JP2018132763A - 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 has a high reliability with a small amount of outgas during an operation of a light-emitting element, has a large taper angle and can maintain an enough emission area.SOLUTION: The photosensitive resin composition for forming a partition wall comprises (A) an ethylenically unsaturated compound, (B) a photopolymerization initiator, and (C) an alkali-soluble resin. The photosensitive resin composition for forming a partition wall has an acid value of 20 mgKOH/g or more with respect to the whole solid content; and the (C) alkali-soluble resin contains an alkali-soluble resin (c) having a partial structure represented by general formula (1) below. In formula (1), Rrepresents an optionally substituted divalent hydrocarbon group having 1 to 4 carbon atoms; and * represents a bonding hand.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 for forming by a photolithography method using a photosensitive resin composition is known.

  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 1 describes that by using a specific alkali-soluble resin, a specific liquid repellent, and a specific surfactant, there is no disconnection of the electrode and it can cope with a high-resolution image.
On the other hand, Patent Document 2 uses a resin in which (meth) acrylic acid is added to bisphenol A type epoxy resin, succinic anhydride is further added, and bisphenol A type epoxy resin is further added. It is described that a coating film excellent in heat-resistant colorability can be obtained.

JP 2010-061093 A JP 2010-150397 A

In recent years, in order to improve the drive life of an element, there is a demand to reduce outgas generated from the partition during light emission after the partition and element formation. The demand for higher brightness is also increasing, and higher performance is required.
When the present inventors examined, it was difficult for the photosensitive resin composition for partition formation of patent document 1 to fully reduce the amount of outgases at the time of light emitting element operation.
Patent Document 2 has no description on the partition wall, and the inventors have studied the application of the photosensitive resin composition described in Patent Document 2 to the partition wall. The area of the opening surrounded by is reduced, and it is difficult to secure a sufficient light emitting area.
Therefore, an object of the present invention is to provide a photosensitive resin composition for forming a partition wall that has a small amount of outgas when the light emitting element is operated, has high reliability, has a high taper angle, and can secure a sufficient light emitting area.
Another object of the present invention is to provide a partition formed using the photosensitive resin composition for forming a partition, an organic electroluminescence device including the partition, an image display device including the organic electroluminescence device, and illumination. To do.

As a result of intensive studies by the present inventors, it has been found that the acid value of the photosensitive resin composition is in a specific range, and that the above problem can be solved by using a resin having a specific partial structure as an alkali-soluble resin, The present invention has been completed.
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 partition wall forming photosensitive resin composition has an acid value of 20 mgKOH / g or more based on the total solid content,
The said (C) alkali-soluble resin contains alkali-soluble resin (c) which has the partial structure represented by following General formula (1), The photosensitive resin composition for partition formation characterized by the above-mentioned.

(In the formula (1), R ¹ represents a divalent hydrocarbon group having 1 to 4 carbon atoms which may have a substituent. * Represents a bond.)

[2] The photosensitive resin composition for partition formation according to [1], wherein the alkali-soluble resin (c) is a resin having a carboxyl group and an ethylenically unsaturated group.
[3] The photosensitive resin composition for forming a partition wall according to [1] or [2], wherein the alkali-soluble resin (c) includes (c1) an epoxy (meth) acrylate resin.
[4] The epoxy (meth) acrylate resin (c1) includes an epoxy (meth) acrylate resin containing a repeating unit structure represented by the following general formula (i), and a partial structure represented by the following general formula (ii): The partition formation according to [3], comprising at least one selected from the group consisting of an epoxy (meth) acrylate resin containing and an epoxy (meth) acrylate resin containing a partial structure represented by the following general formula (iii): Photosensitive resin composition.

(In the formula (i), R ^a represents a hydrogen atom or a methyl group, and R ^b represents a divalent hydrocarbon group which may have a substituent. The benzene ring in the formula (i) (It may be substituted with any substituent. * Represents a bond.)

(In formula (ii), each R ^c independently represents a hydrogen atom or a methyl group. R ^d represents a divalent hydrocarbon group having a cyclic hydrocarbon group as a side chain. * Represents a bond. .)

(In the formula (iii), R ^e represents a hydrogen atom or a methyl group, gamma is a single bond, -CO-, may have a substituent group alkylene group, or may have a substituent group 2 Represents a valent cyclic hydrocarbon group, and the benzene ring in formula (iii) may be further substituted with an arbitrary substituent. * Represents a bond.)

[5] The (c1) epoxy (meth) acrylate resin is a resin obtained by adding an acid or ester compound having an ethylenically unsaturated bond to an epoxy resin, and further adding a polybasic acid or an anhydride thereof. 3] or the photosensitive resin composition for partition formation according to [4].
[6] The photosensitive resin composition for forming a partition wall according to any one of [1] to [5], further comprising (D) a liquid repellent.
[7] The photosensitive resin composition for forming a partition wall according to [6], wherein the (D) liquid repellent contains a liquid repellent having a crosslinking group.
[8] The photosensitive resin composition for forming a partition wall according to any one of [1] to [7], further containing a chain transfer agent.
[9] The photosensitive resin composition for forming a partition wall according to any one of [1] to [8], further comprising an ultraviolet absorber.

[10] A partition composed of the photosensitive resin composition for forming a partition according to any one of [1] to [9].
[11] An organic electroluminescence device comprising the partition wall according to [10].
[12] An image display device comprising the organic electroluminescent element according to [11].
[13] Illumination including the organic electroluminescent element according to [11].

  INDUSTRIAL APPLICABILITY According to the present invention, it is possible to provide a photosensitive resin composition for forming a partition wall that has a small amount of outgas when operating a light emitting device, high reliability, a high taper angle, and a sufficient light emitting area.

FIG. 1 is an explanatory diagram of a method for evaluating the 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”, “(meth) acrylate” means “acrylate and / or methacrylate”, and The “total solid content” means all components other than the solvent in the photosensitive resin composition. 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, “polybasic acid (anhydride)” means “polybasic acid and / or polybasic acid anhydride”.
In the present invention, the weight average molecular weight refers to a polystyrene equivalent weight average molecular weight (Mw) by GPC (gel permeation chromatography).

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 light emitting portion refers to a portion that emits light when electric energy is applied.
In the present invention, * in the chemical formula represents a bond.

[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 partition wall-forming photosensitive resin composition, wherein the partition wall-forming photosensitive resin composition has an acid value of 20 mgKOH / g or more based on the total solid content, and the (C) alkali-soluble resin is described below. It contains an alkali-soluble resin (c) having a partial structure represented by the general formula (1). If necessary, it may further contain other components. For example, (D) a liquid repellent, a chain transfer agent, or an ultraviolet absorber may be included.

  In the present invention, the partition wall is, for example, for partitioning a functional layer (organic layer, light emitting portion) in an active drive organic electroluminescence device, and is for forming a functional layer in the partitioned region (pixel region). This is used for forming pixels composed of functional layers and partition walls by ejecting and drying ink, which is a material of the above.

[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 also 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 possessed by the polyfunctional ethylenic monomer is not particularly limited, but is preferably 2 or more, more preferably 3 or more, still more preferably 4 or more, and particularly preferably 5 or more. Also, it is preferably 15 or less, more preferably 10 or less, still more preferably 8 or less, and particularly preferably 7 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 (manufactured by Shin-Nakamura Chemical Co., Ltd.), UA-306H, UA-510H, UF-8001G (manufactured by Kyoeisha Chemical Co., Ltd.), UV-1700B, UV -7600B, UV-7605B, UV-7630B, UV7640B (manufactured by Nippon Synthetic Chemical Industry Co., Ltd.) and the like.

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, further 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. Further, the number of carbon atoms of the (A) ethylenically unsaturated compound is not particularly limited, but from the viewpoint of sensitivity, liquid repellency, and taper angle, it is preferably 7 or more, more preferably 10 or more, still more preferably 15 or more, and even more. 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, adducts of tri- or higher functional esters (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 preferable.

  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 value, the sensitivity and taper angle during exposure tend to be good, and when it is at most the upper limit value, 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 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 it is at least the lower limit, the sensitivity tends to be good during exposure and the taper angle tends to be good, and when it is at most the upper limit, the developability 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, acetophenone photopolymerization initiators, and benzophenone photopolymerization initiators. Agent, hydroxybenzene photopolymerization initiator, thioxanthone photopolymerization initiator, anthraquinone photopolymerization initiator, ketal photopolymerization initiator, titanocene photopolymerization initiator, halogenated hydrocarbon derivative photopolymerization initiator, organic Boronate photopolymerization initiator, onium salt photopolymerization initiator, sulfone compound photopolymerization initiator, carbamic acid derivative photopolymerization initiator, sulfonamide photopolymerization initiator, triarylmethanol photopolymerization initiator Is mentioned.

  The hexaarylbiimidazole-based photopolymerization initiator is represented by the following general formula (1-1) and / or the following general formula (1-2) from the viewpoint of absorbance and sensitivity, and matching properties with the absorption wavelength of the ultraviolet absorber. Preferred are hexaarylbiimidazole compounds.

In the above formula, R ^{11 to} R ¹³ are each independently an alkyl group having 1 to 4 carbon atoms that may have a substituent, an alkoxy group having 1 to 4 carbon atoms that may have a substituent, or Represents 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'- Tora (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), etc. It is possible.

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, 4- (Diethylamino) chalcone and the like can be mentioned.
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 include di-tert-butylphenyl-3,5-di-tert-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 (tert-butylsulfonyl) methane, phenylsulfonyl (cyclohexylsulfonyl) methane, phenylcarbonyl (phenylsulfonyl) methane, naphthyl Carbonyl (phenylsulfonyl) methane, phenylcarbonyl (naphthylsulfonyl) methane, cyclohexylcarbonyl (phenylsulfonyl) methane, tert-butylcarbonyl (phenylsulfonyl) ) Carbonyl (sulfonyl) methane compounds such as methane, phenylcarbonyl (cyclohexylsulfonyl) methane, phenylcarbonyl (tert-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 (tert-butylsulfonyl) diazomethane, phenylsulfonyl (cyclohexylsulfonyl) diazomethane, bis (Sulfonyl) diazomethane, phenylcarbonyl (phenylsulfonyl) diazomethane, naphthylcarbonyl (phenylsulfur) Carbonyl such as phonyl) diazomethane, phenylcarbonyl (naphthylsulfonyl) diazomethane, cyclohexylcarbonyl (phenylsulfonyl) diazomethane, tert-butylcarbonyl (phenylsulfonyl) diazomethane, phenylcarbonyl (cyclohexylsulfonyl) diazomethane, phenylcarbonyl (tert-butylcarbonyl) diazomethane And (sulfonyl) diazomethane compounds.

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, hexaarylbiimidazole compounds are particularly preferable because of their high absorbance, high surface curability, 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 value, a coating film is formed without developing a film during development, and sufficient liquid repellency tends to occur. When the value is not more than the upper limit value, a desired pattern shape is formed. It tends to be easy to do.

  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 5 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.

Further, it is preferable to use a chain transfer agent in combination with (B) a photopolymerization initiator. By including a chain transfer agent, the taper angle tends to increase, and the contact angle also tends to increase.
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. Since the bond is likely to be cleaved and the chain transfer reaction is liable to occur due to the small SH bond energy, radical deactivation in the vicinity of the surface due to oxygen inhibition and the like can be improved, and the surface curability can be increased, and the taper angle is increased. It is thought that it is effective to do. Further, it is considered that by increasing the surface curability, the outflow of the liquid repellent can be suppressed, and the liquid repellent can be easily fixed in the vicinity of the surface and effective for increasing the contact angle.

  Among chain transfer agents, a mercapto group-containing compound having an aromatic ring and an aliphatic mercapto group-containing compound are preferred from the viewpoint of taper angle and surface curability.

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

In formula (1-3), Z represents —O—, —S—, or —NH—, and R ^{61 to} R ⁶⁴ each independently represents a hydrogen atom or a monovalent substituent.
Among these, from the viewpoint of the taper angle, Z is preferably -S- or -NH-, more preferably -NH-.
From the viewpoint of the taper angle, R ^{61 to} R ⁶⁴ are each independently preferably a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, and more preferably a hydrogen atom.

