Z1), R ^3e represents a hydrogen atom or a halogen atom.
Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
Among these, from the viewpoint of synthesis, R ^3e is preferably a hydrogen atom.

(R ^4e )
In the formula (Z2), R ^4e represents an alkylene group which may have 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, preferably 6 or less, more preferably 4 or less, and still more preferably 3 or less.

Specific examples of the alkylene group include methylene group, ethylene group, propylene group, propylene group, butylene group and the like. Among these, an ethylene group is preferable.
In addition, as the substituent that the alkylene group may have, 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.

Among these, R ^4e is preferably an ethylene group.

(R ^5e )
In the formula (Z2), an alkyl group which may have a substituent is represented.
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, still more preferably 7 or more, and is preferably 15 or less, more preferably 10 or less, More preferably, it is 9 or less.

Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a hepsyl group, an octyl group, and a nonyl group.
The substituents that the alkyl group may have include 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.
Among these, from the viewpoint of the tapered shape, R ^5e is preferably a heptyl group, an octyl group, or a nonyl group.

(R ^6e )
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, preferably 6 or less, more preferably 4 or less, and still more preferably 3 or less.

Specific examples of the alkylene group include methylene group, ethylene group, propylene group, propylene group, butylene group and the like. Among these, an ethylene group is preferable.
In addition, as the substituent that the alkylene group may have, 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.

Among these, from the viewpoint of the taper shape, R ^1e is a tert-butyl group, R ^2e is a group represented by (Z2) (where R ^4e is a methylene group, and R ^5e is an alkyl group having 7 to 9 carbon atoms), A compound in which R ^3e is a hydrogen atom, or R ^1e is a hydrogen atom, R ^2e is a group represented by (Z3) (where R ^6e is a methylene group, and R ^7e is a methyl group), and R ^3e is a hydrogen atom A compound is preferable, R ^1e is a tert-butyl group, R ^2e is a group represented by (Z2) (where R ^4e is a methylene group, and R ^5e is an alkyl group having 7 to 9 carbon atoms), and R ^3e is a hydrogen atom The compound which is is more preferable.

  Other benzotriazole compounds include 2- (5 methyl-2-hydroxyphenyl) benzotriazole, 2- (2-hydroxy-5-tert-butylphenyl) -2H-benzotriazole, octyl-3 [3-tert. -Butyl-4-hydroxy-5- (5-chloro-2H-benzotriazol-2-yl) phenyl] propionate and 2-ethylhexyl-3- [3-tert-butyl-4-hydroxy-5- (5-chloro -2H-benzotriazol-2-yl) phenyl] propionate, 2- [2-hydroxy-3,5-bis (α, α-dimethylbenzyl) phenyl] -2H-benzotriazole, 2- (3-t Butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole, 2- (3,5-di- t-amyl-2-hydroxyphenyl) benzotriazole, 2- (2′-hydroxy-5′-t-octylphenyl) benzotriazole, 2- (2H-benzotriazol-2-yl) -4,6-bis ( 1-methyl-1-phenylethyl) phenol, 2- (2H-benzotriazol-2-yl) -6- (1-methyl-1-phenylethyl) -4- (1,1,3,3-tetramethyl Butyl) phenol.

  Commercially available benzotriazole compounds include, for example, Sumisorb 200, Sumisorb 250, Sumisorb 300, Sumisorb 340, Sumisorb 350 (manufactured by Sumitomo Chemical), JF77, JF78, JF79, JF80, JF83 (Johoku Chemical Industries), TINUVIN PS , TINUVIN 99-2, TINUVIN 109, TINUVIN 384-2, TINUVIN 326, TINUVIN 900, "TINUVIN 928", TINUVIN 928, TINUVIN 1VERB, BORBER 76 B78, EVERSORB80, EVERSORB81 (manufactured by Eizo Chemical Industries, Taiwan), Tomisorb 100, Tomisorb 600 (manufactured by API Corporation), SEESORB701, SEESORB702, SEESORB703, SEESORB706, SEESORB707, SEESORB 709 Etc.).

Examples of triazine compounds include 2- [4,6-di (2,4-xylyl) -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, 2- (2,4-dihydroxyphenyl) -4 , 6-Bis (2,4-dimethylphenyl) -1,3,5-triazine and (2-ethylhexyl-glycidic acid ester reaction product, 2,4-bis "2-hydroxy-4-butoxyphenyl"- 6- (2,4-dibutoxyphenyl) -1,3-5-triazine, etc. Among these, a hydroxyphenyl triazine compound is preferable from the viewpoint of taper angle and exposure sensitivity.
Examples of commercially available triazine compounds include TINUVIN 400, TINUVIN 405, TINUVIN 460, TINUVIN 477, and TINUVIN 479 (manufactured by BASF).

Examples of other ultraviolet absorbers include benzophenone compounds, benzoate compounds, cinnamic acid derivatives, naphthalene derivatives, anthracene and derivatives thereof, dinaphthalene compounds, phenanthroline compounds, and dyes.
More specifically, for example, Sumisorb 130 (manufactured by Sumitomo Chemical), EVERSORB10, EVERSORB11, EVERSORB12 (manufactured by Yongkou Chemical Industries, Taiwan), Tomissorb 800 (manufactured by API Corporation), SESORB100, SESORB101, SESORB101S, SEESORB102, SEESORB103, SEESORB103, SEESORB103, SEESORB103 Benzophenone compounds such as SEESORB106, SEESORB107, and SEESORB151 (manufactured by Cypro Kasei); Sumitsorb 400 (manufactured by Sumitomo Chemical); benzoate compounds such as phenyl salicylate; 2-ethylhexyl cinnamate, 2-ethylhexyl paramethoxycinnamate, isopropyl methoxycinnamate, methoxy Cinnamic acid derivatives such as isoamyl cinnamate; 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, naphthalene derivatives such as 2,7-dihydroxynaphthalene; anthracene, 9,10-dihydroxyanthracene, etc. Anthracene and its derivatives; azo dyes, benzophenone dyes, amino ketone dyes, quinoline dyes, anthraquinone dyes, diphenyl cyanoacrylate dyes, triazine dyes, p-aminobenzoic acid dyes, etc. And the like. Among these, from the viewpoint of exposure sensitivity, cinnamic acid derivatives and naphthalene derivatives are preferably used, and cinnamic acid derivatives are particularly preferably used. These light absorbers can be used alone or in combination of two or more.

  Among these, from the viewpoint of the taper shape, a benzotriazole compound and / or a hydroxyphenyltriazine compound are preferable, and a benzotriazole compound is particularly preferable.

As the ultraviolet absorber, one type of compound may be used alone, or two or more types of compounds may be used in combination.

  The content ratio of the ultraviolet absorber in the photosensitive resin composition of the present invention is usually 0.01% by mass or more, preferably 0.05% by mass or more, more preferably 0.1% by mass with respect to the total solid content. Or more, more preferably 0.5% by mass or more, particularly preferably 1% by mass or more, and 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. The taper angle tends to be increased by setting it to the lower limit value or more, and the sensitivity tends to be increased by setting the upper limit value or less.

  Moreover, (B) As a compounding ratio with respect to a photoinitiator, (B) As a compounding quantity of (D) ultraviolet absorber with respect to 100 mass parts of photoinitiators, it is 1 mass part or more normally, Preferably it is 10 mass parts or more, More preferably 30 parts by mass or more, further preferably 50 parts by mass or more, particularly preferably 80 parts by mass or more, usually 500 parts by mass or less, preferably 300 parts by mass or less, more preferably 200 parts by mass or less, still more preferably. 100 parts by mass or less. The taper angle tends to be increased by setting it to the lower limit value or more, and the sensitivity tends to be increased by setting the upper limit value or less.

[1-1-6] Polymerization inhibitor The photosensitive resin composition for forming a partition wall of the present invention preferably contains a polymerization inhibitor. (E) Since it inhibits radical polymerization by containing a polymerization inhibitor, the taper angle of the resulting partition tends to be increased.
Examples of the polymerization inhibitor include hydroquinone, hydroquinone monomethyl ether, methyl hydroquinone, methoxyphenol, 2,6-di-tert-butyl-4-cresol (BHT) and the like. Among these, hydroquinone or methoxyphenol is preferable from the viewpoint of the ability to inhibit polymerization, and methylhydroquinone is more preferable.

  It is preferable that a polymerization inhibitor contains 1 type (s) or 2 or more types. Usually, when producing (C) an alkali-soluble resin, a polymerization inhibitor may be contained in the resin, and it may be used as the (E) polymerization inhibitor of the present invention or contained in the resin. In addition to the polymerization inhibitor used, the same or different polymerization inhibitor may be added during the production of the photosensitive resin composition.

  The content of the polymerization inhibitor in the photosensitive resin composition is usually 0.0005% by mass or more, preferably 0.001% by mass or more, more preferably 0.005% by mass or more with respect to the total solid content of the photosensitive resin composition. It is 01 mass% or more, and is usually 0.1 mass% or less, preferably 0.08 mass% or less, more preferably 0.05 mass% or less. There exists a tendency which can make a taper angle high by setting it as the said lower limit or more, and there exists a tendency which can maintain a high sensitivity by setting it as the said upper limit or less.

[1-1-7] Thermal Polymerization Initiator Furthermore, the partition wall-forming photosensitive resin composition of the present invention may contain a thermal polymerization initiator. By containing a thermal polymerization initiator, there is a tendency that the degree of crosslinking of the film can be increased. Specific examples of such a thermal polymerization initiator include azo compounds, organic peroxides and hydrogen peroxide. These may be used alone or in combination of two or more.

  When a thermal polymerization initiator is used in combination with the photopolymerization initiator in the hope of improving sensitivity and increasing the crosslink density of the film, the total content of these is the photopolymerization initiator in the photosensitive resin composition described above. The combined proportion of the photopolymerization initiator and the thermal polymerization initiator is preferably a thermal polymerization initiator with respect to 100 parts by mass of the photopolymerization initiator from the viewpoint of sensitivity. It is preferable to set it as 5-300 mass parts.

[1-1-8] Amino Compound The photosensitive resin composition for forming a partition wall of the present invention may contain an amino compound in order to promote thermosetting. 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. Moreover, it is 0.5 mass% or more normally, Preferably it is 1 mass% or more. There exists a tendency which can maintain storage stability by setting it as the said upper limit or less, and there exists a tendency which can ensure sufficient thermosetting by setting it as the said lower limit or more.