  Specifically, 2-mercaptobenzothiazole, 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 3-mercapto-1,2,4-triazole, 2-mercapto-4 (3H) -quinazoline, β-mercaptonaphthalene And mercapto group-containing compounds having an aromatic ring such as 1,4-dimethylmercaptobenzene, and 2-mercaptobenzothiazole and 2-mercaptobenzimidazole are preferable from the viewpoint of taper angle.

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

In formula (1-4), m represents an integer of 0 to 4, and n represents an integer of 2 to 4. R ⁷¹ and R ⁷² each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. X represents an n-valent group.

In the general formula (1-4), m is preferably 1 or 2 from the viewpoint of ease of synthesis. From the viewpoint of surface curability, n is preferably 3 or 4, and more preferably 4.
Moreover, as an alkyl group of ^R71 and ^R72, a C1-C3 thing is preferable from a viewpoint of surface curability. From the viewpoint of surface curability, at least one of R ⁷¹ and R ⁷² , for example, R ⁷² is preferably a hydrogen atom, and in this case, R ⁷¹ is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. It is preferable.

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

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

In formula (1-5), R ⁷³ represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a methylol group. Among R ⁷³ , an ethyl group is preferable from the viewpoint of a taper angle.

In the formula (1-6), R ⁷⁴ represents an alkylene group having 1 to 4 carbon atoms. Among R ⁷⁴ , an ethylene group is preferable from the viewpoint of a taper angle.

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

  Specifically, butanediol bis (3-mercaptopropionate), butanediol bisthioglycolate, ethylene glycol bis (3-mercaptopropionate), ethylene glycol bisthioglycolate, trimethylolpropane tris (3- Mercaptopropionate), trimethylolpropane tristhioglycolate, trishydroxyethyl tristhiopropionate, pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tris (3-mercaptopropionate), butanediol bis (3-mercaptobutyrate), ethylene glycol bis (3-mercaptobutyrate), trimethylolpropane tris (3-mercaptobutyrate), pentaerythritol tetrakis ( -Mercaptobutyrate), pentaerythritol tris (3-mercaptobutyrate), 1,3,5-tris (3-mercaptobutyloxyethyl) -1,3,5-triazine-2,4,6 (1H, 3H , 5H) -trione and the like.

  Among these, 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, and pentaerythritol tetrakis (3-mercaptopropionate) and pentaerythritol tetrakis (3-mercaptobutyrate) are more preferred.

  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-mercaptobenzoimidazole, and 2-mercaptobenzoxazole, and a photopolymerization initiator are combined to produce light. It is preferred to use it as a polymerization 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 surface curability, 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 increasing the taper angle, it is preferable to use a mercapto group-containing compound having an aromatic ring and an aliphatic mercapto group-containing compound in combination. For example, one or more selected from the group consisting of 2-mercaptobenzothiazole, 2-mercaptobenzimidazole, and 2-mercaptobenzoxazole, pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tetrakis (3-mercapto It is preferable to use one or more selected from the group consisting of butyrate) 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. When the value is not less than the lower limit value, the sensitivity is high and the taper angle and the contact angle tend to be high, and when the value is not more than the upper limit value, a desired pattern tends to be easily formed.

  As the chain transfer agent, when the mercapto group-containing compound having an aromatic ring and the aliphatic mercapto group-containing compound are used in combination, the content ratio is 100 parts by mass of the mercapto group-containing compound having an aromatic ring. In contrast, the aliphatic mercapto group-containing compound is usually 10 parts by mass or more, preferably 50 parts by mass or more, more preferably 80 parts by mass or more, and usually 400 parts by mass or less, preferably 300 parts by mass or less. Preferably it is 200 mass parts or less, More preferably, it is 150 mass parts or less. When it is at least the lower limit value, the taper angle tends to be high, and when it is at most the upper limit value, the surface curability tends to be high and the contact angle tends to be high.

  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 is more preferable, and 150 parts by mass or less is particularly preferable. When the value is not less than the lower limit, the sensitivity tends to be high, and the taper angle and the contact angle tend to be high. When the value is not more than the upper limit, a desired pattern tends to be easily formed.

  A sensitizer may be used in combination with the photopolymerization initiator. Sensitivity is improved by the sensitizer, and at the same time, the light transmittance to the inside of the photosensitive resin composition is decreased, so that the taper angle tends to be increased.

As the sensitizer, a sensitizer usually used in this field can be used. The sensitizer is characterized in that the energy obtained by absorption is transferred to the photopolymerization initiator, or electrons are exchanged with the photopolymerization initiator to efficiently promote the reaction radical polymerization reaction. Examples of such sensitizers include unsaturated ketones represented by chalcone derivatives and dibenzalacetone, 1,2-diketone compounds represented by benzyl and camphorquinone, benzoin compounds, fluorenes, and the like. Compounds, naphthoquinone compounds, anthraquinone compounds, xanthene compounds, thioxanthene compounds, xanthone compounds, thioxanthone compounds, coumarin compounds, ketocoumarin compounds, cyanine compounds, merocyanine compounds, oxonol derivatives, etc. Polymethine dyes, acridine compounds, azine compounds, thiazine compounds, oxazine compounds, indoline compounds, azulene compounds, azurenium compounds, squarylium compounds, porphyrin compounds, tetraphenylporphyrin compounds Products, triarylmethane compounds, tetrabenzoporphyrin compounds, tetrapyrazinoporphyrazine compounds, phthalocyanine compounds, tetraazaporphyrazine compounds, tetraquinoxalyloporphyrazine compounds, naphthalocyanine compounds, subphthalocyanine compounds Examples thereof include compounds, pyrylium compounds, thiopyrylium compounds, tetraphyrin compounds, annulene compounds, spiropyran compounds, spirooxazine compounds, thiospiropyran compounds, metal arene complexes, organic ruthenium complexes, and benzophenone compounds.
These may be used alone or in combination of two or more.

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

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

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

  The content of the sensitizer in the photosensitive resin composition is usually 0.1% by mass or more, preferably 0.3% by mass or more, more preferably 0.00% by mass, based on the total solid content of the photosensitive resin composition. 5% by mass or more, more preferably 0.8% by mass or more, still more preferably 1% by mass or more, particularly preferably 1.2% by mass or more, and usually 10% by mass or less, preferably 7% by mass or less, More preferably, it is 5 mass% or less, More preferably, it is 3 mass% or less. When the value is not less than the lower limit value, the sensitivity tends to be improved and the taper angle tends to be increased. 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, a resin having a carboxyl group is preferable because a partition wall having an appropriate taper angle can be obtained and the liquid repellent agent can be prevented from flowing out due to thermal melting of the partition wall surface during post-baking, so that the liquid repellency can be maintained. A resin having a polymerizable unsaturated group is more preferred.

(Alkali-soluble resin (c) having a partial structure represented by the general formula (1))
In the present invention, among the alkali-soluble resins, an alkali-soluble resin (c) having a partial structure represented by the following general formula (1) (hereinafter sometimes abbreviated as “resin (c)”) is preferable. Thus, by using an alkali-soluble resin having a partial structure represented by the general formula (1), that is, a partial structure corresponding to an acid component having a short carbon number and being easily pyrolyzed, heat at the time of forming the partition wall Since most of the acid component is removed as a gas at the time of curing, it is considered that the amount of outgas generation when driving the organic electroluminescence device is small and the reliability is improved.

Formula (1), R ¹ represents a divalent hydrocarbon group of 1 to 4 carbon atoms which may have a substituent. * Represents a bond.

(R ¹ )
In the general formula (1), R ¹ represents a divalent hydrocarbon group of 1 to 4 carbon atoms which may have a substituent. Examples of the divalent hydrocarbon group include an alkylene group and an alkenylene group.

  The alkylene group may be linear or branched, but is preferably linear from the viewpoint of development solubility. Although the carbon number is not particularly limited, it is usually preferably 1 or more and 2 or more, and usually 4 or less and 3 or less. When the amount is not less than the lower limit, the remaining film ratio tends to be high, and when the amount is not more than the upper limit, the amount of outgas generated during light emission of the element tends to be reduced.

  Specific examples of the alkylene group include a methylene group, an ethylene group, a propylene group, and a butylene group. From the viewpoint of reducing outgas, a methylene group or an ethylene group is preferable, and an ethylene group is more preferable.

  The alkenylene group may be linear or branched, but is preferably linear from the viewpoint of development solubility. The number of carbon atoms is not particularly limited, but is usually 2 or more, and usually 4 or less and 3 or less. When the amount is not less than the lower limit, the remaining film ratio tends to be high, and when the amount is not more than the upper limit, the amount of outgas generated during light emission of the element tends to be reduced.

  Specific examples of the alkenylene group include an ethenylene group, a propenylene group, and a butyleneylene group, and an ethenylene group is preferable from the viewpoint of outgassing.

  Although the substituent which the C1-C4 bivalent hydrocarbon group may have is not specifically limited, For example, a halogen atom, an alkoxy group, a benzoyl group, a hydroxyl group etc. are mentioned, From a viewpoint of the ease of synthesis | combination Is preferably unsubstituted.

Among these, from the viewpoint of reducing outgas, R ¹ is preferably a C 1-4 divalent alkylene group, more preferably a methylene group or an ethylene group, and even more preferably an ethylene group.

The alkali-soluble resin (c) is not particularly limited as long as it has a partial structure represented by the general formula (1). From the viewpoint of development solubility, (c1) epoxy ( A (meth) acrylate resin and / or (c2) an acrylic copolymer resin is preferred. Moreover, (c1) epoxy (meth) acrylate resin is preferable from the viewpoint of reducing outgas, and (c2) acrylic copolymer resin is preferable from the viewpoint of taper angle.
The (c1) epoxy (meth) acrylate resin is described in detail below.

[(C1) Epoxy (meth) acrylate resin]
(C1) An epoxy (meth) acrylate resin is obtained by adding an ethylenically unsaturated monocarboxylic acid or ester compound to an epoxy resin, optionally reacting an isocyanate group-containing compound, and further adding a polybasic acid or its anhydride. Resin. 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 resin via an ester bond (—COO—). The thing which one carboxy group of the polybasic acid or its anhydride was added to the hydroxyl group produced in that case is mentioned. Moreover, when adding a polybasic acid or its anhydride, what was added by adding a polyhydric alcohol simultaneously is also mentioned. Furthermore, the resin obtained by reacting the carboxy group of the resin obtained by the above reaction with a compound having a functional group capable of further reaction is also included in the (c1) epoxy (meth) acrylate resin.
As described above, the epoxy (meth) acrylate resin has substantially no epoxy group in terms of chemical structure and is not limited to “(meth) acrylate”, but an epoxy compound (epoxy resin) is a raw material. In addition, since “(meth) acrylate” is a representative example, it is named in accordance with conventional usage.

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 type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, phenol novolac epoxy resin, cresol novolac epoxy resin, biphenyl novolac epoxy resin, trisphenol epoxy resin, phenol and dicyclopentane Polymerized epoxy resin, dihydroxylfluorene type epoxy resin, dihydroxyalkyleneoxylfluorene type epoxy resin, diglycidyl etherified product of 9,9-bis (4′-hydroxyphenyl) fluorene, 1,1-bis (4 '-Hydroxyphenyl) 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 type epoxy resin, phenol novolac epoxy resin, cresol novolac epoxy resin, polymerized epoxy resin of phenol and dicyclopentadiene, 9,9-bis (4′-hydroxyphenyl) fluorene The diglycidyl etherified product is preferably bisphenol A type epoxy resin.

  Examples of the ethylenically unsaturated monocarboxylic acid include (meth) acrylic acid, crotonic acid, maleic acid, fumaric acid, citraconic acid, and the like, and pentaerythritol tri (meth) acrylate succinic anhydride adduct, pentaerythritol tri ( (Meth) acrylate tetrahydrophthalic anhydride adduct, dipentaerythritol penta (meth) acrylate succinic anhydride adduct, dipentaerythritol penta (meth) acrylate phthalic anhydride adduct, dipentaerythritol penta (meth) acrylate tetrahydrophthalic anhydride Examples include 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. These may be used alone or in combination of two or more. Among these, succinic anhydride, maleic anhydride, and itaconic anhydride are preferable, and succinic anhydride is more preferable from the viewpoint of introducing the partial structure represented by the general formula (1) into the resin. .

By using a polyhydric alcohol, (c1) the molecular weight of the 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.