  Examples of the amino compound include an amino compound having at least two methylol groups as functional groups and alkoxymethyl groups obtained by subjecting the methylol group to alcohol condensation modification having 1 to 8 carbon atoms. Specifically, for example, melamine resin obtained by polycondensation of melamine and formaldehyde; benzoguanamine resin obtained by polycondensation of benzoguanamine and formaldehyde; glycoluril resin obtained by polycondensation of glycoluril and formaldehyde; urea and formaldehyde Examples include polycondensed urea resins; resins obtained by copolycondensation of two or more of melamine, benzoguanamine, glycoluril, and urea with formaldehyde; modified resins obtained by alcohol condensation modification of methylol groups of the above-described resins. These may be used alone or in combination of two or more. Among the amino compounds, melamine resins and modified resins thereof are preferable, modified resins having a methylol group modification ratio of 70% or more are more preferable, and modified resins having 80% or more are particularly preferable.

  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 manufactured by Cytec Corporation, 703, 701, 266, 267, 285, 232, 235, 238, 1141, 272, 254, 202, 1156, 1158, and “Nikarak” (registered trademark) MW-390, MW-100LM manufactured by Sanwa Chemical Co., Ltd. MX-750LM, MW-30M, MX-45, MX-302 and the like. Examples of the benzoguanamine resin and modified resins thereof include “Cymel” (registered trademark) 1123, 1125, and 1128 manufactured by Cytec Corporation. Examples of the glycoluril resin and the modified resin thereof include “Cymel” (registered trademark) 1170, 1171, 1174, 1172 manufactured by Cytec, and “Nicarak” (registered trademark) MX manufactured by Sanwa Chemical Co., Ltd. -270 and the like. Examples of the urea resin and the modified resin thereof include “UFR” (registered trademark) 65 and 300 manufactured by Cytec, and “Nicarak” (registered trademark) MX-290 manufactured by Sanwa Chemical Co., Ltd. It is done.

[1-1-9] Colorant The photosensitive resin composition for forming a partition wall of the present invention may contain a colorant for the purpose of coloring the partition wall. As the colorant, known colorants such as pigments and dyes can be used. For example, when using a pigment, a known dispersant or dispersion aid may be used in combination so that the pigment can be stably present in the photosensitive resin composition without agglomeration. In particular, by coloring the liquid repellent partition wall black, there is an effect that a clear pixel display can be obtained. In addition to black dyes, black pigments, carbon black, titanium black, and the like as black colorants, mixing with organic pigments to color black is also effective as an effect of imparting low conductivity. The content of the colorant is usually 60% by mass or less, preferably 40% by mass or less, based on the total solid content of the photosensitive resin composition, from the viewpoints of plate making properties and color characteristics.

[1-1-10] Coating property improving agent and development improving agent The photosensitive resin composition for forming a partition wall of the present invention contains a coating property improving agent and a developing improving agent in order to improve coating property and development solubility. It may be. As the coatability improver or development improver, for example, known cationic, anionic, nonionic, fluorine-based, and silicone-based surfactants can be used. Further, as the development improver, known ones such as organic carboxylic acids or anhydrides thereof can be used. Moreover, the content is 20 mass% or less normally with respect to the total solid of the photosensitive resin composition from a viewpoint of a sensitivity, Preferably it is 10 mass% or less.

[1-1-11] Silane Coupling Agent It is also preferable to add a silane coupling agent to the photosensitive resin composition for forming a partition wall of the present invention in order to improve adhesion to the substrate. Various types of silane coupling agents such as epoxy, methacrylic, amino, and imidazole can be used, and epoxy and imidazole silane coupling agents are particularly preferable from the viewpoint of improving adhesion. The content is usually 20% by mass or less, preferably 15% by mass or less, based on the total solid content of the photosensitive resin composition, from the viewpoint of adhesion.

[1-1-12] Inorganic filler Further, the photosensitive resin composition for forming a partition wall according to the present invention further improves the strength as a cured product and has a moderate interaction with an alkali-soluble resin (formation of a matrix structure). ) May contain an inorganic filler for the purpose of improving the flatness of the coating film and improving the taper angle. Examples of such inorganic fillers include talc, silica, alumina, barium sulfate, magnesium oxide, and those obtained by surface treatment with various silane coupling agents.

  The average particle size of these inorganic fillers is usually 0.005 to 20 μm, preferably 0.01 to 10 μm. Here, the average particle diameter referred to in the present embodiment is a value measured with a laser diffraction / scattering particle size distribution measuring device such as manufactured by Beckman Coulter. Among these inorganic fillers, silica sol and silica sol-modified product are particularly preferably blended because they tend to be excellent in the effect of improving the taper angle as well as the dispersion stability. When the photosensitive resin composition for forming a partition wall of the present invention contains these inorganic fillers, the content thereof is usually 5% by mass or more, preferably 10% by mass, based on the total solid content, from the viewpoint of sensitivity. These are usually 80% by mass or less, preferably 70% by mass or less.

[1-1-13] Solvent The photosensitive resin composition for forming a partition wall of the present invention usually contains a solvent and is used in a state where each of the above-mentioned components is dissolved or dispersed in the solvent (hereinafter, including the solvent). The photosensitive resin composition may be referred to as “photosensitive resin composition solution”). Although there is no restriction | limiting in particular as the solvent, For example, the organic solvent described below is mentioned.