  (C1) The acid value of the epoxy (meth) acrylate resin is not particularly limited, but is preferably 10 mgKOH / g or more, more preferably 20 mgKOH / g or more, still more preferably 40 mgKOH / g or more, and even more preferably 60 mgKOH / g or more, 80 mgKOH / g or more is particularly preferred, 200 mgKOH / g or less is preferred, 180 mgKOH / g or less is more preferred, 150 mgKOH / g or less is more preferred, 120 mgKOH / g or less is even more preferred, and 100 mgKOH / g or less is particularly preferred. Residues are reduced and the taper angle tends to be increased when the lower limit value is exceeded, and outgassing during device light emission tends to be reduced when the upper limit value is reached.

  (C1) The weight average molecular weight (Mw) of the 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. When the amount is not less than the lower limit, outgas at the time of light emission of the element tends to be reduced, and when the amount is not more than the upper limit, the residue tends to be reduced.

  (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 50% by mass or more, and further preferably 70% by mass or more, 80 mass% or more is still more preferable, 90 mass% or more is especially preferable, and it is 100 mass% or less normally. There exists a tendency for outgas to reduce by setting it as the said lower limit or more.

  (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 an acid having an ethylenically unsaturated bond (ethylenically unsaturated monocarboxylic acid) or an ester compound is added in the presence of a catalyst and a thermal polymerization inhibitor. A method can be used in which the reaction is continued and the reaction is continued by adding a polybasic acid or anhydride thereof.

  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 or its 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 produced in the addition reaction. The amount can be a chemical equivalent.

  (C1) The epoxy (meth) acrylate resin may include a partial structure other than the general formula (1), and is represented by the following general formula (i) from the viewpoint of outgassing during device light emission. An epoxy (meth) acrylate resin containing a unit structure, an epoxy (meth) acrylate resin containing a partial structure represented by the following general formula (ii), and an epoxy (meta) containing a partial structure represented by the following general formula (iii) It is preferable to contain at least one selected from the group consisting of acrylate resins.

  (C1) The epoxy (meth) acrylate resin is preferably an epoxy (meth) acrylate resin (c1-1) containing a repeating unit represented by the following general formula (i) from the viewpoint of outgassing during device light emission. . One reason is that it has a rigid main skeleton and is difficult to decompose against heat.

In formula (i), R ^a represents a hydrogen atom or a methyl group, and R ^b represents a divalent hydrocarbon group which may have a substituent. The benzene ring in formula (i) may be further substituted with an arbitrary substituent. * Represents a bond.

(R ^b )
In the formula (i), R ^b represents a divalent hydrocarbon group which may have a substituent.
Examples of the divalent hydrocarbon group include a divalent aliphatic group, a divalent aromatic ring group, a group in which one or more divalent aliphatic groups are linked to one or more divalent aromatic ring groups. Can be mentioned.

  Examples of the divalent aliphatic group include linear, branched, and cyclic groups. Among these, a linear one is preferable from the viewpoint of development solubility, and a cyclic one is preferable from the viewpoint of reducing penetration of the developer into the exposed portion. The number of carbon atoms is usually 1 or more, preferably 3 or more, more preferably 6 or more, 20 or less, more preferably 15 or less, and even more preferably 10 or less. By setting it as the said lower limit or more, there exists a tendency for image development adhesiveness to improve, and there exists a tendency for a residue to reduce by setting it as the said upper limit or less.

Specific examples of the divalent linear aliphatic group include a methylene group, an ethylene group, an n-propylene group, an n-butylene group, an n-hexylene group, and an n-heptylene group. Among these, a methylene group is preferable from the viewpoint of reducing residues.
Specific examples of the divalent branched aliphatic group include a divalent linear aliphatic group as described above, a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n- Examples include a structure having a butyl group, an iso-butyl group, a sec-butyl group, a tert-butyl group, or the like.
The number of rings of the divalent cyclic aliphatic group is not particularly limited, but is usually preferably 1 or more and 2 or more, and usually 10 or less and 5 or less. There exists a tendency for a remaining-film rate to improve by setting it as the said lower limit or more, and there exists a tendency for a residue to reduce by setting it as the said upper limit or less. Specific examples of the divalent aliphatic group include a cyclohexane ring, a cycloheptane ring, a cyclodecane ring, a cyclododecane ring, a norbornane ring, an isobornane ring, an adamantane ring, a cyclododecane ring, and the like, by removing two hydrogen atoms. Group. Among these, a group obtained by removing two hydrogen atoms from the adamantane ring is preferable from the viewpoint of development adhesion.

  Examples of the substituent that the divalent aliphatic group may have include an alkoxy group having 1 to 5 carbon atoms such as a methoxy group and an ethoxy group; a hydroxyl group; a nitro group; a cyano group; and a carboxyl group. Among these, unsubstituted is preferable from the viewpoint of ease of synthesis.

  Examples of the divalent aromatic ring group include a divalent aromatic hydrocarbon ring group and a divalent aromatic heterocyclic group. The number of carbon atoms is usually 4 or more, preferably 5 or more, more preferably 6 or more, 20 or less, more preferably 15 or less, and even more preferably 10 or less. By setting it as the said lower limit or more, there exists a tendency for image development adhesiveness to improve, and there exists a tendency for a residue to reduce by setting it as the said upper limit or less.

The aromatic hydrocarbon ring in the divalent aromatic hydrocarbon ring group may be a single ring or a condensed ring. Examples of the divalent aromatic hydrocarbon ring group include a benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, tetracene ring, pyrene ring, benzpyrene ring, chrysene ring having two free valences, Examples include a triphenylene ring, an acenaphthene ring, a fluoranthene ring, and a fluorene ring.
In addition, the aromatic heterocyclic ring in the aromatic heterocyclic group may be a single ring or a condensed ring. Examples of the divalent aromatic heterocyclic group include a furan ring, a benzofuran ring, a thiophene ring, a benzothiophene ring, a pyrrole ring, a pyrazole ring, an imidazole ring, an oxadiazole ring, and an indole having two free valences. Ring, carbazole ring, pyrroloimidazole ring, pyrrolopyrazole ring, pyrrolopyrrole ring, thienopyrrole ring, thienothiophene ring, furopyrrole ring, furofuran ring, thienofuran ring, benzisoxazole ring, benzisothiazole ring, benzimidazole ring, pyridine ring, Examples include pyrazine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, isoquinoline ring, sinoline ring, quinoxaline ring, phenanthridine ring, benzimidazole ring, perimidine ring, quinazoline ring, quinazolinone ring, and azulene ring. That. Among these, from the viewpoint of photocurability, a benzene ring or naphthalene ring having two free valences is preferable, and a benzene ring having two free valences is more preferable.

  Examples of the substituent that the divalent aromatic ring group may have include a hydroxyl group, a methyl group, a methoxy group, an ethyl group, an ethoxy group, a propyl group, and a propoxy group. Among these, unsubstituted is preferable from the viewpoint of curability.

In addition, as a group in which one or more divalent aliphatic groups and one or more divalent aromatic ring groups are linked, one or more of the above divalent aliphatic groups and the above divalent aromatic group are used. And a group in which one or more cyclic groups are linked.
The number of divalent aliphatic groups is not particularly limited, but is usually preferably 1 or more and 2 or more, usually 10 or less, preferably 5 or less, and more preferably 3 or less. By setting it as the said lower limit or more, there exists a tendency for image development adhesiveness to improve, and there exists a tendency for a residue to reduce by setting it as the said upper limit or less.
The number of divalent aromatic ring groups is not particularly limited, but is usually preferably 1 or more and 2 or more, usually 10 or less, preferably 5 or less, and more preferably 3 or less. By setting it as the said lower limit or more, there exists a tendency for image development adhesiveness to improve, and there exists a tendency for a residue to reduce by setting it as the said upper limit or less.

  Specific examples of the group in which one or more divalent aliphatic groups and one or more divalent aromatic ring groups are linked include groups represented by the following formulas (i-A) to (i-E), etc. Is mentioned. Among these, a group represented by the following formula (i-A) is preferable from the viewpoint of the rigidity of the skeleton and the hydrophobicity of the film.

As described above, the benzene ring in formula (i) may be further substituted with an arbitrary substituent. Examples of the substituent include a hydroxyl group, a methyl group, a methoxy group, an ethyl group, an ethoxy group, a propyl group, and a propoxy group. The number of substituents is not particularly limited, either one or two or more.
Among these, unsubstituted is preferable from the viewpoint of curability.

  The repeating unit structure represented by the general formula (i) is preferably a repeating unit structure represented by the following general formula (i-1) from the viewpoint of development solubility. The repeating unit structure represented by the formula (i-1) includes a partial structure represented by the general formula (1) in the formula.

In formula (i-1), R ^a and R ^b have the same meaning as in formula (i). R ¹ has the same meaning as that of formula (1). * Represents a bond. The benzene ring in formula (i-1) may be further substituted with an arbitrary substituent.

  The repeating unit structure represented by the formula (i-1) contained in one molecule of the epoxy (meth) acrylate resin (c1-1) may be one type or two or more types.

  Moreover, the number of the repeating unit structure represented by the formula (i) contained in one molecule of the epoxy (meth) acrylate resin (c1-1) is not particularly limited, but is preferably 1 or more, more preferably 2 or more. 3 or more is more preferable, 10 or less is preferable, and 8 or less is more preferable. By setting it as the said lower limit or more, there exists a tendency for image development adhesiveness to improve, and there exists a tendency for a residue to reduce by setting it as the said upper limit or less.

  The number of repeating unit structures represented by the formula (i-1) contained in one molecule of the epoxy (meth) acrylate resin (c1-1) is not particularly limited, but is preferably 1 or more and 2 or more. More preferably, 3 or more is more preferable, 10 or less is preferable, and 8 or less is more preferable. By setting it as the said lower limit or more, there exists a tendency for image development adhesiveness to improve, and there exists a tendency for a residue to reduce by setting it as the said upper limit or less.

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

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

In formula (ii), each R ^c independently represents a hydrogen atom or a methyl group. R ^d represents a divalent hydrocarbon group having a cyclic hydrocarbon group as a side chain. * Represents a bond.

(R ^d )
In the formula (ii), R ^d represents a divalent hydrocarbon group having a cyclic hydrocarbon group as a side chain.
Examples of the cyclic hydrocarbon group include an aliphatic ring group and an aromatic ring group.

The number of rings that the aliphatic ring group has is not particularly limited, but is usually preferably 1 or more and 2 or more, and usually 10 or less, preferably 5 or less, and more preferably 3 or less. By setting it as the said lower limit or more, there exists a tendency for image development adhesiveness to improve, and there exists a tendency for a residue to reduce by setting it as the said upper limit or less.
The number of carbon atoms in the aliphatic cyclic group is usually 4 or more, preferably 6 or more, more preferably 8 or more, preferably 40 or less, more preferably 30 or less, still more preferably 20 or less, and particularly preferably 15 or less. preferable. By setting it as the said lower limit or more, there exists a tendency for image development adhesiveness to improve, and there exists a tendency for a residue to reduce by setting it as the said upper limit or less.
Specific examples of the aliphatic ring in the aliphatic ring group include a cyclohexane ring, a cycloheptane ring, a cyclodecane ring, a cyclododecane ring, a norbornane ring, an isobornane ring, an adamantane ring, and a cyclododecane ring. Among these, an adamantane ring is preferable from the viewpoint of development adhesion.

On the other hand, the number of rings that the aromatic ring group has is not particularly limited, but is usually 1 or more, preferably 2 or more, more preferably 3 or more, and usually 10 or less, preferably 5 or less, and more preferably 4 or less. When the amount is not less than the lower limit, the residue tends to be reduced, and when the amount is not more than the upper limit, the development adhesion tends to be improved.
Examples of the aromatic ring group include an aromatic hydrocarbon ring group and an aromatic heterocyclic group. The number of carbon atoms in the aromatic ring group is usually 4 or more, preferably 6 or more, more preferably 8 or more, still more preferably 10 or more, particularly preferably 12 or more, and preferably 40 or less, preferably 30 or less. More preferably, it is more preferably 20 or less, and particularly preferably 15 or less. When the amount is not less than the lower limit, the residue tends to be reduced, and when the amount is not more than the upper limit, the development adhesion tends to be improved.
Specific examples of the aromatic ring in the aromatic ring group include benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, tetracene ring, pyrene ring, benzpyrene ring, chrysene ring, triphenylene ring, acenaphthene ring, fluoranthene ring, Examples include fluorene ring. Among these, a fluorene ring is preferable from the viewpoint of patterning characteristics.

  Further, the divalent hydrocarbon group in the divalent hydrocarbon group having a cyclic hydrocarbon group as a side chain is not particularly limited. For example, a divalent aliphatic group, a divalent aromatic ring group, one or more And a group in which one or more divalent aromatic ring groups are linked to each other.

  Examples of the divalent aliphatic group include linear, branched, and cyclic groups. Among these, a linear one is preferable from the viewpoint of development solubility, and a cyclic one is preferable from the viewpoint of reducing penetration of the developer into the exposed portion. The number of carbon atoms is usually 1 or more, preferably 3 or more, more preferably 6 or more, 25 or less, more preferably 20 or less, and even more preferably 15 or less. By setting it as the said lower limit or more, there exists a tendency for image development adhesiveness to improve, and there exists a tendency for a residue to reduce by setting it as the said upper limit or less.

Specific examples of the divalent linear aliphatic group include a methylene group, an ethylene group, an n-propylene group, an n-butylene group, an n-hexylene group, and an n-heptylene group. Among these, a methylene group is preferable from the viewpoint of residues.
Specific examples of the divalent branched aliphatic group include a divalent linear aliphatic group as described above, a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n- Examples include a structure having a butyl group, an iso-butyl group, a sec-butyl group, a tert-butyl group, or the like.
The number of rings that the divalent cyclic aliphatic group has is not particularly limited, but is usually preferably 1 or more and 2 or more, usually 10 or less, preferably 5 or less, and more preferably 3 or less. By setting it as the said lower limit or more, there exists a tendency for image development adhesiveness to improve, and there exists a tendency for a residue to reduce by setting it as the said upper limit or less. Specific examples of the divalent aliphatic group include a cyclohexane ring, a cycloheptane ring, a cyclodecane ring, a cyclododecane ring, a norbornane ring, an isobornane ring, an adamantane ring, a cyclododecane ring, and the like, by removing two hydrogen atoms. Group. Among these, a group obtained by removing two hydrogen atoms from the adamantane ring is preferable from the viewpoint of development adhesion.

  Examples of the substituent that the divalent aliphatic group may have include an alkoxy group having 1 to 5 carbon atoms such as a methoxy group and an ethoxy group; a hydroxyl group; a nitro group; a cyano group; and a carboxyl group. Among these, unsubstituted is preferable from the viewpoint of ease of synthesis.

  Examples of the divalent aromatic ring group include a divalent aromatic hydrocarbon ring group and a divalent aromatic heterocyclic group. The carbon number is usually 4 or more, preferably 5 or more, more preferably 6 or more, 30 or less, more preferably 20 or less, and even more preferably 15 or less. By setting it as the said lower limit or more, there exists a tendency for image development adhesiveness to improve, and there exists a tendency for a residue to reduce by setting it as the said upper limit or less.

The aromatic hydrocarbon ring in the divalent aromatic hydrocarbon ring group may be a single ring or a condensed ring. Examples of the divalent aromatic hydrocarbon ring group include a benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, tetracene ring, pyrene ring, benzpyrene ring, chrysene ring having two free valences, Examples include a triphenylene ring, an acenaphthene ring, a fluoranthene ring, and a fluorene ring.
In addition, the aromatic heterocyclic ring in the aromatic heterocyclic group may be a single ring or a condensed ring. Examples of the divalent aromatic heterocyclic group include a furan ring, a benzofuran ring, a thiophene ring, a benzothiophene ring, a pyrrole ring, a pyrazole ring, an imidazole ring, an oxadiazole ring, and an indole having two free valences. Ring, carbazole ring, pyrroloimidazole ring, pyrrolopyrazole ring, pyrrolopyrrole ring, thienopyrrole ring, thienothiophene ring, furopyrrole ring, furofuran ring, thienofuran ring, benzisoxazole ring, benzisothiazole ring, benzimidazole ring, pyridine ring, Examples include pyrazine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, isoquinoline ring, sinoline ring, quinoxaline ring, phenanthridine ring, benzimidazole ring, perimidine ring, quinazoline ring, quinazolinone ring, and azulene ring. That. Among these, from the viewpoint of photocurability, a benzene ring or naphthalene ring having two free valences is preferable, and a benzene ring having two free valences is more preferable.

  Examples of the substituent that the divalent aromatic ring group may have include a hydroxyl group, a methyl group, a methoxy group, an ethyl group, an ethoxy group, a propyl group, and a propoxy group. Among these, unsubstituted is preferable from the viewpoint of curability.

In addition, as a group in which one or more divalent aliphatic groups and one or more divalent aromatic ring groups are linked, one or more of the above divalent aliphatic groups and the above divalent aromatic group are used. And a group in which one or more cyclic groups are linked.
The number of divalent aliphatic groups is not particularly limited, but is usually preferably 1 or more and 2 or more, usually 10 or less, preferably 5 or less, and more preferably 3 or less. By setting it as the said lower limit or more, there exists a tendency for image development adhesiveness to improve, and there exists a tendency for a residue to reduce by setting it as the said upper limit or less.
The number of divalent aromatic ring groups is not particularly limited, but is usually preferably 1 or more and 2 or more, usually 10 or less, preferably 5 or less, and more preferably 3 or less. By setting it as the said lower limit or more, there exists a tendency for image development adhesiveness to improve, and there exists a tendency for a residue to reduce by setting it as the said upper limit or less.

  Specific examples of the group in which one or more divalent aliphatic groups and one or more divalent aromatic ring groups are linked include groups represented by the above formulas (iA) to (iE), etc. Is mentioned. Among these, from the viewpoint of residue reduction, the group represented by the formula (i-C) is preferable.

  The bonding mode of the cyclic hydrocarbon group which is a side chain with respect to these divalent hydrocarbon groups is not particularly limited. For example, one hydrogen atom of an aliphatic group or an aromatic ring group is substituted with the side chain. And a mode in which a cyclic hydrocarbon group which is a side chain including one of the carbon atoms of the aliphatic group is formed.

  Moreover, it is preferable that the partial structure represented by the said general formula (ii) is a partial structure represented by the following general formula (ii-1) from a viewpoint of image development adhesiveness.

In formula (ii-1), R ^c has the same meaning as in formula (ii). R ^α represents a monovalent cyclic hydrocarbon group which may have a substituent. n is an integer of 1 or more. The benzene ring in formula (ii-1) may be further substituted with an arbitrary substituent.

(R ^α )
In the formula (ii-1), R ^α represents a monovalent cyclic hydrocarbon group which may have a substituent.
Examples of the cyclic hydrocarbon group include an aliphatic ring group and an aromatic ring group.

The number of rings that the aliphatic cyclic group has is not particularly limited, but is usually preferably 1 or more and 2 or more, and usually 6 or less, preferably 4 or less, and more preferably 3 or less. By setting it as the said lower limit or more, there exists a tendency for image development adhesiveness to improve, and there exists a tendency for a residue to reduce by setting it as the said upper limit or less.
The number of carbon atoms in the aliphatic cyclic group is usually 4 or more, preferably 6 or more, more preferably 8 or more, preferably 40 or less, more preferably 30 or less, still more preferably 20 or less, and particularly preferably 15 or less. preferable. By setting it as the said lower limit or more, there exists a tendency for image development adhesiveness to improve, and there exists a tendency for a residue to reduce by setting it as the said upper limit or less.
Specific examples of the aliphatic ring in the aliphatic ring group include a cyclohexane ring, a cycloheptane ring, a cyclodecane ring, a cyclododecane ring, a norbornane ring, an isobornane ring, an adamantane ring, and a cyclododecane ring. Among these, an adamantane ring is preferable from the viewpoint of development adhesion.

On the other hand, the number of rings of the aromatic ring group is not particularly limited, but is usually 1 or more, preferably 2 or more, more preferably 3 or more, and usually 10 or less and 5 or less. By setting it as the said lower limit or more, there exists a tendency for image development adhesiveness to improve, and there exists a tendency for a residue to reduce by setting it as the said upper limit or less.
Examples of the aromatic ring group include an aromatic hydrocarbon ring group and an aromatic heterocyclic group. The carbon number of the aromatic ring group is usually 4 or more, preferably 5 or more, more preferably 6 or more, 30 or less, more preferably 20 or less, and even more preferably 15 or less. By setting it as the said lower limit or more, there exists a tendency for image development adhesiveness to improve, and there exists a tendency for a residue to reduce by setting it as the said upper limit or less.
Specific examples of the aromatic ring in the aromatic ring group include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, and a fluorene ring. Among these, a fluorene ring is preferable from the viewpoint of development adhesion.

  Examples of the substituent that the cyclic hydrocarbon group may have include a hydroxyl group, a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, C1-C5 alkyl groups, such as an amyl group and an iso-amyl group; C1-C5 alkoxy groups, such as a methoxy group and an ethoxy group; A hydroxyl group; A nitro group; A cyano group; A carboxyl group etc. are mentioned. Among these, unsubstituted is preferable from the viewpoint of ease of synthesis.

  n represents an integer of 1 or more, preferably 2 or more, and more preferably 3 or less. By setting it as the said lower limit or more, there exists a tendency for image development adhesiveness to improve, and there exists a tendency for a residue to reduce by setting it as the said upper limit or less.

Among these, R ^α is preferably a monovalent aliphatic ring group, and more preferably an adamantyl group, from the viewpoint of strong film curing degree and electrical characteristics.

  As described above, the benzene ring in formula (ii-1) may be further substituted with an arbitrary substituent. Examples of the substituent include a hydroxyl group, a methyl group, a methoxy group, an ethyl group, an ethoxy group, a propyl group, and a propoxy group. The number of substituents is not particularly limited, either one or two or more. Among these, unsubstituted is preferable from the viewpoint of curability.

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

  Moreover, it is preferable that the partial structure represented by the said general formula (ii) is a partial structure represented by the following general formula (ii-2) from a viewpoint of image development adhesiveness.

In formula (ii-2), R ^c has the same meaning as in formula (ii). ^Rβ represents a divalent cyclic hydrocarbon group which may have a substituent. The benzene ring in formula (ii-2) may be further substituted with an arbitrary substituent.

(R ^β )
In the formula (ii-2), R ^β represents a divalent cyclic hydrocarbon group which may have a substituent.
Examples of the cyclic hydrocarbon group include an aliphatic ring group and an aromatic ring group.

The number of rings that the aliphatic ring group has is not particularly limited, but is usually preferably 1 or more and 2 or more, and usually 10 or less and 5 or less. By setting it as the said lower limit or more, there exists a tendency for image development adhesiveness to improve, and there exists a tendency for a residue to reduce by setting it as the said upper limit or less.
Moreover, carbon number of an aliphatic cyclic group is 4 or more normally, 6 or more are preferable, 8 or more are more preferable, 40 or less are preferable, 35 or less are more preferable, and 30 or less are more preferable. By setting it as the said lower limit or more, there exists a tendency for image development adhesiveness to improve, and there exists a tendency for a residue to reduce by setting it as the said upper limit or less.
Specific examples of the aliphatic ring in the aliphatic ring group include a cyclohexane ring, a cycloheptane ring, a cyclodecane ring, a cyclododecane ring, a norbornane ring, an isobornane ring, an adamantane ring, and a cyclododecane ring. Among these, an adamantane ring is preferable from the viewpoint of development adhesion.

On the other hand, the number of rings of the aromatic ring group is not particularly limited, but is usually 1 or more, preferably 2 or more, more preferably 3 or more, and usually 10 or less and 5 or less. By setting it as the said lower limit or more, there exists a tendency for image development adhesiveness to improve, and there exists a tendency for a residue to reduce by setting it as the said upper limit or less.
Examples of the aromatic ring group include an aromatic hydrocarbon ring group and an aromatic heterocyclic group. The carbon number of the aromatic ring group is usually 4 or more, preferably 6 or more, more preferably 8 or more, and 10 The above is more preferable, 40 or less is preferable, 30 or less is more preferable, 20 or less is further preferable, and 15 or less is particularly preferable. By setting it as the said lower limit or more, there exists a tendency for image development adhesiveness to improve, and there exists a tendency for a residue to reduce by setting it as the said upper limit or less.
Specific examples of the aromatic ring in the aromatic ring group include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, and a fluorene ring. Among these, a fluorene ring is preferable from the viewpoint of development adhesion.