  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-t-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, tri Ethylene glycol monomethyl ether Glycol monoalkyl ethers such as triethylene glycol monoethyl ether and tripropylene glycol methyl ether; ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether Glycol dialkyl ethers such as dipropylene glycol dimethyl ether; 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 -Glycol alkyl ethers such as butyl ether acetate, dipropylene glycol monomethyl ether acetate, triethylene glycol monomethyl ether acetate, triethylene glycol monoethyl ether acetate, 3-methyl-3-methoxybutyl acetate, 3-methoxy-1-butyl acetate Acete Glycol diacetates such as ethylene glycol diacetate, 1,3-butylene glycol diacetate and 1,6-hexanol diacetate; alkyl acetates such as cyclohexanol acetate; amyl ether, diethyl ether, dipropyl ether , Ethers such as diisopropyl ether, dibutyl ether, diamyl ether, ethyl isobutyl ether, dihexyl ether; 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, methoxymethyl pentano Ketones such as: methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, butanediol, diethylene glycol, dipropylene glycol, triethylene glycol, methoxymethylpentanol, glycerin, benzyl alcohol, etc. Monohydric or polyhydric alcohols; aliphatic hydrocarbons such as n-pentane, n-octane, diisobutylene, n-hexane, hexene, isoprene, dipentene, dodecane; cyclohexane, methylcyclohexane, methylcyclohexene, bicyclohexyl Such as alicyclic hydrocarbons; aromatic hydrocarbons such as benzene, toluene, xylene, cumene; amyl formate, ethyl formate, ethyl acetate, acetic acid Chill, propyl acetate, amyl acetate, methyl isobutyrate, ethylene glycol acetate, ethyl propionate, propyl propionate, butyl butyrate, isobutyl butyrate, methyl isobutyrate, ethyl caprylate, butyl stearate, ethyl benzoate, 3- Linear or cyclic such as methyl ethoxypropionate, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, butyl 3-methoxypropionate, γ-butyrolactone Esters; alkoxycarboxylic acids such as 3-methoxypropionic acid and 3-ethoxypropionic acid; halogenated hydrocarbons such as butyl chloride and amyl chloride; ether ketones such as methoxymethylpentanone Down like; acetonitrile, nitriles such as benzonitrile: is tetrahydrofuran, dimethyl tetrahydrofuran, tetrahydrofuran, such as dimethoxytetrahydrofuran.

  Commercially available solvents corresponding to the above include mineral spirit, Barsol # 2, Apco # 18 Solvent, Apco thinner, Soal Solvent No. 1 and no. 2, Solvesso # 150, Shell TS28 Solvent, carbitol, ethyl carbitol, butyl carbitol, methyl cellosolve, ethyl cellosolve, ethyl cellosolve acetate, methyl cellosolve acetate, diglyme (all trade names) and the like.

  The solvent is capable of dissolving or dispersing each component in the photosensitive resin composition, and is selected according to the method of using the photosensitive resin composition of the present invention. It is preferable to select one having a boiling point in the range of 60 to 280 ° C. under atmospheric pressure. More preferably, it has a boiling point of 70 ° C. or higher and 260 ° C. or lower. For example, propylene glycol monomethyl ether, 3-methoxy-1-butanol, propylene glycol monomethyl ether acetate, and 3-methoxy-1-butyl acetate are preferable.

  These solvents can be used alone or in combination of two or more. These solvents have a total solid content in the photosensitive resin composition solution of 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 Is preferably used in an amount of 50% by mass or less, more preferably 40% by mass or less, and still more preferably 30% by mass or less. There exists a tendency which can suppress generation | occurrence | production of a coating nonuniformity by setting it as the said lower limit or more, and there exists a tendency which can suppress generation | occurrence | production of a foreign material, a repellency, etc. by setting it as the said upper limit or less.

[1-2] Preparation Method of Photosensitive Resin Composition for Partition Formation The photosensitive resin composition for partition formation of the present invention is prepared by mixing the above components with a stirrer. In addition, you may filter using a membrane filter etc. so that the prepared photosensitive resin composition may become uniform.

[2] Partition Wall and Method for Forming the Partition The photosensitive resin composition of the present invention can be suitably used for forming a partition wall, particularly a partition wall for partitioning an organic layer of an organic electroluminescent element.
The method for forming the partition using the partition forming photosensitive resin composition described above is not particularly limited, and a conventionally known method can be employed. Examples of the method of forming the partition include, for example, a coating step of applying a photosensitive resin composition for partition formation on a substrate to form a photosensitive resin composition layer, and an exposure step of exposing the photosensitive resin composition layer. The method including these is mentioned. Specific examples of such a bank forming method include an inkjet method and a photolithography method.

  In the ink jet method, a photosensitive resin composition for forming a partition whose viscosity is adjusted by dilution with a solvent or the like is used as ink, and ink droplets are ejected onto a substrate by an ink jet method along a predetermined partition pattern. The resin composition is applied onto a substrate to form an uncured partition pattern. Then, an uncured partition wall pattern is exposed to form a cured partition wall on the substrate. The exposure of the uncured partition pattern is performed in the same manner as the exposure process in the photolithography method described later, except that a mask is not used.

  In the photolithography method, a photosensitive resin composition for forming a partition wall is applied to the entire surface of a substrate where a partition wall is formed to form a photosensitive resin composition layer. The formed photosensitive resin composition layer is exposed according to a predetermined partition wall pattern, and then the exposed photosensitive resin composition layer is developed to form partition walls on the substrate.