  Examples of the substituent that the cyclic hydrocarbon group may have include a hydroxyl group, a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, C1-C5 alkyl groups, such as an amyl group and an iso-amyl group; C1-C5 alkoxy groups, such as a methoxy group and an ethoxy group; A hydroxyl group; A nitro group; A cyano group; A carboxyl group etc. are mentioned. Among these, unsubstituted is preferable from the viewpoint of simplicity of synthesis.

Among these, from the viewpoint of curability, it is preferable that R ^beta is a divalent aliphatic cyclic group, and more preferably a divalent adamantane ring group.
On the other hand, from the viewpoint of developing adhesiveness, it is preferred that R ^beta is a divalent aromatic ring group, and more preferably a divalent fluorene ring group.

  As described above, the benzene ring in formula (ii-2) may be further substituted with an arbitrary substituent. Examples of the substituent include a hydroxyl group, a methyl group, a methoxy group, an ethyl group, an ethoxy group, a propyl group, and a propoxy group. The number of substituents is not particularly limited, either one or two or more. Among these, unsubstituted is preferable from the viewpoint of curability.

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

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

In formula (ii-3), R ^c and R ^d have the same meaning as in formula (ii). R ¹ is synonymous with the formula (1).

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

  In addition, the number of partial structures represented by the formula (ii) contained in one molecule of the epoxy (meth) acrylate resin (c1-2) is not particularly limited, but is preferably 1 or more, more preferably 3 or more, Moreover, 20 or less is preferable, 15 or less is more preferable, and 10 or less is further more preferable. By setting it as the said lower limit or more, there exists a tendency for image development adhesiveness to improve, and there exists a tendency for a residue to reduce by setting it as the said upper limit or less.

  On the other hand, the (c1) epoxy (meth) acrylate resin is an epoxy (meth) acrylate resin (c1-3) containing a partial structure represented by the following general formula (iii) from the viewpoint of reducing outgas at the time of device light emission. It is preferable that

In formula (iii), R ^e represents a hydrogen atom or a methyl group, and γ represents a single bond, —CO—, an alkylene group which may have a substituent, or a divalent which may have a substituent. Represents a cyclic hydrocarbon group. The benzene ring in formula (iii) may be further substituted with an arbitrary substituent. * Represents a bond.

(Γ)
In the formula (iii), γ represents a single bond, —CO—, an alkylene group which may have a substituent, or a divalent cyclic hydrocarbon group which may have a substituent.

  The alkylene group may be linear or branched, but is preferably linear from the viewpoint of development solubility, and is preferably branched from the viewpoint of development adhesion. Although the carbon number is not specifically limited, 1 or more and 2 or more are preferable normally, and 6 or less and 4 or less are preferable normally. By setting it as the said lower limit or more, there exists a tendency for image development adhesiveness to improve, and there exists a tendency for a residue to reduce by setting it as the said upper limit or less.

  Specific examples of the alkylene group include a methylene group, an ethylene group, a propylene group, a butylene group, a hexylene group, and a heptylene group, and an ethylene group or a propylene group is preferable from the viewpoint of compatibility between development adhesion and development solubility. A propylene group is more preferable.

  Examples of the substituent that the alkylene group may have include an alkoxy group having 1 to 5 carbon atoms such as a methoxy group and an ethoxy group; a hydroxyl group; a nitro group; a cyano group; and a carboxyl group. Among these, unsubstituted is preferable from the viewpoint of ease of synthesis.

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

The number of rings that the aliphatic ring group has is not particularly limited, but is usually preferably 1 or more and 2 or more, and usually 10 or less and 5 or less. By setting it as the said lower limit or more, there exists a tendency for image development adhesiveness to improve, and there exists a tendency for a residue to reduce by setting it as the said upper limit or less.
Moreover, carbon number of an aliphatic cyclic group is 4 or more normally, 6 or more are preferable, 8 or more are more preferable, 40 or less are preferable, 35 or less are more preferable, and 30 or less are more preferable. By setting it as the said lower limit or more, there exists a tendency for image development adhesiveness to improve, and there exists a tendency for a residue to reduce by setting it as the said upper limit or less.
Specific examples of the aliphatic ring in the aliphatic ring group include a cyclohexane ring, a cycloheptane ring, a cyclodecane ring, a cyclododecane ring, a norbornane ring, an isobornane ring, an adamantane ring, and a cyclododecane ring. Among these, an adamantane ring is preferable from the viewpoint of development adhesion.

On the other hand, the number of rings of the aromatic ring group is not particularly limited, but is usually 1 or more, preferably 2 or more, more preferably 3 or more, and usually 10 or less and 5 or less. By setting it as the said lower limit or more, there exists a tendency for image development adhesiveness to improve, and there exists a tendency for a residue to reduce by setting it as the said upper limit or less.
Examples of the aromatic ring group include an aromatic hydrocarbon ring group and an aromatic heterocyclic group. Further, the carbon number of the aromatic ring group is usually 4 or more, preferably 6 or more, more preferably 8 or more, further preferably 10 or more, more preferably 40 or less, more preferably 30 or less, and further preferably 20 or less. Preferably, 15 or less is particularly preferable. By setting it as the said lower limit or more, there exists a tendency for image development adhesiveness to improve, and there exists a tendency for a residue to reduce by setting it as the said upper limit or less.
Specific examples of the aromatic ring in the aromatic ring group include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, and a fluorene ring. Among these, a fluorene ring is preferable from the viewpoint of development adhesion.

  Examples of the substituent that the cyclic hydrocarbon group may have include a hydroxyl group, a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, C1-C5 alkyl groups, such as an amyl group and an iso-amyl group; C1-C5 alkoxy groups, such as a methoxy group and an ethoxy group; A hydroxyl group; A nitro group; A cyano group; A carboxyl group etc. are mentioned. Among these, unsubstituted is preferable from the viewpoint of simplicity of synthesis.

  Among these, from the viewpoint of reducing residues, γ is preferably an alkylene group which may have a substituent, and more preferably a dimethylmethylene group.

  As described above, the benzene ring in formula (iii) may be further substituted with an arbitrary substituent. Examples of the substituent include a hydroxyl group, a methyl group, a methoxy group, an ethyl group, an ethoxy group, a propyl group, and a propoxy group. The number of substituents is not particularly limited, either one or two or more. Among these, unsubstituted is preferable from the viewpoint of curability.

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

In formula (iii-1), R ^e and γ have the same meaning as in formula (iii). R ¹ has the same meaning as that of formula (1). * Represents a bond. The benzene ring in formula (iii-1) may be further substituted with an arbitrary substituent.

  Moreover, the number of the repeating unit structure represented by the formula (iii) contained in one molecule of the epoxy (meth) acrylate resin (c1-3) is not particularly limited, but is preferably 1 or more, more preferably 5 or more. 10 or more is more preferable, 18 or less is preferable, and 15 or less is more preferable. By setting it as the said lower limit or more, there exists a tendency for image development adhesiveness to improve, and there exists a tendency for a residue to reduce by setting it as the said upper limit or less.

  In addition, the number of the repeating unit structure represented by the formula (iii-1) contained in one molecule of the epoxy (meth) acrylate resin (c1-3) is not particularly limited, but is preferably 1 or more and 3 or more. More preferably, 5 or more is more preferable, 18 or less is preferable, and 15 or less is more preferable. By setting it as the said lower limit or more, there exists a tendency for image development adhesiveness to improve, and there exists a tendency for a residue to reduce by setting it as the said upper limit or less.

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

[(C2) Acrylic copolymer resin]
Next, (c2) the acrylic copolymer resin will be described in detail. (C2) The acrylic copolymer resin is not particularly limited as long as it has a partial structure represented by the general formula (1), but from the viewpoint of curability, it has an ethylenically unsaturated group in the side chain. Preferably there is.

(Partial structure represented by general formula (I))
(C2) Although the partial structure containing the side chain which has an ethylenically unsaturated group contained in acrylic copolymer resin is not specifically limited, From a viewpoint of development solubility, for example, the part represented by the following general formula (I) It preferably includes a structure.

In the formula (I), R ^A represents a hydrogen atom or a methyl group. R ^B represents an alkenyl group which may have a substituent or a group represented by the following general formula (II). * Represents a bond.

In formula (II), R ^C 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.

(R ^B )
In the formula (I), R ^B 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 ^B 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. There exists a tendency for image development adhesiveness to improve by setting it as the said lower limit or more, and there exists a tendency for sclerosis | hardenability to improve by setting it as the said upper limit or less.

  Specific examples of the alkenyl group include ethenyl group, propenyl group, butyryl group, cyclohexenyl group and the like. Among these, from the viewpoint of 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.

The R ^B, in view of curability and developability Among these, preferred are ethenyl group or a propenyl group, and more preferably an ethenyl group.

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

Examples of the alkenyl group for R ^C 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. There exists a tendency for image development adhesiveness to improve by setting it as the said lower limit or more, and there exists a tendency for sclerosis | hardenability to improve by setting it as the said upper limit or less.

  Specific examples of the alkenyl group include ethenyl group, propenyl group, butyryl group, cyclohexenyl group and the like. Among these, from the viewpoint of 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, A sulfone group etc. are mentioned. 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 ^C represents an alkenyl group which may have a substituent, and among these, from the viewpoint of developability, an ethenyl group or a propenyl group is preferable, and an ethenyl group is more preferable. .

(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. There exists a tendency for adhesiveness to improve by setting it as the said lower limit or more, and there exists a tendency for sclerosis | hardenability to improve by setting it as the said upper limit or less.

  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 curability, 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 preferred from the viewpoint of development adhesion. 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. By setting it as the said lower limit or more, there exists a tendency for image development adhesiveness to improve, and there exists a tendency for a residue to reduce by setting it as the said upper limit or less.
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 a ring, a benzpyrene ring, a chrysene ring, a triphenylene ring, an acenaphthene ring, a fluoranthene ring, a fluorene ring, and the like.
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 Ring, and 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, A sulfone group etc. are mentioned. 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. By setting it as the said lower limit or more, there exists a tendency for image development adhesiveness to improve, and there exists a tendency for a residue to reduce by setting it as the said upper limit or less.

  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 developability, 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.

  Moreover, it is preferable that the repeating unit structure represented by the said general formula (I) is a repeating unit structure represented by the following general formula (I-1) from a developable viewpoint. In addition, the repeating unit structure represented by the formula (I-1) includes a partial structure represented by the general formula (1) in the formula.

In formula (I-1), R ^A and R ^B have the same meanings as in formula (I). R ¹ has the same meaning as that of formula (1).

  Moreover, it is preferable that the repeating unit structure represented by the said general formula (I) is a repeating unit structure represented by the following general formula (I-2) from a viewpoint of a sensitivity.

In formula (I-2), R ^A and R ^B have the same meanings as those in formula (I).

  (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 30 mol% or more. Is more preferably 50 mol% or more, particularly preferably 70 mol% or more, most preferably 80 mol% or more, more preferably 99 mol% or less, more preferably 97 mol% or less, and 95 mol% or less. Is more preferable. When the amount is not less than the lower limit, the residue tends to be reduced, and when the amount is not more than the upper limit, the development adhesion tends to be improved.

  (C2) The content of the partial structure represented by the general formula (I-1) contained in the acrylic copolymer resin is not particularly limited, but is preferably 1 mol% or more, more preferably 5 mol% or more, and 10 mol. % Or more is more preferable, 15 mol% or more is further more preferable, 20 mol% or more is particularly preferable, 99 mol% or less is preferable, 60 mol% or less is more preferable, 40 mol% or less is further preferable, and 30 mol% is more preferable. % Or less is particularly preferable. When the amount is not less than the lower limit, the sensitivity tends to increase and the residue tends to be reduced. When the amount is not more than the upper limit, the development adhesion tends to be improved.

  (C2) The content of the partial structure represented by the general formula (I-2) contained in the acrylic copolymer resin is not particularly limited, but is preferably 5 mol% or more, more preferably 10 mol% or more, and 20 mol%. The above is more preferable, 30 mol% or more is more preferable, 40 mol% or more is particularly preferable, 50 mol% or more is most preferable, 99 mol% or less is preferable, 90 mol% or less is more preferable, and 80 mol%. The following is more preferable, and 70 mol% or less is particularly preferable. The sensitivity tends to be increased by setting it to the lower limit value or more, and the developability tends to be improved by setting the upper limit value or less.

(Partial structure represented by 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 development adhesion, for example, the following general formula (I It is preferable that the partial structure represented by ') is included.

In the above formula (I ′), R ^D represents a hydrogen atom or a methyl group, and R ^E 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 ^E )
In the formula (I ′), R ^E 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 in R ^E 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. By setting it as the said lower limit or more, film | membrane intensity | strength becomes high and there exists a tendency for image development adhesiveness to improve, and there exists a tendency for a residue to reduce by setting it as the said upper limit or less.

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 film strength, 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 in R ^E 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. By setting it as the said lower limit or more, there exists a tendency for image development adhesiveness to improve, and there exists a tendency for a residue to reduce by setting it as the said upper limit or less.
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 a ring, a benzpyrene ring, a chrysene ring, a triphenylene ring, an acenaphthene ring, a fluoranthene ring, a fluorene ring, and the like.
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 Ring, and azulene ring. Among these, from the viewpoint of curability, 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 ^E 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. By setting it as the said lower limit or more, there exists a tendency for image development adhesiveness to improve, and there exists a tendency for a residue to reduce by setting it as the said upper limit or less.

Specific examples of the alkenyl group include ethenyl group, propenyl group, butyryl group, cyclohexenyl group and the like. Among these, from the viewpoint of 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 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 ^E 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 ratio of the partial structure represented by the general formula (I ′) contained in the acrylic copolymer resin is not particularly limited, but is preferably 0.5 mol% or more, more preferably 1 mol% or more, and 1 0.5 mol% or more is more preferable, 2 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, and 30 mol% or less is more preferable. 10 mol% or less is particularly preferable. By setting it as the said lower limit or more, there exists a tendency for image development adhesiveness to improve, and there exists a tendency for a residue to reduce by setting it as the said upper limit or less.

(Partial structure represented by general formula (I ''))
(C2) When 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. It is preferable that a partial structure is included.

In the above formula (I ″), R ^F represents a hydrogen atom or a methyl group, R ^G represents an alkyl group which may have a substituent, an alkenyl 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. t represents an integer of 0 to 5.

(R ^G )
In the above formula (I ″), R ^G is an optionally substituted alkyl group, an optionally substituted alkenyl group, an optionally substituted alkynyl group, 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 ^G 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. By setting it as the said lower limit or more, there exists a tendency for image development adhesiveness to improve, and there exists a tendency for a residue to reduce by setting it as the said upper limit or less.

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 development adhesion, 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 in R ^G include a linear, branched or cyclic alkenyl group. 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. By setting it as the said lower limit or more, there exists a tendency for image development adhesiveness to improve, and there exists a tendency for a residue to reduce by setting it as the said upper limit or less.

Specific examples of the alkenyl group include ethenyl group, propenyl group, butyryl group, cyclohexenyl group and the like. Among these, from the viewpoint of 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 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 ^G 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 liquid repellency.

^Examples of the alkoxy group in R ^G include a linear, branched or cyclic alkoxy group. 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. By setting it as the said lower limit or more, there exists a tendency for image development adhesiveness to improve, and there exists a tendency for a residue to reduce by setting it as the said upper limit or less.

  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 in ^RG include a linear, branched or cyclic alkyl sulfide group. 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. By setting it as the said lower limit or more, there exists a tendency for image development adhesiveness to improve, and there exists a tendency for a residue to reduce by setting it as the said upper limit or less.

Specific examples of the alkyl sulfide group include a methyl sulfide group, an ethyl sulfide group, a propyl sulfide group, and a butyl sulfide group. Among these, a methyl sulfide group or an ethyl sulfide group is preferable from the viewpoint of developability.
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 ^G is an alkyl group which may have a substituent, an alkenyl group which may have a substituent, a hydroxyl group, a carboxyl group, a halogen atom, an alkoxy group, a hydroxyalkyl group, a thiol group, Alternatively, an alkyl sulfide group which may have a substituent is represented, and among these, from the viewpoint of developability, a hydroxyl group or a carboxyl group is preferable, and a carboxyl group is more preferable.

(T)
In the formula (I ″), t represents an integer of 0 to 5. From the viewpoint of developability, it is preferably 2 or less, more preferably 1 or less, and even more preferably 0.

  (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 1 mol% or more, more preferably 2 mol% or more, and 3 mol % Or more 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 further preferable, 30 mol% or less is more preferable, 20 mol % Or less is particularly preferable, and 10 mol% or less is most preferable. By setting it as the said lower limit or more, there exists a tendency for image development adhesiveness to improve, and there exists a tendency for a residue to reduce by setting it as the said upper limit or less.

(Partial structure represented by general formula (I ′ ″))
(C2) When the acrylic copolymer resin includes a partial structure represented by the general formula (I), the other partial structure is represented by the following general formula (I ′ ″) from the viewpoint of developability. A partial structure is preferably included.

In the above formula (I ′ ″), R ^H represents a hydrogen atom or a methyl group.

  (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 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 the amount is not less than the lower limit, the residue tends to be reduced, and when the amount is not more than the upper limit, the development adhesion tends to be improved. 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.

  (C2) The acid value of the acrylic copolymer resin is not particularly limited, but is preferably 5 mgKOH / g or more, more preferably 10 mgKOH / g or more, further preferably 30 mgKOH / g or more, more preferably 40 mgKOH / g or more, and 50 mgKOH / g g or more is particularly preferred, 100 mgKOH / g or less is preferred, 90 mgKOH / g or less is more preferred, 70 mgKOH / g or less is more preferred, and 60 mgKOH / g or less is even more preferred. When the amount is not less than the lower limit, the residue tends to be reduced, and when the amount is not more than the upper limit, the development adhesion tends to be improved.

  (C2) The weight average molecular weight (Mw) of the acrylic copolymer resin is not particularly limited, but is preferably 1000 or more, more preferably 2000 or more, still more preferably 3000 or more, still more preferably 4000 or more, and particularly preferably 5000 or more. In addition, it is usually 30000 or less, preferably 20000 or less, more preferably 15000 or less, and further preferably 10,000 or less. Especially preferably, it is 7000 or less. By setting it as the said lower limit or more, there exists a tendency for image development adhesiveness to improve, and there exists a tendency for a residue to reduce by setting it as the said upper limit or less.

  (C) The content ratio of (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, and more preferably 15% by mass or more from the viewpoint of developability. Is more preferably 20% by mass or more, usually 100% by mass or less, more preferably 80% by mass or less, and further preferably 50% by mass or less. When it is at least the lower limit, the development solubility tends to be good, and when it is at most the upper limit, the taper angle tends to be high.

  In (C) alkali-soluble resin, either (c1) epoxy (meth) acrylate resin or (c2) acrylic copolymer resin may be contained alone, or both may be contained. Furthermore, resins other than (c1) and (c2) may be included. For example, (C) the alkali-soluble resin itself may be provided with liquid repellency by including an alkali-soluble resin having a fluorine atom-containing functional group.

  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. It is preferably 30% by mass or more, particularly preferably 40% by mass or more, and usually 90% by mass or less, preferably 70% by mass or less, more preferably 60% by mass or less, and particularly preferably 50% by mass or less. There exists a tendency for developability to improve by making it into the said lower limit or more, and there exists a tendency to reduce the outgas at the time of element light emission by making it into the said upper limit or less.

  The content of the alkali-soluble resin (c) 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. It is preferably 30% by mass or more, particularly preferably 40% by mass or more, and usually 90% by mass or less, preferably 70% by mass or less, more preferably 60% by mass or less, and particularly preferably 50% by mass or less. When the amount is not less than the lower limit value, the outgas at the time of light emission of the element tends to be reduced, and when the value is not more than the upper limit value, the reduction of the film tends to be suppressed.

  (C) The content of the alkali-soluble resin (c) in the alkali-soluble resin is usually 10% by mass or more, preferably 30% by mass or more, more preferably 50% by mass or more, still more preferably 70% by mass or more, particularly preferably. Is 90% by mass or more and usually 100% by mass or less. When it is at least the lower limit, the developability is improved, and the outgas during light emission of the element tends to be reduced.

  The content ratio of (A) ethylenically unsaturated compound and (C) alkali-soluble resin in the total solid content is usually 5% by mass or more, preferably 10% by mass or more, more preferably, based on the total solid content. 30% by mass or more, more preferably 50% by mass or more, still more preferably 70% by mass or more, particularly preferably 80% by mass or more, most preferably 85% by mass or more, and usually 99% by mass or less. Preferably it is 97 mass% or less, More preferably, it is 95 mass% or less. When the amount is not less than the lower limit, the curability tends to be improved, and when the amount is not more than the upper limit, there is a tendency to reduce the outgas at the time of device light emission.

  Moreover, as a compounding ratio of (C) alkali-soluble resin with respect to (A) ethylenically unsaturated compound in the photosensitive resin composition, 50 mass parts or more with respect to 100 mass parts of (A) ethylenically unsaturated compound. Preferably, 60 parts by mass or more is more preferable, 70 parts by mass or more is more preferable, 80 parts by mass or more is particularly preferable, 400 parts by mass or less is preferable, 300 parts by mass or less is more preferable, and 200 parts by mass or less is more preferable. 100 parts by mass or less is particularly preferable. There exists a tendency for image development adhesiveness to improve by setting it as the said lower limit or more, and there exists a tendency for sclerosis | hardenability to improve 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 light emitting portion (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 “Megafuck F116”, “Megafuck F120”, “Megafuck F142D”, “Megafuck F144D”, “Megafuck F150”, “Megafuck F160”, manufactured by DIC, “Mega Fuck F171”, “Mega Fuck F172”, “Mega Fuck F173”, “Mega Fuck F177”, “Mega Fuck F178A”, “Mega Fuck F178K”, “Mega Fuck F179”, “Mega Fuck F183”, “Mega Fuck F183” Fuck F184, Mega Fuck F191, Mega Fuck F812, Mega Fuck F815, Mega Fuck F824, Mega Fuck F833, Mega Fuck RS101, Mega Fuck RS102, Mega Fuck RS105 , "Me “Fuck RS201”, “Megafuck RS202”, “Megafuck RS301”, “Megafuck RS303” “Megafuck RS304”, “Megafuck RS401”, “Megafuck RS402”, “Megafuck RS501”, “Megafuck RS502” , “Megafuck RS-72-K”, “DEFENSA MCF300”, “DEFENSA MCF310”, “DEFENSA MCF312”, “DEFENSA MCF323”, “FLORARD FC430”, “FLORARD FC431”, “FC-4430” manufactured by 3M Japan "FC-4432", "Asahi Guard AG710", "Surflon S-382", "Surflon SC-101", "Surflon SC-102", "Surflon SC-10" manufactured by Asahi Glass Co., Ltd. 3 ”,“ Surflon SC-104 ”,“ Surflon SC-105 ”,“ Surflon SC-106 ”,“ Optool DAC-HP ”manufactured by Daikin Industries, Ltd., and other commercially available fluorine-containing organic compounds are used. be able to.

  Thus, in the case of using a fluorine-based compound as the liquid repellent, the fluorine atom content in the liquid repellent is not particularly limited, but preferably the fluorine atom content is preferably 1% by mass or more, 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 post-baking is suppressed, so that 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. Is preferable, 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 perfluorododecyl sulfonate, 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 ”,“ 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] Polymerization inhibitor The photosensitive resin composition for forming a partition wall of the present invention may contain a polymerization inhibitor. It is considered that the taper angle of the obtained partition wall can be increased because it contains a polymerization inhibitor and inhibits radical polymerization.
Examples of the polymerization inhibitor include hydroquinone, hydroquinone monomethyl ether, methylhydroquinone, methoxyphenol, 2,6-di-tert-butyl-4-cresol (BHT) and the like. Among these, 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 the (C) alkali-soluble resin is produced, a polymerization inhibitor may be contained in the resin, which may be used as the polymerization inhibitor of the present invention, or the polymerization inhibitor in the resin. In addition, 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 0.3 mass% or less normally, Preferably it is 0.2 mass% or less, More preferably, it is 0.1 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.