  In the coating process in which a photosensitive resin composition is applied onto a substrate in a photolithography method, a contact transfer type coating device such as a roll coater, a reverse coater, a bar coater, or a spinner (rotary type) is formed on the substrate on which a partition wall is to be formed. The photosensitive resin composition is applied using a non-contact type coating apparatus such as a coating apparatus or a curtain flow coater, and the solvent is removed by drying as necessary to form a photosensitive resin composition layer.

Next, in the exposure step, using a negative mask, the photosensitive resin composition is irradiated with active energy rays such as ultraviolet rays and excimer laser light, and the photosensitive resin composition layer is partially applied according to the bank pattern. To expose. For the exposure, a light source that emits ultraviolet rays such as a high-pressure mercury lamp, an ultra-high pressure mercury lamp, a xenon lamp, or a carbon arc lamp can be used. The amount of exposure varies depending on the composition of the photosensitive resin composition, but is preferably about 10 to 400 mJ / cm ² , for example.

  Next, in the developing step, the barrier ribs are formed by developing the exposed photosensitive resin composition layer with a developer according to the pattern of the barrier ribs. The development method is not particularly limited, and an immersion method, a spray method, or the like can be used. Specific examples of the developer include organic ones such as dimethylbenzylamine, monoethanolamine, diethanolamine, and triethanolamine, and aqueous solutions such as sodium hydroxide, potassium hydroxide, sodium carbonate, ammonia, and quaternary ammonium salts. Can be mentioned. An antifoaming agent or a surfactant can also be added to the developer.

  Thereafter, the partition walls after development are post-baked and cured by heating. Post baking is preferably performed at 150 to 250 ° C. for 15 to 60 minutes.

  The substrate used for forming the partition wall is not particularly limited, and is appropriately selected according to the type of the organic electroluminescence element manufactured using the substrate on which the partition wall is formed. Suitable materials for the substrate include glass and various resin materials. Specific examples of the resin material include polyesters such as polyethylene terephthalate; polyolefins such as polyethylene and polypropylene; polycarbonates; poly (meth) methacrylic resins; polysulfones; Among these substrate materials, glass and polyimide are preferable because of excellent heat resistance. Moreover, according to the kind of organic electroluminescent element manufactured, you may provide transparent electrode layers, such as ITO and ZnO, in advance on the surface of the board | substrate with which a partition is formed.

[3] Organic electroluminescent element The organic electroluminescent element of the present invention includes a partition composed of the above-described photosensitive resin composition for forming a partition.
Various organic electroluminescent elements are manufactured using the substrate provided with the barrier rib pattern manufactured by the method described above. The method for forming the organic electroluminescent element is not particularly limited, but preferably, after forming a partition pattern on the substrate by the above method, ink is injected into a region surrounded by the partition on the substrate to form a pixel or the like. An organic electroluminescent element is manufactured by forming an organic layer.

  In the case where the partition wall has a skirt shape, the ink for forming the organic layer is repelled by the skirt portion of the partition wall, so that the region surrounded by the partition wall may not be sufficiently covered with the ink for forming the organic layer. On the other hand, by forming a good shape without skirting, the region surrounded by the partition walls can be sufficiently covered with the ink for forming the organic layer. Thereby, for example, the problem of halation in the organic EL display element can be solved.

  As the solvent used when forming the ink for forming the 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 film formed 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, isopropyl alcohol, ethyl acetate, and butyl acetate, 3-phenoxytoluene, Etc. In addition, a surfactant, an antioxidant, a viscosity modifier, an ultraviolet absorber, and the like can be added to the ink.

  As a method for injecting ink into the region surrounded by the partition wall, 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 is appropriately selected according to the type of the organic electroluminescent element to be produced. When the ink is injected by an ink jet method, the viscosity of the ink is not particularly limited as long as the ink can be discharged well from the ink jet head, but is preferably 4 to 20 mPa · s, and more preferably 5 to 10 mPa · s. The viscosity of the ink can be adjusted by adjusting the solid content in the ink, changing the solvent, adding a viscosity modifier, or the like.

[4] Image display device The image display device of the present invention includes the organic electroluminescence device described above. As long as it includes an organic electroluminescent element, the type and structure of the image display device are not particularly limited, and for example, it can be assembled according to a conventional method using an active drive type organic electroluminescent element. For example, the image display device of the present invention is formed by a method as described in “Organic EL Display” (Ohm, published on August 20, 2004, by Shizushi Tokito, Chiba Adachi, and Hideyuki Murata). can do. For example, an organic electroluminescent element that emits white light and a color filter may be combined to display an image, or organic electroluminescent elements having different emission colors such as RGB may be combined to display an image.

[5] Illumination The illumination of the present invention includes the above-described organic electroluminescent element. There is no restriction | limiting in particular about a model or a structure, It can assemble in accordance with a conventional method using the organic electroluminescent element of this invention. The organic electroluminescence element may be a simple matrix driving method or an active matrix driving method.
In order for the illumination of the present invention to emit white light, an organic electroluminescent element that emits white light may be used. In addition, organic electroluminescent elements having different emission colors may be combined so that each color is mixed to become white, or the color mixing ratio can be adjusted to provide a color adjustment function.

  Hereinafter, although the specific example is given and demonstrated about the photosensitive resin composition for partition formation of this invention, this invention is not limited to a following example, unless the summary is exceeded.

[1] Production of barrier rib-forming photosensitive resin composition Each component was used in a blending ratio (parts by mass) shown in Table 1, and propylene glycol monomethyl ether so that the total solid content was 25% by mass. Each component was stirred until it became uniform using acetate, and the photosensitive resin composition for partition formation of an Example and a comparative example was prepared. In addition, the numerical value in Table 1 means the value of solid content.
In addition, the symbol in a table | surface represents the following.

a-1: Dipentaerythritol hexaacrylate (DPHA) (manufactured by Nippon Kayaku Co., Ltd.)
b-1: 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole (manufactured by Hodogaya Chemical Co., Ltd.)

d-1: RS72K (manufactured by DIC, fluorine-based, oligomer having an ethylenic double bond)
e-1: 2-mercaptobenzimidazole (manufactured by Tokyo Chemical Industry Co., Ltd.)
e-2: Pentaerythritol tetrakis (3-mercaptopropionate) (manufactured by Sakai Chemical Co., Ltd.)
f-1: TINUVIN 384-2 (manufactured by BASF)
g-1: PM21 (made by Nippon Kayaku Co., Ltd.)

c-1: The following ethylenically unsaturated group-containing resin (corresponding to epoxy acrylate resin / resin represented by the general formula (C1-2))
400 parts by mass of an epoxy compound represented by the following formula (a mixture of those having a weight average molecular weight of 3900, wherein n is 1 to 20), 102 parts by mass of acrylic acid, 0.3 parts by mass of p-methoxyphenol, triphenylphosphine 5 The reaction vessel was charged with parts by mass and 264 parts by mass of propylene glycol monomethyl ether acetate, and stirred at 95 ° C. until the acid value became 3 mgKOH / g or less. Next, 91 parts by mass of tetrahydrophthalic anhydride was further added and reacted at 95 ° C. for 4 hours. An alkali-soluble resin having a solid content acid value of 60 mg-KOH / g and a polystyrene-reduced weight average molecular weight (Mw) of 6800 measured by GPC. (C-1) A solution was obtained.

c-2: The following ethylenically unsaturated group-containing resin (equivalent to a resin represented by epoxy acrylate resin / general formula (C1-3))
100 parts by mass of a bisphenol A type epoxy compound represented by the following formula (epoxy equivalent 186 g / eq, a mixture of those in which n is 1 to 20), 40 parts by mass of acrylic acid, 0.06 parts by mass of p-methoxyphenol, The reaction vessel was charged with 2.4 parts by mass of triphenylphosphine and 126 parts by mass of propylene glycol monomethyl ether acetate, and stirred at 95 ° C. until the acid value became 5 mg-KOH / g or less. Subsequently, 12 parts by mass of propylene glycol monomethyl ether acetate was added to 80 parts by mass of the reaction solution obtained by the above reaction, 5 parts by mass of succinic anhydride was added, and the mixture was reacted at 95 ° C. for 3 hours to obtain a solid content acid value of 40 mg-KOH. / G, an alkali-soluble resin (c-2) solution having a weight average molecular weight (Mw) in terms of polystyrene of 8000 measured by GPC was obtained.

c-3: The following ethylenically unsaturated group-containing resin (epoxy acrylate resin / corresponding to the resin represented by the general formula (C1-6))
CCR-1332 (Nippon Kayaku Co., Ltd.) Cresol novolac epoxy acrylate resin solution. The weight average molecular weight (Mw) in terms of polystyrene measured by GPC was 6500, and the solid content acid value was 60 mg-KOH / g.

c-4: The following acrylic copolymer resin (equivalent to (C2) acrylic copolymer resin)
A copolymer resin containing tricyclodecane methacrylate / styrene / glycidyl methacrylate (molar ratio: 0.02 / 0.05 / 0.93) as a constituent monomer is subjected to an addition reaction of acrylic acid with an equal amount of glycidyl methacrylate, followed by anhydrous tetrahydro An alkali-soluble acrylic copolymer resin in which phthalic acid is added at a molar ratio of 0.1 to 1 mol of the above copolymer resin. The weight average molecular weight (Mw) in terms of polystyrene measured by GPC was 9000, and the solid content acid value was 24.3 mg-KOH / g.

[2] Formation and Evaluation of Partition Wall A performance evaluation method will be described below.

(Creation of contact angle measurement board)
Using a spinner, a coating solution (the photosensitive resin composition for forming a partition wall) was applied on the ITO film of a glass substrate having an ITO film formed on the surface so as to have a thickness of 2.0 μm after heat curing. Then, it was heated and dried on a hot plate at 100 ° C. for 2 minutes, and the obtained coating film was exposed by shaking the exposure dose in the range of 60 to 140 mJ / cm ² without using a mask (less than 100 mJ, every 10 mJ, 100 to 500 mJ is every 20 mJ, and over 500 mJ is every 50 mJ). At this time, the intensity at a wavelength of 365 nm was 40 mW / cm ² . Subsequently, after spray development for 60 seconds with 2.38 mass% TMAH (tetramethylammonium hydroxide) aqueous solution of 24 degreeC, it wash | cleaned for 10 second with the pure water. This substrate was heat-cured in an oven at 230 ° C. for 30 minutes to obtain a cured product.