[1-1-6] 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 an ultraviolet absorber, it is possible to improve the taper angle shape after development or to eliminate the residue 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.
Examples of the ultraviolet absorber include benzotriazole compounds, triazine compounds, benzophenone compounds, benzoate compounds, cinnamic acid derivatives, naphthalene derivatives, anthracene and derivatives thereof, dinaphthalene compounds, phenanthroline compounds, dyes, and the like.
These ultraviolet absorbers can be used alone or in combination of two or more.

  Among these, from the viewpoint of increasing the taper angle, benzotriazole compounds and / or hydroxyphenyltriazine compounds are preferable, and benzotriazole compounds are particularly preferable.

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

In the above 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 following general formula (Z2), or the following general formula (Z3 ) Represents a group represented by 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 Formula (Z1), R ^1e and R ^2e are each independently a hydrogen atom, an alkyl group which may have a substituent, a group represented by General Formula (Z2), or General Formula (Z3). Represents the group represented.
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 a tapered shape, R ^5e is preferably a heptyl group, an octyl group, or a nonyl group.

(R ^6e )
In the formula (Z3), R ^6e 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, from the viewpoint of a tapered shape, R ^1e is a tert-butyl group, R ^2e is a group represented by the formula (Z2) (where R ^4e is an ethylene group, and R ^5e is an alkyl group having 7 to 9 carbon atoms). R ^3e is a hydrogen atom, or R ^1e is a hydrogen atom, R ^2e is a group represented by the above formula (Z3) (where R ^6e is an ethylene group, R ^7e is a methyl group), and R ^3e is a hydrogen atom Wherein R ^1e is a tert-butyl group, R ^2e is a group represented by the above formula (Z2) (where R ^4e is an ethylene group, R ^5e is an alkyl group having 7 to 9 carbon atoms), R ^3e A compound in which is a hydrogen atom is more preferred.

  Specific examples of the benzotriazole-based compound include 2- (5-methyl-2-hydroxyphenyl) benzotriazole, 2- (2-hydroxy-5-tert-butylphenyl) -2H-benzotriazole, and 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 -Tert-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole, 2 -(3,5-di-tert-amyl-2-hydroxyphenyl) benzotriazole, 2- (2'-hydroxy-5'-tert-octylphenyl) benzotriazole, benzenepropanoic acid, 3- (2H-benzotriazole 2-yl) -5- (1,1-dimethylethyl) -4-hydroxy, C7-9 side chain and linear alkyl ester compound, 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) -Tetramethylbutyl) phenol. Among these, from the viewpoint of taper angle and exposure sensitivity, 3- (2H-benzotriazol-2-yl) -5- (1,1-dimethylethyl) -4-hydroxy, C7-9 side chain and linear alkyl Ester compounds are preferred.

  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 , TINUVIN99-2, TINUVIN109, TINUVIN384-2, TINUVIN326, TINUVIN900, TINUVIN928, TINUVIN1130 (manufactured by BASF), EVERSORB70, EVERSORB71, EVERSORB72, EVERSORB73, EVERSERB74, 75 , EVERSORB81 (manufactured by Yongkou Chemical Industry Co., Taiwan), Tomissorb 100, Tomisorb 600 (manufactured by API Corporation), SEESORB701, SEESORB702, SEESORB703, SEESORB706, SEESORB707, SEESORB709 (Ryutsuka Chemical Co., Ltd.), RUV 93 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).

  Other UV absorbers include, for example, Sumisorb 130 (manufactured by Sumitomo Chemical Co., Ltd.), EVERSORB10, EVERSORB11, EVERSORB12 (manufactured by Eikko Chemical Industries, Ltd.), Tomissorb 800 (manufactured by API Corporation), SESORB100, SESORB101, SESORB101S, SEESORB102, SEESORB102, SEESORB102 Benzophenone compounds such as SEESORB105, 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, and isopropyl methoxycinnamate Cinnamic acid derivatives such as isoamyl methoxycinnamate; -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 -Naphthalene derivatives such as dihydroxynaphthalene, 1,7-dihydroxynaphthalene, 1,8-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene; anthracene, 9,10-dihydroxy Anthracene such as anthracene and derivatives thereof; azo dyes, benzophenone dyes, amino ketone dyes, quinoline dyes, anthraquinone dyes, diphenyl cyanoacrylate dyes, triazine dyes, p-amino acid And dyes such as benzoic acid dyes. 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.

  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 the 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, more preferably 50 parts by mass or more, particularly preferably 80 parts by mass or more, and usually 500 parts by mass or less, preferably 300 parts by mass or less, more preferably 200 parts by mass or less, still more preferably 150 parts by mass. It is as follows. 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.

[1-1-7] 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 ratio 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.
On the other hand, for the purpose of reducing the outgas from the partition walls, it is desirable to make the partition walls transparent, and the content ratio of the colorant in that case is preferably 10 mass with respect to the total solid content of the photosensitive resin composition. % Or less, more preferably 5% by mass or less, and particularly preferably 0% by mass.

[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 rate 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] Phosphate-based adhesion improver It is also preferable to add a phosphate-based adhesion improver to the photosensitive resin composition for forming a partition wall of the present invention in order to improve the adhesion to the substrate. As the phosphate-based adhesion improver, (meth) acryloyloxy group-containing phosphates are preferable, and those represented by the following general formulas (Va), (Vb), and (Vc) are particularly preferable.

In the general formulas (Va), (Vb), and (Vc), R ⁸ represents a hydrogen atom or a methyl group, r and r ′ are each independently an integer of 1 to 10, and s is 1, 2, or 3. .

  The content ratio of the phosphoric acid-based adhesion improver 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 0.00% by mass relative to the total solid content. 1% by mass or more, more preferably 0.2% by mass or more, particularly preferably 0.4% by mass or more, and usually 15% by mass or less, preferably 10% by mass or less, more preferably 5% by mass or less, More preferably, it is 3 mass% or less, Most preferably, it is 1 mass% or less. There exists a tendency for adhesiveness to become favorable by setting it as the said lower limit or more, and there exists a tendency which can maintain the preservability of a photosensitive composition by setting it as the said upper limit or less.

[1-1-13] Inorganic filler In addition, the photosensitive resin composition for forming a partition wall of the present invention is further improved in 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 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.

[1-1-14] 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 diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, dipropylene glycol dimethyl ether Glycol dialkyl ethers such as: ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol mono-n-butyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether Cetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, methoxybutyl acetate, 3-methoxybutyl acetate, methoxypentyl acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol mono-n-butyl ether acetate, dipropylene Glycol alkyl ether acetates such as glycol monomethyl ether acetate, triethylene glycol monomethyl ether acetate, triethylene glycol monoethyl ether acetate, 3-methyl-3-methoxybutyl acetate, 3-methoxy-1-butyl acetate; Acetate, 1 Glycol diacetates such as 1,3-butylene glycol diacetate and 1,6-hexanol diacetate; alkyl acetates such as cyclohexanol acetate; amyl ether, diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, diamyl ether Ethers such as ethyl isobutyl ether and 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 Ketones such as hexyl ketone, methyl nonyl ketone, methoxymethyl pentanone; methanol, ethanol Mono- or polyhydric alcohols such as propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, butanediol, diethylene glycol, dipropylene glycol, triethylene glycol, methoxymethylpentanol, glycerin, benzyl alcohol; n- Aliphatic hydrocarbons such as pentane, n-octane, diisobutylene, n-hexane, hexene, isoprene, dipentene, dodecane; alicyclic hydrocarbons such as cyclohexane, methylcyclohexane, methylcyclohexene, bicyclohexyl; benzene Aromatic hydrocarbons such as toluene, xylene, cumene; amyl formate, ethyl formate, ethyl acetate, butyl acetate, propyl acetate, amyl acetate, methyl acetate Butyrate, ethylene glycol acetate, ethyl propionate, propyl propionate, butyl butyrate, isobutyl butyrate, methyl isobutyrate, ethyl caprylate, butyl stearate, ethyl benzoate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate Linear or cyclic esters such as methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, butyl 3-methoxypropionate, γ-butyrolactone; 3-methoxypropionic acid, 3- Alkoxycarboxylic acids such as ethoxypropionic acid; halogenated hydrocarbons such as butyl chloride and amyl chloride; ether ketones such as methoxymethylpentanone; acetonitrile and benzonitrile Such nitriles: 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 (1013.25 hPa). 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. When it is at least the lower limit, a coating film tends to be obtained even for a high film thickness, and when it is at most the upper limit, there is a tendency for appropriate coating uniformity to be obtained.

[1-2] Physical Properties of Photosensitive Resin Composition for Forming Partitions Acid properties are listed as physical properties of the photosensitive resin composition for forming partition walls of the present invention. The acid value with respect to the total solid content of the photosensitive resin composition for forming a partition wall of the present invention is 20 mgKOH / g or more. By setting the photosensitive resin composition for forming a partition to the above lower limit or more, the solubility in a developer is increased, the unexposed portion can be sufficiently dissolved and removed, and the taper angle of the resulting partition is increased. Conceivable.

  The acid value with respect to the total solid content of the partition wall forming photosensitive resin composition is not particularly limited as long as it is 20 mgKOH / g or more, preferably 22 mgKOH / g or more, more preferably 24 mgKOH / g or more, and further 26 mgKOH / g or more. Preferably, 28 mgKOH / g or more is particularly preferred, usually 60 mgKOH / g or less, 55 mgKOH / g or less is preferred, 50 mgKOH / g or less is more preferred, 40 mgKOH / g or less is more preferred, and 35 mgKOH / g or less is particularly preferred. The solubility in the developer is high when the lower limit value is exceeded, and the taper angle tends to be high because the unexposed areas can be sufficiently dissolved and removed. Tends to be good.

[1-3] Preparation method of photosensitive resin composition for forming barrier ribs The photosensitive resin composition for forming barrier ribs of the present invention is prepared by mixing the above-described 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 Forming Method of Partition Wall 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 (light emitting part) of an organic electroluminescence device.
The method for forming the partition (bank) using the photosensitive resin composition for forming a partition 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. A specific example of such a bank formation method is a photolithography method.

  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 optical elements are manufactured using a substrate having a partition 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.
Examples of the type of organic electroluminescent element include a bottom emission type and a top emission type.
In the bottom emission type, for example, a partition is formed on a glass substrate on which transparent electrodes are stacked, and a hole transport layer, a light emitting layer, an electron transport layer, and a metal electrode layer are stacked in an opening surrounded by the partition. The On the other hand, in the top emission type, for example, a partition is formed on a glass substrate on which a metal electrode layer is stacked, and an electron transport layer, a light emitting layer, a hole transport layer, and a transparent electrode layer are stacked in an opening surrounded by the partition. Created.
In addition, as a light emitting layer, the organic electroluminescent layer as described in Unexamined-Japanese-Patent No. 2009-146691 and patent 5734681 is mentioned. Further, quantum dots as described in Japanese Patent No. 5653387 and Japanese Patent No. 5653101 may be used.