(Evaluation of contact angle of cured product)
Since the curability varies depending on the sensitivity of the composition, the amount of exposure necessary for causing liquid repellency in the cured product varies depending on the composition. Here, the exposure amount at which liquid repellency is generated represents the exposure amount necessary for the contact angle of the resulting cured product to isoamyl benzoate to be 10 ° or more. Specifically, the contact angle to the isoamyl benzoate of the cured product on the contact angle measurement substrate prepared by changing the exposure amount is measured, and the minimum exposure value of the substrate having liquid repellency is determined as the minimum exposure. Table 2 shows the contact angle of the substrate prepared with the minimum exposure amount. The contact angle was measured using a Drop Master 500 contact angle measuring device manufactured by Kyowa Interface Science Co., Ltd. under conditions of 23 ° C. and 50% humidity. A larger contact angle represents higher liquid repellency.

(Create partition walls)
Using a spinner, a coating solution (the photosensitive resin composition for forming a partition wall) was applied on the ITO film of a glass substrate having an ITO film formed on the surface so as to have a thickness of 2.0 μm after heat curing. Thereafter, it was dried by heating on a hot plate at 100 ° C. for 2 minutes. The obtained coating film was exposed using a photomask. The exposure amount was the minimum exposure amount at which the liquid repellency obtained in the above evaluation was generated, and the exposure gap was 16 μm. As the photomask, a mask having a lattice-like opening (having a plurality of covering portions of 80 μm × 280 μm at intervals of 40 μm) was used. Next, in the same manner as in the preparation of the contact angle measurement substrate, development was performed with a TMAH aqueous solution, followed by heat curing to obtain a lattice-like partition wall.

(Appropriate evaluation of barrier rib inkjet coating)
In the substrate having the grid-like partition walls described above, inkjet coating was performed on a pixel portion surrounded by the grid-like partition walls using DMP-2831 manufactured by Fuji Film. As the ink, a solvent (isoamyl benzoate) was used alone, and it was applied at 120 pL (condition 1) and more severe condition 80 pL (condition 2) per pixel to evaluate wettability. As the entire area of the pixel is wetted and spread, there are fewer residues at the time of creating the partition wall, and the developability is better. Furthermore, 160 pL of ink was applied, and the presence or absence of breakage (a phenomenon in which the ink crosses the partition wall and enters the adjacent pixel portion) was evaluated. The liquid repellency is so high that it does not break.
[Evaluation of wettability (120 pL (condition 1), 80 pL (condition 2))]
O: Ink spread throughout the pixel.
Δ: A portion where the ink did not spread partially occurred in the pixel.
X: Ink did not spread at all in the pixel.
[Fracture evaluation (160pL)]
○: Ink did not overflow from inside the pixel.
Δ: Ink partially overflowed from the inside of the pixel to the upper surface of the partition wall.
X: Ink overflowed from the inside of the pixel to the entire upper surface of the partition wall.

(Measurement of taper angle of bulkhead)
Cut the lattice-like partition wall described above to create a SEM observation sample for cross-sectional observation, observe the cross-sectional shape of the partition wall using a scanning electron microscope (SEM, manufactured by Keyence Corporation), measure the taper angle, The results are shown in Table 2.
In this sectional view, the boundary surface between the partition wall 1 and the ITO film 2 is S and the height of the partition wall is H as shown in FIG. A point having a height of ½ of H on the hypotenuse of the partition wall is A, a tangent to the hypotenuse at the point A is T, and an angle between the tangent T and the boundary surface S is measured to obtain a taper angle.
The higher the taper angle, the better the developability and the less likely the residue is generated.

(Creation of gas amount measurement substrate)
A spinner was used to apply a coating solution (the partition wall-forming photosensitive resin composition) to a thickness of 2.0 μm after heat-curing on the ITO film of a glass substrate having an ITO film formed on the surface. Thereafter, the film was heated and dried on a hot plate at 100 ° C. for 2 minutes, and the obtained coating film was exposed without using a mask at the minimum exposure amount at which the liquid repellency described above was generated. At this time, the intensity at a wavelength of 365 nm was 40 mW / cm ² . Next, as with the contact angle measurement substrate preparation, development was performed with a TMAH aqueous solution, followed by heat curing in an oven at 230 ° C. for 30 minutes to obtain a cured product.

(Measurement of gas amount)
The gas out measurement substrate (40 mm x 8 mm, 4 sheets) was analyzed by GC / MS (Agilent Technologies, product name "5973N") when heated at 230 ° C for 20 minutes in a heating furnace. The total area of all detected peak components was calculated. Next, it converted into the amount of toluene using the calibration curve from the sum total of the detected peak area, and remove | divided by the measured board | substrate area, and calculated the outgas amount (ng / cm < ² >) of toluene conversion per unit area. The calibration curve was prepared by measuring GC / MS using toluene having a known concentration, and plotting the amount of toluene and the peak area value of the detected gas.

  From Table 2, the (C2) resin alone of Comparative Example 2 has a large taper angle and good wetting and spreading properties, but has a large outgas amount. On the other hand, the (C1) resin alone of Comparative Example 1 has a small outgas amount and is good, but has a small taper angle and poor wettability. On the other hand, it can be seen that the systems using the (C1) resin and the (C2) resin in Examples 1 to 3 have a large taper angle, good wettability and a small outgas amount.