  When the taper angle of the partition wall is low and the bottom of the partition wall has a trailing shape as shown in FIG. 1, even if a vapor deposition layer is formed on the upper portion of the partition wall, no light is emitted. In addition, when the light emitting layer is formed by the ink jet method, the organic layer forming ink is repelled by the skirt portion of the partition wall, so that the region surrounded by the partition wall may not be uniformly covered with the organic layer forming ink. is there. In contrast, by forming a good shape with a high taper angle and no skirting, it is possible to emit light within the region surrounded by the partition walls, and in the ink jet method, the ink for forming the organic layer is more uniform. Can be coated. 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 walls, an inkjet 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] Preparation of barrier rib-forming photosensitive resin composition Propylene glycol monomethyl ether was used so that each component was used in the blending ratio (parts by mass) shown in Table 1 and 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: Megafax RS-72-K (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, ultraviolet absorber)
g-1: KAYAMER PM-21 (manufactured by Nippon Kayaku Co., Ltd.)

c-1: The following ethylenically unsaturated group-containing resin ((c1) epoxy (meth) acrylate resin / partial structure represented by general formula (1) and partial structure represented by general formula (iii) Equivalent to resin)
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 mgKOH / 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, 4.5 parts by mass of succinic anhydride was added, and the mixture was reacted at 95 ° C. for 3 hours. / G, The alkali-soluble resin (c-1) solution whose weight average molecular weight (Mw) of polystyrene conversion measured by GPC was 8000 was obtained.

c-2: The following ethylenically unsaturated group-containing resin ((c1) epoxy (meth) acrylate resin / partial structure represented by general formula (1) and partial structure represented by general formula (iii) Equivalent to resin)
100 parts by mass of a bisphenol A type epoxy compound represented by the above formula as in c-1 (epoxy equivalent 186 g / eq, a mixture of n in the formula of 1 to 20), 40 parts by mass of acrylic acid, p-methoxyphenol 0.06 parts by mass, 2.4 parts by mass of triphenylphosphine, and 126 parts by mass of propylene glycol monomethyl ether acetate were charged into a reaction vessel and stirred at 95 ° C. until the acid value became 5 mgKOH / g or less. Next, 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, 2.3 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 30 mg KOH. / G, an alkali-soluble resin (c-2) solution having a polystyrene-equivalent weight average molecular weight (Mw) of 8300 measured by GPC was obtained.

c-3: The following acrylic copolymer resin (corresponding to (c2) acrylic copolymer resin / resin including the partial structure represented by the general formula (1) and the partial structure represented by the general formula (I))
A copolymer resin having tricyclodecane methacrylate / styrene / glycidyl methacrylate (molar ratio: 0.02 / 0.045 / 0.935) as a constituent monomer is subjected to an addition reaction with an equal amount of acrylic acid and the glycidyl methacrylate, and further anhydrous. An alkali-soluble acrylic copolymer resin (c-3) solution in which succinic acid is added in a molar ratio of 0.095 to 1 mol of the above copolymer resin. The solvent is propylene glycol monomethyl ether acetate. The weight average molecular weight (Mw) in terms of polystyrene measured by GPC was 9700, and the solid content acid value was 23.8 mgKOH / g.

c-4: The following acrylic copolymer resin (corresponding to (c2) acrylic copolymer resin / resin including the partial structure represented by the general formula (1) and the partial structure represented by the general formula (I))
A copolymer resin containing tricyclodecane methacrylate / styrene / glycidyl methacrylate (molar ratio: 0.032 / 0.069 / 0.899) as a constituent monomer is subjected to an addition reaction of an equal amount of acrylic acid with the glycidyl methacrylate, and further anhydrous. An alkali-soluble acrylic copolymer resin (c-4) solution in which succinic acid is added in a molar ratio of 0.24 to 1 mol of the above copolymer resin. The solvent is propylene glycol monomethyl ether acetate. The weight average molecular weight (Mw) in terms of polystyrene measured by GPC was 4800, and the solid content acid value was 62.1 mgKOH / g.

c-5: The following acrylic copolymer resin A copolymer resin containing tricyclodecane methacrylate / styrene / glycidyl methacrylate (molar ratio: 0.3 / 0.1 / 0.6) as a constituent monomer, and acrylic acid as glycidyl methacrylate An alkali-soluble acrylic copolymer resin (c-5) solution in which tetrahydrophthalic anhydride was further added in an equivalent amount with respect to 1 mol of the copolymer resin so that the molar ratio was 0.39. The solvent is propylene glycol monomethyl ether acetate. The weight average molecular weight (Mw) in terms of polystyrene measured by GPC was 8400, and the solid content acid value was 81.4 mgKOH / g.

  The physical property evaluation of the photosensitive resin composition for partition formation was performed by the method described below.

(Measurement of acid value)
The acid value can be measured by the method described in JIS K 0070-1992. In addition to directly measuring the photosensitive resin composition, the acid value of the photosensitive resin composition may be calculated from the acid value and content of the resin. The calculated values of the acid value (resist acid value) relative to the total solid content of the photosensitive resin compositions of Examples 1 and 2 and Comparative Examples 1 to 3 are shown in Table 1.

(Creation of gas amount measurement substrate)
The said photosensitive resin composition for partition formation was apply | coated so that it might become a thickness of 1.7 micrometers after heat-hardening (post-baking) using the spinner on the glass substrate. Thereafter, it was dried by heating on a hot plate at 95 ° C. for 2 minutes, and the obtained coating film was exposed at an exposure amount of 100 mJ / cm ² without using a mask. At this time, the intensity at a wavelength of 365 nm was 7.5 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 (post-baked) for 30 minutes at 230 ° C. in an oven to obtain a gas amount measurement substrate with 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. However, the calculation was performed excluding the peak corresponding to tetramethylammonium derived from the aqueous solution of TMAH (tetramethylammonium hydroxide). 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 results are shown in Table 1. The calibration curve was prepared by measuring GC / MS using toluene with a known concentration and plotting the amount of toluene and the peak area value of the detected gas.

(Creation of contact angle measurement board)
The said photosensitive resin composition for partition formation was apply | coated so that it might become a thickness of 1.7 micrometers after heat-hardening (post-baking) using the spinner on the glass substrate. Thereafter, it was dried by heating on a hot plate at 95 ° C. for 2 minutes, and the obtained coating film was exposed at an exposure amount of 100 mJ / cm ² without using a mask. At this time, the intensity at a wavelength of 365 nm was 7.5 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 (post-baked) for 30 minutes at 230 ° C. in an oven to obtain a contact angle measurement substrate with a cured product.

(Measurement of contact angle)
The contact angle was measured with a Drop Master 500 contact angle measuring device manufactured by Kyowa Interface Science Co., Ltd. under conditions of 23 ° C. and 50% humidity. 0.7 μL of propylene glycol methyl ether acetate was dropped on the cured product of the contact angle measurement substrate, and the contact angle after 1 second was measured. The measurement results are shown in Table 1. A larger contact angle represents higher liquid repellency.

[2] Formation and Evaluation of Partition Wall A performance evaluation method will be described below.
(Formation of partition walls)
The partition wall-forming photosensitive resin composition was applied to a thickness of 1.7 μm after heat-curing (post-baking) using a spinner on the ITO film of a glass substrate having an ITO film formed on the surface. Thereafter, the film was dried by heating on a hot plate at 95 ° C. for 2 minutes. A photomask (a mask having a plurality of covering portions of 80 μm × 280 μm at intervals of 40 μm) was used for the obtained coating film at an exposure gap of 16 μm at a wavelength of 365 nm. Exposure was performed using ultraviolet rays having an intensity of 7.5 mW / cm ² so that the exposure amount was 100 mJ / cm ² . The ultraviolet irradiation at this time was performed under air. Next, the film was spray-developed with a 2.38 mass% TMAH (tetramethylammonium hydroxide) aqueous solution at 24 ° C. for 60 seconds and then washed with pure water for 1 minute. By these operations, unnecessary portions were removed, and the substrate on which the pattern was formed was heat-cured (post-baked) in an oven at 230 ° C. for 30 minutes to form lattice-like partition walls.

(Evaluation of taper angle and line width of partition wall, area of opening)
A sample for cross-sectional observation was prepared by cutting the lattice-like partition wall described above, and the cross-sectional shape of the partition wall was observed using a scanning electron microscope (SEM, manufactured by Keyence Corporation), and the taper angle and the line width were measured. . The cross-sectional shape of the partition walls was observed in a substantially trapezoidal shape.
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. In the hypotenuse of the partition wall, a tangent line between the hypotenuse and the boundary surface S is defined as T, and an angle formed by the tangent line 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 to be generated.
Moreover, the opening width (horizontal width, vertical width) of the lower part of a partition was measured, and the area of the opening part was computed by multiplying them. Table 1 shows the results of the taper angle, the line width of the taper lower part, and the area of the opening. The area of the opening is a relative value with respect to the area of the corresponding mask shielding part. The smaller the taper angle, the larger the line width of the partition wall and the smaller the area of the opening.

From Table 1, the outgas generation amount of the substrate obtained by using the photosensitive resin composition containing each of the resins (c-1) to (c-4) to which succinic acid was added is the resin (tetrahydrophthalic acid added) ( It was found to be significantly less than that of the substrate obtained using the photosensitive resin composition containing c-5).
Thus, the photosensitive resin composition containing a resin with an acid having a short carbon chain such as succinic acid is more sensitive to the photosensitive resin composition containing a resin having an acid having a long carbon chain such as tetrahydrophthalic acid. It was confirmed that the amount of outgas generated was smaller under the gas measurement conditions of 230 ° C. heating after heat curing by post baking at 230 ° C. for 30 minutes. This is considered to be because an acid having a short carbon chain such as succinic acid is almost eliminated and removed during post-baking, and no gas is generated during subsequent heating at 230 ° C.

  From Table 1, when the photosensitive resin composition of Comparative Examples 1 and 2 having a low acid value is used, the taper angle is low, while when the photosensitive resin composition of Examples 1 and 2 having a high acid value is used, the taper angle is low. I found it to be higher. In addition, it was confirmed that the area of the opening was small when a photosensitive resin composition having a low acid value was used, and the area of the opening was increased when a photosensitive resin composition having a high acid value was used. . If the acid value of the photosensitive resin composition is low, the solubility of the unexposed portion in the developer is lowered, and the deep layer portion of the coating film is not sufficiently developed and the taper angle is lowered. It is considered that by increasing the acid value, the solubility of the unexposed area in the developer can be increased, the unexposed area can be sufficiently dissolved and removed, and the taper angle is increased.

1: partition wall 2: ITO film 3: glass substrate T: tangent line with oblique side in contact with boundary surface H: height of partition wall S: boundary surface between partition wall and ITO film

Claims (13)

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 partition wall forming photosensitive resin composition has an acid value of 20 mgKOH / g or more based on the total solid content,
The said (C) alkali-soluble resin contains alkali-soluble resin (c) which has the partial structure represented by following General formula (1), The photosensitive resin composition for partition formation characterized by the above-mentioned.

(In the formula (1), R ¹ represents a divalent hydrocarbon group having 1 to 4 carbon atoms which may have a substituent. * Represents a bond.)   The photosensitive resin composition for partition formation of Claim 1 whose said alkali-soluble resin (c) is resin which has a carboxyl group and an ethylenically unsaturated group.   The photosensitive resin composition for partition formation of Claim 1 or 2 in which the said alkali-soluble resin (c) contains (c1) epoxy (meth) acrylate resin. The (c1) epoxy (meth) acrylate resin is an epoxy (meth) acrylate resin containing a repeating unit structure represented by the following general formula (i), an epoxy having a partial structure represented by the following general formula (ii) ( The photosensitivity for partition formation of Claim 3 containing at least 1 sort (s) chosen from the group which consists of a (meth) acrylate resin and the epoxy (meth) acrylate resin containing the partial structure represented by the following general formula (iii). Resin composition.

(In the formula (i), R ^a represents a hydrogen atom or a methyl group, and R ^b represents a divalent hydrocarbon group which may have a substituent. The benzene ring in the formula (i) (It may be substituted with any substituent. * Represents a bond.)

(In formula (ii), each R ^c independently represents a hydrogen atom or a methyl group. R ^d represents a divalent hydrocarbon group having a cyclic hydrocarbon group as a side chain. * Represents a bond. .)

(In the formula (iii), R ^e represents a hydrogen atom or a methyl group, gamma is a single bond, -CO-, may have a substituent group alkylene group, or may have a substituent group 2 Represents a valent cyclic hydrocarbon group, and the benzene ring in formula (iii) may be further substituted with an arbitrary substituent. * Represents a bond.)   The (c1) epoxy (meth) acrylate resin is a resin obtained by adding an acid or ester compound having an ethylenically unsaturated bond to an epoxy resin and further adding a polybasic acid or an anhydride thereof. 5. The photosensitive resin composition for forming a partition wall according to 4.   Furthermore, (D) The photosensitive resin composition for partition formation of any one of Claims 1-5 containing a liquid repellent.   The photosensitive resin composition for partition formation according to claim 6, wherein the (D) liquid repellent contains a liquid repellent having a crosslinking group.   Furthermore, the photosensitive resin composition for partition formation of any one of Claims 1-7 containing a chain transfer agent.   Furthermore, the photosensitive resin composition for partition formation of any one of Claims 1-8 containing a ultraviolet absorber.   The partition comprised with the photosensitive resin composition for partition formation of any one of Claims 1-9.   An organic electroluminescent device comprising the partition wall according to claim 10.   The image display apparatus containing the organic electroluminescent element of Claim 11.   The illumination containing the organic electroluminescent element of Claim 11.

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