  This is because the (C1) resin alone has a lower outgas amount than the rigid main skeleton, but it has poor solubility in the developer due to the aromatic ring in the main skeleton of the resin. This is probably because the remaining film removal is insufficient. On the other hand, (C2) resin alone has good permeability of the developer and is developed to the lower part of the coating film and the taper angle is high, but the side chain in the resin molecule is easily broken by heat and has high thermal decomposability, The outgas amount is thought to be increasing. On the other hand, it is considered that by using the (C1) resin and the (C2) resin in combination, it is possible to suppress the outgas amount while ensuring sufficient development solubility.

  Further, when Examples 1 to 3 are compared, as shown in the wet spreading property and taper angle of Condition 2, among the (C1) resins, the (C1-3) resin (c-2 resin) has even better wet spreading properties. It can be seen that the taper angle is large and good. This is presumably because the (C1-3) resin has more developability because it has fewer hydrophobic groups (aromatic rings) in the main skeleton of the resin molecule than other resins. Moreover, it turns out that the amount of outgas is also decreasing. This is because the polybasic acid anhydride used in (C1-1) resin and (C1-3) resin is tetrahydrophthalic anhydride, whereas the polybasic acid used in (C1-2) resin. It is considered that because the anhydride is succinic anhydride, the outgas after the partition wall was made is less.

1: partition wall 2: ITO film 3: glass substrate A: point of height which becomes 1/2 of H on the oblique side of the partition wall H: height of the partition wall S: boundary surface between the partition wall and the ITO film

Claims (14)

A photosensitive resin composition for forming a partition wall comprising (A) an ethylenically unsaturated compound, (B) a photopolymerization initiator, and (C) an alkali-soluble resin,
The (C) alkali-soluble resin contains (C1) an epoxy (meth) acrylate resin, and (C2) an acrylic copolymer resin having an ethylenically unsaturated group in the side chain. Resin composition. The photosensitive resin composition for partition formation according to claim 1, wherein the (C2) acrylic copolymer resin includes a partial structure represented by the following general formula (I).

(In formula (I), R ¹ represents a hydrogen atom or a methyl group. R ² represents an alkenyl group which may have a substituent or a group represented by the following general formula (II). R ³ represents Represents a hydrogen atom or a group represented by the following general formula (III).)

(In the formula (II), R ⁴ represents an alkenyl group which may have a substituent. Α represents an alkylene group which may have a substituent, an arylene group which may have a substituent, Or an alkenylene group which may have a substituent, * represents a bond to the carbonyl carbon.

(In the above formula (III), β is a residue of a dicarboxylic acid.) The partition formation according to claim 1 or 2, wherein the (C1) epoxy (meth) acrylate resin contains at least one of the resins represented by the following general formulas (C1-1) to (C1-6). Photosensitive resin composition.

(In formula (C1-1), R ¹¹¹ represents a hydrogen atom, a halogen atom, an alkyl group, or an aryl group, and n ¹¹¹ represents an integer of 0 to 20.)

(In the formula (C1-2), R ¹²¹ represents a hydrogen atom, a halogen atom, an alkyl group or an aryl group, and n ¹²¹ represents an integer of 0 to 20.)

(In the formula (C1-3), R ¹³¹ represents a hydrogen atom, a halogen atom, an alkyl group or an aryl group. M ¹³¹ and n ¹³¹ each independently represents an integer of 0 to 20. γ is a single bond, —CO. —, —CH ₂ —, —C (CH ₃ ) ₂ —, a group represented by the following formula (IV), or a group represented by the following formula (V): δ represents a hydrogen atom or a polybasic acid residue. )

(In the formula (C1-4), R ¹⁴¹ represents an alkyl group or a halogen atom, and p represents an integer of 0 to 4.)

(In the formula (C1-6), R ¹⁶¹ represents a hydrogen atom, a halogen atom, an alkyl group or an aryl group, and n ¹⁶¹ represents an integer of 0 to 20.
In the formulas (C1-1) to (C1-6), A represents a group represented by the following general formula (VI). )

(In formula (VI), R ¹⁷¹ represents a hydrogen atom or a methyl group, R ¹⁷² represents an alkylene group, m ¹⁷¹ represents an integer of 0 to 10. δ represents a hydrogen atom or a polybasic acid residue. Represents.)   The (C1) epoxy (meth) acrylate resin is a resin obtained by adding an ethylenically unsaturated monocarboxylic acid or an ester compound to an epoxy resin and further reacting with a polybasic acid or an anhydride thereof. The photosensitive resin composition for partition formation of any one of these.   The photosensitive resin composition for partition formation of any one of Claims 1-4 whose content rate of the (C1) epoxy (meth) acrylate resin in the said (C) alkali-soluble resin is 30-95 mass%. .   The photosensitive resin composition for partition formation of any one of Claims 1-5 whose average acid value of said (C) alkali-soluble resin is 50 mg-KOH / g or less.   Furthermore, (D) The photosensitive resin composition for partition formation of any one of Claims 1-6 containing a liquid repellent.   The photosensitive resin composition for partition formation according to claim 7, wherein the liquid repellent (D) has a crosslinking group.   Furthermore, the photosensitive resin composition for partition formation of any one of Claims 1-8 containing a chain transfer agent.   Furthermore, the photosensitive resin composition for partition formation of any one of Claims 1-9 containing a ultraviolet absorber.   The partition comprised with the photosensitive resin composition for partition formation of any one of Claims 1-10.   An organic electroluminescent device comprising the partition wall according to claim 11.   The image display apparatus containing the organic electroluminescent element of Claim 12.   The illumination containing the organic electroluminescent element of Claim 12.

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